U.S. patent application number 17/604161 was filed with the patent office on 2022-06-30 for chemically linked silk fibroin coatings and methods of making and using thereof.
This patent application is currently assigned to EVOLVED BY NATURE, INC.. The applicant listed for this patent is EVOLVED BY NATURE, INC.. Invention is credited to Gregory H. ALTMAN, Carlos J. BOSQUES, Marius COSTACHE, Xiuzhu FEI, Enrico MORTARINO, Maria UFRET.
Application Number | 20220205165 17/604161 |
Document ID | / |
Family ID | |
Filed Date | 2022-06-30 |
United States Patent
Application |
20220205165 |
Kind Code |
A1 |
FEI; Xiuzhu ; et
al. |
June 30, 2022 |
CHEMICALLY LINKED SILK FIBROIN COATINGS AND METHODS OF MAKING AND
USING THEREOF
Abstract
Chemically linked silk fibroin coatings and methods of making
and using thereof are disclosed herein. Also disclosed are articles
coated with such coatings, which can include chemical or physical
modifiers.
Inventors: |
FEI; Xiuzhu; (Charlotte,
NC) ; COSTACHE; Marius; (Lexington, MA) ;
MORTARINO; Enrico; (Hickory, NC) ; UFRET; Maria;
(Grafton, MA) ; BOSQUES; Carlos J.; (Arlington,
MA) ; ALTMAN; Gregory H.; (Providence, RI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EVOLVED BY NATURE, INC. |
Medford |
MA |
US |
|
|
Assignee: |
EVOLVED BY NATURE, INC.
Medford
MA
|
Appl. No.: |
17/604161 |
Filed: |
April 16, 2020 |
PCT Filed: |
April 16, 2020 |
PCT NO: |
PCT/US2020/028589 |
371 Date: |
October 15, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62834711 |
Apr 16, 2019 |
|
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International
Class: |
D06M 15/15 20060101
D06M015/15 |
Claims
1. An article comprising a coated substrate, wherein the coating
comprises silk fibroin or silk fibroin fragments and a chemical
modifier or a physical modifier.
2. The article of claim 1, wherein the chemical modifier is
chemically linked to one or more of a silk fibroin side group and a
silk fibroin terminal group.
3. The article of claim 2, wherein the silk fibroin side group and
the silk fibroin terminal group are independently selected from an
amine group, a carboxyl group, a hydroxyl group, a thiol group, and
a sulfhydryl group.
4. The article of claim 1, wherein the chemical modifier is
chemically linked to one or more functional groups on the
substrate.
5. The article of claim 1, wherein the chemical modifier comprises
one or more of a chemically linked functional group, or functional
group residue, and a linker.
6. The article of claim 1, wherein the chemical modifier comprises
one or more of --CR.sup.a.sub.2--, --CR.sup.a.dbd.CR.sup.a--,
--C.ident.C--, -aryl-, -heteroaryl-, --O--, --S--, --OC(O)--,
--N(R.sup.a)--, --N.dbd.N--, .dbd.N--, --C(O)--, --C(O)O--,
--OC(O)N(R.sup.a)--, --C(O)N(R.sup.a)--, --N(R.sup.a)C(O)O--,
--N(R.sup.a)C(O)--, --N(R.sup.a)C(O)N(R.sup.a)--,
--N(R.sup.a)C(NR.sup.a)N(R.sup.a)--, --N(R.sup.a)S(O).sub.t--,
--S(O).sub.tO--, --S(O).sub.tN(R.sup.a)--,
--S(O).sub.tN(R.sup.a)C(O)--, --OP(O)(OR.sup.a)O--, wherein t is 1
or 2, and wherein at each independent occurrence R.sup.a is
selected from hydrogen, alkyl, alkenyl, fluoroalkyl, carbocyclyl,
carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl,
heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl.
7. (canceled)
8. The article of claim 1, wherein the coating comprises silk
fibroin or silk fibroin fragments with an average weight average
molecular weight from about 5 kDa to about 144 kDa.
9. The article of claim 1, wherein the coating comprises silk
fibroin or silk fibroin fragments with an average weight average
molecular weight from about 1 kDa to about 5 kDa, from about 5 kDa
to about 10 kDa, from about 6 kDa to about 17 kDa, from about 10
kDa to about 15 kDa, from about 15 kDa to about 20 kDa, from about
17 kDa to about 39 kDa, from about 20 kDa to about 25 kDa, from
about 25 kDa to about 30 kDa, from about 30 kDa to about 35 kDa,
from about 35 kDa to about 40 kDa, from about 39 kDa to about 80
kDa, from about 40 kDa to about 45 kDa, from about 45 kDa to about
50 kDa, from about 60 kDa to about 100 kDa, or from about 80 kDa to
about 144 kDa.
10. The article of claim 1, wherein the coating comprises silk
fibroin or silk fibroin fragments with a polydispersity between 1
and about 5.0.
11. The article of claim 1, wherein the coating comprises silk
fibroin or silk fibroin fragments which prior to coating the
substrate are stable in a solution.
12. The article of claim 1, wherein the coating comprises silk
fibroin or silk fibroin fragments which prior to coating the
substrate do not spontaneously or gradually gelate and do not
visibly change in color or turbidity when in a solution for at
least 10 days.
13. The article of claim 1, wherein the substrate includes one or
more of a fiber, a thread, a yarn, a fabric, a textile, a cloth, or
a hide.
14. The article of claim 13, wherein the fabric, textile, or cloth
is woven or nonwoven.
15. The article of claim 13, wherein the fiber, thread, or yarn
comprises one or more of polyester, recycled polyester, Mylar,
cotton, nylon, recycled nylon, polyester-polyurethane copolymer,
rayon, acetate, aramid (aromatic polyamide), acrylic, ingeo
(polylactide), lurex (polyamide-polyester), olefin
(polyethylene-polypropylene), and combinations thereof.
16. The article of claim 13, wherein the fiber, thread, or yarn
comprises one or more of alpaca fiber, alpaca fleece, alpaca wool,
lama fiber, lama fleece, lama wool, cotton, cashmere, sheep fiber,
sheep fleece, sheep wool, byssus, chiengora, qiviut, yak, rabbit,
lambswool, mohair wool, camel hair, angora wool, silkworm silk,
abaca fiber, coir fiber, flax fiber, jute fiber, kapok fiber, kenaf
fiber, raffia fiber, bamboo fiber, hemp, modal fiber, pina, ramie,
sisal, and soy protein fiber.
17. The article of claim 13, wherein the fiber, thread, or yarn
comprises one or more of mineral wool, mineral cotton, man-made
mineral fiber, fiberglass, glass, glasswool, stone wool, rock wool,
slagwool, glass filaments, asbestos fibers, and ceramic fibers.
18. A method of coating a substrate with a coating comprising silk
fibroin or silk fibroin fragments and a chemical modifier or a
physical modifier, the method comprising applying to the substrate
at least one composition comprising silk fibroin or silk fibroin
fragments with an average weight average molecular weight from
about 1 kDa to about 144 kDa, and a polydispersity between 1 and
about 5.0.
19. The method of claim 18, further comprising applying to the
substrate a chemical modifier or a physical modifier selected from
a wetting agent, a detergent, a sequestering or dispersing agent,
an enzyme, a bleaching agent, an antifoaming agent, an
anti-creasing agent, a dye dispersing agent, a dye leveling agent,
a dye fixing agent, a dye special resin agent, a dye anti-reducing
agent, a pigment dye system anti-migrating agent, a pigment dye
system binder, a delave agent, a wrinkle free treatment, a
softener, a handle modifier, a waterborne polyurethane dispersion,
a finishing resin, an oil or water repellant, a flame retardant, a
crosslinker, an activator, a thickener for technical finishing, or
any combination thereof.
20. The method of claim 19, wherein the crosslinker or the
activator are independently selected from a N-hydroxysuccinimide
ester crosslinker, an imidoester crosslinker, a sulfosuccinimidyl
aminobenzoate, a methacrylate, a silane, a silicate, an alkyne
compound, an azide compound, an aldehyde, a carbodiimide
crosslinker, a dicyclohexyl carbodiimide activator, a dicyclohexyl
carbodiimide crosslinker, a maleimide crosslinker, a haloacetyl
crosslinker, a pyridyl disulfide crosslinker, a hydrazide
crosslinker, an alkoxyamine crosslinker, a reductive amination
crosslinker, an aryl azide crosslinker, a diazirine crosslinker, an
azide-phosphine crosslinker, a transferase crosslinker, a hydrolase
crosslinker, a transglutaminase crosslinker, a peptidase
crosslinker, an oxidoreductase crosslinker, a tyrosinase
crosslinker, a laccase crosslinker, a peroxidase crosslinker, a
lysyl oxidase crosslinker, and combinations thereof.
21-25. (canceled)
26. The method of claim 18, further comprising dyeing the substrate
prior to or after applying to the substrate the at least one
composition comprising silk fibroin or silk fibroin fragments.
27. (canceled)
Description
FIELD
[0001] The disclosure relates to chemically linked silk fibroin
coatings and methods of making and using thereof, for example use
of such chemically linked fibroin in coated articles, including
various fabric and leather apparel, and various fabric and leather
products for use in home and automotive applications.
BACKGROUND
[0002] Silk is a natural polymer produced by a variety of insects
and spiders, and comprises a filament core protein, silk fibroin,
and a glue-like coating consisting of a non-filamentous protein,
sericin. Silk fibers are light weight, breathable, and
hypoallergenic. Silk is comfortable when worn next to the skin and
insulates very well; keeping the wearer warm in cold temperatures
and is cooler than many other fabrics in warm temperatures.
SUMMARY
[0003] The disclosure relates to articles including one or more
coated substrates, wherein the coatings include silk protein
fragments (SPF) as defined herein, including without limitation
silk fibroin or silk fibroin fragments, and a chemical modifier or
a physical modifier. In some embodiments, the chemical modifier is
chemically linked to one or more of a silk fibroin side group and a
silk fibroin terminal group. In some embodiments, the silk fibroin
side group and the silk fibroin terminal group are independently
selected from an amine group, an amide group, a carboxyl group, a
hydroxyl group, a thiol group, and a sulfhydryl group. In some
embodiments, the chemical modifier is chemically linked to one or
more functional groups on the substrate. In some embodiments, the
functional group on the substrate is selected from an amine group,
an amide group, a carboxyl group, a hydroxyl group, a thiol group,
and a sulfhydryl group. In some embodiments, the chemical modifier
includes one or more of a chemically linked functional group, or
functional group residue, and a linker. In some embodiments, the
chemical modifier includes one or more of --CR.sup.a.sub.2--,
--CR.sup.a.dbd.CR.sup.a--, --C.ident.C--, -alkyl-, -alkenyl-,
-alkynyl-, -aryl-, -heteroaryl-, --O--, --S--, --OC(O)--,
--N(R.sup.a)--, --N.dbd.N--, .dbd.N--, --C(O)--, --C(O)O--,
--OC(O)N(R.sup.a)--, --C(O)N(R.sup.a)--, --N(R.sup.a)C(O)O--,
--N(R.sup.a)C(O)--, --N(R.sup.a)C(O)N(R.sup.a)--,
--N(R.sup.a)C(NR.sup.a)N(R.sup.a)--, --N(R.sup.a)S(O).sub.t--,
--S(O).sub.tO--, --S(O).sub.tN(R.sup.a)--,
--S(O).sub.tN(R.sup.a)C(O)--, --OP(O)(OR.sup.a)O--, wherein t is 1
or 2, and wherein at each independent occurrence R.sup.a is
selected from hydrogen, alkyl, alkenyl, fluoroalkyl, carbocyclyl,
carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl,
heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl. In some
embodiments, the coating includes one or more of low molecular
weight silk fibroin or silk fibroin fragments, medium molecular
weight silk fibroin or silk fibroin fragments and high molecular
weight silk fibroin or silk fibroin fragments. In some embodiments,
the coating includes SPF as defined herein, including without
limitation silk fibroin or silk fibroin fragments, with an average
weight average molecular weight from about 5 to about 144 kDa. In
some embodiments, the coating includes SPF as defined herein,
including without limitation silk fibroin or silk fibroin
fragments, with an average weight average molecular weight from
about 1 kDa to about 5 kDa, from about 5 kDa to about 10 kDa, from
about 6 kDa to about 17 kDa, from about 10 kDa to about 15 kDa,
from about 15 kDa to about 20 kDa, from about 17 kDa to about 39
kDa, from about 20 kDa to about 25 kDa, from about 25 kDa to about
30 kDa, from about 30 kDa to about 35 kDa, from about 35 kDa to
about 40 kDa, from about 39 kDa to about 80 kDa, from about 40 kDa
to about 45 kDa, from about 45 kDa to about 50 kDa, from about 60
kDa to about 100 kDa, or from about 80 kDa to about 144 kDa. In
some embodiments, the coating includes SPF as defined herein,
including without limitation silk fibroin or silk fibroin
fragments, with a polydispersity between 1 and about 5.0. In some
embodiments, the coating includes SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, which
prior to coating the substrate are stable in a solution. In some
embodiments, the coating includes SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, which
prior to coating the substrate do not spontaneously or gradually
gelate and/or do not visibly change in color or turbidity when in a
solution for at least 10 days. In some embodiments, the substrate
includes one or more of a fiber, a thread, a yarn, a fabric, a
textile, a cloth, or a hide. In some embodiments, the fabric,
textile, or cloth is woven or nonwoven. In some embodiments, the
fiber, thread, or yarn includes one or more of polyester, recycled
polyester, Mylar, cotton, nylon, recycled nylon,
polyester-polyurethane copolymer, rayon, acetate, aramid (aromatic
polyamide), acrylic, ingeo (polylactide), lurex
(polyamide-polyester), olefin (polyethylene-polypropylene), and
combinations thereof. In some embodiments, the fiber, thread, or
yarn includes one or more of alpaca fiber, alpaca fleece, alpaca
wool, lama fiber, lama fleece, lama wool, cotton, cashmere, sheep
fiber, sheep fleece, sheep wool, byssus, chiengora, qiviut, yak,
rabbit, lambswool, mohair wool, camel hair, angora wool, silkworm
silk, abaca fiber, coir fiber, flax fiber, jute fiber, kapok fiber,
kenaf fiber, raffia fiber, bamboo fiber, hemp, modal fiber, pina,
ramie, sisal, and soy protein fiber. In some embodiments, the
fiber, thread, or yarn includes one or more of mineral wool,
mineral cotton, man-made mineral fiber, fiberglass, glass,
glasswool, stone wool, rock wool, slagwool, glass filaments,
asbestos fibers, and ceramic fibers.
[0004] The disclosure also relates to a method of coating a
substrate with a coating including SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, and a
chemical modifier or a physical modifier, the method including
applying to the substrate at least one composition including SPF as
defined herein, including without limitation silk fibroin or silk
fibroin fragments, with an average weight average molecular weight
from about 1 kDa to about 144 kDa, and a polydispersity between 1
and about 5.0. In some embodiments, the method further includes
applying to the substrate a chemical modifier or a physical
modifier selected from a wetting agent, a detergent, a sequestering
or dispersing agent, an enzyme, a bleaching agent, an antifoaming
agent, an anti-creasing agent, a dye dispersing agent, a dye
leveling agent, a dye fixing agent, a dye special resin agent, a
dye anti-reducing agent, a pigment dye system anti-migrating agent,
a pigment dye system binder, a delave agent, a wrinkle free
treatment, a softener, a handle modifier, a waterborne polyurethane
dispersion, a finishing resin, an oil or water repellant, a flame
retardant, a crosslinker, an activator, a thickener for technical
finishing, or any combination thereof. In some embodiments, the
crosslinker or the activator are independently selected from a
N-hydroxysuccinimide ester crosslinker, an imidoester crosslinker,
a sulfosuccinimidyl aminobenzoate, a methacrylate, a silane, a
silicate, an alkyne compound, an azide compound, an aldehyde, a
carbodiimide crosslinker, a dicyclohexyl carbodiimide activator, a
dicyclohexyl carbodiimide crosslinker, a maleimide crosslinker, a
haloacetyl crosslinker, a pyridyl disulfide crosslinker, a
hydrazide crosslinker, an alkoxyamine crosslinker, a reductive
amination crosslinker, an aryl azide crosslinker, a diazirine
crosslinker, an azide-phosphine crosslinker, a transferase
crosslinker, a hydrolase crosslinker, a transglutaminase
crosslinker, a peptidase crosslinker, an oxidoreductase
crosslinker, a tyrosinase crosslinker, a laccase crosslinker, a
peroxidase crosslinker, a lysyl oxidase crosslinker, and
combinations thereof. In some embodiments, the composition includes
low molecular weight SPF as defined herein, including without
limitation silk fibroin or silk fibroin fragments. In some
embodiments, the composition includes medium molecular weight SPF
as defined herein, including without limitation silk fibroin or
silk fibroin fragments. In some embodiments, the composition
includes high molecular weight SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments. In some
embodiments, the composition includes a chemical fabric softener.
In some embodiments, the composition includes a Bronsted acid. In
some embodiments, the method further includes dyeing the substrate
prior to applying to the substrate the at least one composition
including SPF as defined herein, including without limitation silk
fibroin or silk fibroin fragments. In some embodiments, the method
further includes dyeing the substrate after applying to the
substrate the at least one composition including SPF as defined
herein, including without limitation silk fibroin or silk fibroin
fragments.
[0005] The disclosure also relates to a method of coating a
substrate with a coating including SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, and a
chemical modifier or a physical modifier, for example a
crosslinker, the method including applying to the substrate at
least one composition including SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, with an
average weight average molecular weight from about 1 kDa to about
144 kDa, and a polydispersity between 1 and about 5.0, wherein the
chemical modifier or physical modifier, for example the
crosslinker, is added "in-situ," i.e., at the same time the SPF as
defined herein, including without limitation silk fibroin or silk
fibroin fragments, are added to the substrate, for example a
fabric.
[0006] The disclosure also relates to a method of coating a
substrate with a coating including SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, and a
chemical modifier or a physical modifier, for example a
crosslinker, the method including applying to the substrate at
least one composition including SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, with an
average weight average molecular weight from about 1 kDa to about
144 kDa, and a polydispersity between 1 and about 5.0, wherein the
chemical modifier or physical modifier, for example the
crosslinker, is added to the SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, to
create a modified silk fibroin, which is thereafter applied to the
substrate, for example a fabric.
[0007] The disclosure relates to articles including one or more
coated substrates, the articles including, but not being limited
to, apparel, padding, shoes, gloves, luggage, furs, jewelry and
bags, configured to be worn or carried on the body, that is at
least partially surface treated with a composition, for example a
solution, of pure silk fibroin-based protein fragments of the
present disclosure so as to result in a silk coating on the
product. In some embodiments, the solutions of silk fibroin-based
proteins or fragments thereof may be aqueous solutions, organic
solutions, or emulsions. In an embodiment, the product is
manufactured from a textile material. In an embodiment, the product
is manufactured from a non-textile material. In an embodiment,
desired additives can be added to an aqueous solution of pure silk
fibroin-based protein fragments of the present disclosure so as to
result in a silk coating having desired additives.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The presently disclosed embodiments will be further
explained with reference to the attached drawings. The drawings
shown are not necessarily to scale, with emphasis instead generally
being placed upon illustrating the principles of the presently
disclosed embodiments.
[0009] FIG. 1A illustrates a synthetic scheme for conjugating silk
fibroin to a reactive linker, which is then reacted to a group on a
substrate. FIG. 1B illustrates a synthetic scheme for chemical
modification and purification of silk molecules; the pH of the silk
solutions was 7-8 prior to addition of crosslinker; the pH dropped
significantly upon addition of the crosslinker; the pH was then
adjusted to 8.5, and the samples were either dialyzed against water
or purified via TFF against water; the pH was adjusted to 4-5 for
fabric coatings. FIG. 1C illustrates a synthetic scheme for in situ
modification of silk; the pH of the silk solutions was 6-7 prior to
addition of crosslinker; the pH dropped significantly upon addition
of the crosslinker; the solution was filtered and used within hours
for fabric coatings without purification or pH adjustments.
[0010] FIG. 2 illustrates some examples of chemically linked
Silk-Substrate constructs, including Silk-Linker-Substrate
constructs.
[0011] FIG. 3 illustrates a synthetic scheme for conjugating a
substrate to a reactive linker, which is then reacted to silk
fibroin; several Silk-Linker-Substrate constructs are depicted
including an amino-silane based linker.
[0012] FIGS. 4A and 4B illustrate comparative vertical wicking test
results for samples coated with chemically modified silk fibroin
(STI-17100706-D001: coated with silk-conjugate; STI-17100706-D002:
coated with silk only; STI-17100706-D003: coated with precursor
linker only; STI-17100706: control), tested after a number (T) of
laundering cycles (T=0, FIG. 4A; T=3 FIG. 4B; samples coated with a
silk-conjugate, and samples coated with silk only improve wicking
compared to an unfinished control sample; samples coated with a
silk-conjugate shows better wicking than samples coated with silk
only; unfinished control samples, and samples coated with a
precursor linker only show almost no wicking.
[0013] FIGS. 5A and 5B illustrate comparative absorbency test
results for samples coated with chemically modified silk fibroin
(STI-17100706-D001: coated with silk-conjugate; STI-17100706-D002:
coated with silk only; STI-17100706-D003: coated with precursor
linker only; STI-17100706: control), tested after a number (T) of
laundering cycles (T=0, FIG. 5A; T=3 FIG. 5B); samples coated with
a silk-conjugate, and samples coated with silk only have a
significantly improved absorbency, and samples coated with a
silk-conjugate absorb better than samples coated with silk only;
unfinished control samples and samples coated with the precursor
linker only do not absorb for T=0.
[0014] FIGS. 6A and 6B illustrate comparative dry rate test results
for samples coated with chemically modified silk fibroin
(STI-17100706-D001: coated with silk-conjugate; STI-17100706-D002:
coated with silk only; STI-17100706-D003: coated with precursor
linker only; STI-17100706: control), tested after a number (T) of
laundering cycles (T=0, FIG. 6A; T=3 FIG. 6B); samples coated with
a silk-conjugate have an improved dry rate compared to the
unfinished sample; samples coated with silk only have lower dry
rate than unfinished control samples (FIG. 6A); for T=3 samples
coated with a silk-conjugate show significant improvements (FIG.
6B).
[0015] FIGS. 7A-7D illustrate comparative vertical wicking test
results for samples coated with chemically modified silk fibroin
(control: FIG. 7A; coated with silk only: FIG. 7B; coated with
in-situ modified silk: FIG. 7C; coated with purified
silk-conjugate: FIG. 7D), tested after a number (T) of laundering
cycles (0, 3, and 20).
[0016] FIGS. 8A-8D illustrate comparative absorbency test results
for samples coated with chemically modified silk fibroin (control:
FIG. 8A; coated with silk only: FIG. 8B; coated with in-situ
modified silk: FIG. 8C; coated with purified silk-conjugate: FIG.
8D), tested after a number (T) of laundering cycles (0, 3, and
20).
[0017] FIGS. 9A-9D illustrate comparative dry rate test results for
samples coated with chemically modified silk fibroin (control: FIG.
9A; coated with silk only: FIG. 9B; coated with in-situ modified
silk: FIG. 9C; coated with purified silk-conjugate: FIG. 9D),
tested after a number (T) of laundering cycles (0, 3, and 20).
[0018] FIG. 10 illustrates comparative absorbency test results for
samples coated with silk fibroin chemically modified with natural
crosslinkers (control sample, sample coated with silk only, sample
coated with silk modified with caffeic acid, sample coated with
silk modified with genipin).
[0019] FIGS. 11A-D illustrate the data analysis by PEAKS software
for the mass spectrum obtained for functionalized silk samples:
077-027-1 (FIG. 11A), 077-024-2 (FIG. 11B), 077-028-2 (FIG. 11C)
and 077-030-1 (FIG. 11D).
[0020] FIGS. 12A-B show the electrophoresis gel for silk
fibroin-based protein fragments (FIG. 12A), and functionalized silk
fibroin-based protein fragments samples 077-024-2 (Lane 3),
077-027-1 (Lane 4), 077-027-2 (Lane 5), 077-028-2 (Lane 6), and
077-030-1 (Lane 7) (FIG. 12B). Lane 1 of FIG. 12B shows BioRad IEF
Standards of molecular weight bands. Lane 2 of FIG. 12B shows IEF
Sample buffer. Lane 8 of FIG. 12B shows MC-1. Lane 9 of FIG. 12B
shows 5700-SP. Lane 10 of FIG. 12B shows DBr-7. Lane 11 of FIG. 12B
shows Ser-1. FIG. 12A shows the electrophoresis gel from several
Activated Silks.TM., and FIG. 12B shows the electrophoresis gel for
chemically modified Activated Silks.TM..
[0021] FIG. 13 shows the SEC-RI chromatograms of two modified
Mid-MW silks (098-29-02, and 098-30-02) compared to an unmodified
Mid-MW weight silk.
[0022] FIG. 14A-B show the m/z and ms2 fragmentation patterns for
two subunits: heavy chain (FIG. 14A), light chain (FIG. 14B) in the
mass spectra for the modified Low-MW silk (077-027-1).
[0023] FIG. 15A-C show the m/z and ms2 fragmentation patterns for
all three subunits: heavy chain (FIG. 15A), light chain (FIG. 15B),
and fibrohexamerin (FIG. 15C) in the mass spectra for the modified
Low-MW silk (077-024-2).
[0024] FIG. 16 shows the m/z and ms2 fragmentation patterns light
chain in the mass spectrum for the modified Low-MW silk
(077-028-2).
[0025] FIG. 17 shows the m/z and ms2 fragmentation patterns light
chain in the mass spectrum for the modified Low-MW silk
(077-030-1).
[0026] FIG. 18 is a flow chart showing various embodiments for
producing pure silk fibroin protein fragments (SPFs) of the present
disclosure.
[0027] FIG. 19 is a flow chart showing various parameters that can
be modified during the process of producing a silk protein fragment
solution of the present disclosure during the extraction and the
dissolution steps.
[0028] While the above-identified drawings set forth presently
disclosed embodiments, other embodiments are also contemplated, as
noted in the discussion. This disclosure presents illustrative
embodiments by way of representation and not limitation. Numerous
other modifications and embodiments can be devised by those skilled
in the art which fall within the scope and spirit of the principles
of the presently disclosed embodiments.
DETAILED DESCRIPTION
[0029] SPF Definitions and Properties As used herein, "silk protein
fragments" (SPF) include one or more of: "silk fibroin fragments"
as defined herein; "recombinant silk fragments" as defined herein;
"spider silk fragments" as defined herein; "silk fibroin-like
protein fragments" as defined herein; and/or "chemically modified
silk fragments" as defined herein. SPF may have any molecular
weight values or ranges described herein, and any polydispersity
values or ranges described herein. As used herein, in some
embodiments the term "silk protein fragment" also refers to a silk
protein that comprises or consists of at least two identical
repetitive units which each independently selected from
naturally-occurring silk polypeptides or of variations thereof,
amino acid sequences of naturally-occurring silk polypeptides, or
of combinations of both.
[0030] SPF Molecular Weight and Polydispersity
[0031] In an embodiment, a composition of the present disclosure
includes SPF having an average weight average molecular weight
ranging from 6 kDa to 17 kDa. In an embodiment, a composition of
the present disclosure includes SPF having a weight average
molecular weight ranging from 17 kDa to 39 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from 39 kDa to 80
kDa. In an embodiment, a composition of the present disclosure
includes SPF having an average weight average molecular weight
ranging from about 1 to about 5 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 5 to
about 10 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 10 to about 15 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 15 to
about 20 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 20 to about 25 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 25 to
about 30 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 30 to about 35 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 35 to
about 40 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 40 to about 45 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 45 to
about 50 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 50 to about 55 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 55 to
about 60 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 60 to about 65 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 65 to
about 70 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 70 to about 75 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 75 to
about 80 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 80 to about 85 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 85 to
about 90 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 90 to about 95 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 95 to
about 100 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 100 to about 105 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 105 to
about 110 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 110 to about 115 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 115 to
about 120 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 120 to about 125 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 125 to
about 130 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 130 to about 135 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 135 to
about 140 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 140 to about 145 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 145 to
about 150 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 150 to about 155 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 155 to
about 160 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 160 to about 165 kDa. I In an embodiment,
a composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 165 to
about 170 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 170 to about 175 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 175 to
about 180 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 180 to about 185 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 185 to
about 190 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 190 to about 195 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 195 to
about 200 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 200 to about 205 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 205 to
about 210 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 210 to about 215 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 215 to
about 220 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 220 to about 225 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 225 to
about 230 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 230 to about 235 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 235 to
about 240 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 240 to about 245 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 245 to
about 250 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 250 to about 255 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 255 to
about 260 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 260 to about 265 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 265 to
about 270 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 270 to about 275 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 275 to
about 280 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 280 to about 285 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 285 to
about 290 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 290 to about 295 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 295 to
about 300 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 300 to about 305 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 305 to
about 310 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 310 to about 315 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 315 to
about 320 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 320 to about 325 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 325 to
about 330 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 330 to about 335 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 335 to
about 340 kDa. In an embodiment, a composition of the present
disclosure includes SPF having an average weight average molecular
weight ranging from about 340 to about 345 kDa. In an embodiment, a
composition of the present disclosure includes SPF having an
average weight average molecular weight ranging from about 345 to
about 350 kDa.
[0032] In some embodiments, compositions of the present disclosure
include SPF compositions selected from compositions #1001 to #2450,
having weight average molecular weights selected from about 1 kDa
to about 145 kDa, and a polydispersity range selected from between
1 and about 5 (including, without limitation, a polydispersity of
1), between 1 and about 1.5 (including, without limitation, a
polydispersity of 1), between about 1.5 and about 2, between about
1.5 and about 3, between about 2 and about 2.5, between about 2.5
and about 3, between about 3 and about 3.5, between about 3.5 and
about 4, between about 4 and about 4.5, and between about 4.5 and
about 5:
TABLE-US-00001 MW PDI (about) (about) 1-5 1-1.5 1.5-2 1.5-3 2-2.5
2.5-3 3-3.5 3.5-4 4-4.5 4.5-5 1 kDa 1001 1002 1003 1004 1005 1006
1007 1008 1009 1010 2 kDa 1011 1012 1013 1014 1015 1016 1017 1018
1019 1020 3 kDa 1021 1022 1023 1024 1025 1026 1027 1028 1029 1030 4
kDa 1031 1032 1033 1034 1035 1036 1037 1038 1039 1040 5 kDa 1041
1042 1043 1044 1045 1046 1047 1048 1049 1050 6 kDa 1051 1052 1053
1054 1055 1056 1057 1058 1059 1060 7 kDa 1061 1062 1063 1064 1065
1066 1067 1068 1069 1070 8 kDa 1071 1072 1073 1074 1075 1076 1077
1078 1079 1080 9 kDa 1081 1082 1083 1084 1085 1086 1087 1088 1089
1090 10 kDa 1091 1092 1093 1094 1095 1096 1097 1098 1099 1100 11
kDa 1101 1102 1103 1104 1105 1106 1107 1108 1109 1110 12 kDa 1111
1112 1113 1114 1115 1116 1117 1118 1119 1120 13 kDa 1121 1122 1123
1124 1125 1126 1127 1128 1129 1130 14 kDa 1131 1132 1133 1134 1135
1136 1137 1138 1139 1140 15 kDa 1141 1142 1143 1144 1145 1146 1147
1148 1149 1150 16 kDa 1151 1152 1153 1154 1155 1156 1157 1158 1159
1160 17 kDa 1161 1162 1163 1164 1165 1166 1167 1168 1169 1170 18
kDa 1171 1172 1173 1174 1175 1176 1177 1178 1179 1180 19 kDa 1181
1182 1183 1184 1185 1186 1187 1188 1189 1190 20 kDa 1191 1192 1193
1194 1195 1196 1197 1198 1199 1200 21 kDa 1201 1202 1203 1204 1205
1206 1207 1208 1209 1210 22 kDa 1211 1212 1213 1214 1215 1216 1217
1218 1219 1220 23 kDa 1221 1222 1223 1224 1225 1226 1227 1228 1229
1230 24 kDa 1231 1232 1233 1234 1235 1236 1237 1238 1239 1240 25
kDa 1241 1242 1243 1244 1245 1246 1247 1248 1249 1250 26 kDa 1251
1252 1253 1254 1255 1256 1257 1258 1259 1260 27 kDa 1261 1262 1263
1264 1265 1266 1267 1268 1269 1270 28 kDa 1271 1272 1273 1274 1275
1276 1277 1278 1279 1280 29 kDa 1281 1282 1283 1284 1285 1286 1287
1288 1289 1290 30 kDa 1291 1292 1293 1294 1295 1296 1297 1298 1299
1300 31 kDa 1301 1302 1303 1304 1305 1306 1307 1308 1309 1310 32
kDa 1311 1312 1313 1314 1315 1316 1317 1318 1319 1320 33 kDa 1321
1322 1323 1324 1325 1326 1327 1328 1329 1330 34 kDa 1331 1332 1333
1334 1335 1336 1337 1338 1339 1340 35 kDa 1341 1342 1343 1344 1345
1346 1347 1348 1349 1350 36 kDa 1351 1352 1353 1354 1355 1356 1357
1358 1359 1360 37 kDa 1361 1362 1363 1364 1365 1366 1367 1368 1369
1370 38 kDa 1371 1372 1373 1374 1375 1376 1377 1378 1379 1380 39
kDa 1381 1382 1383 1384 1385 1386 1387 1388 1389 1390 40 kDa 1391
1392 1393 1394 1395 1396 1397 1398 1399 1400 41 kDa 1401 1402 1403
1404 1405 1406 1407 1408 1409 1410 42 kDa 1411 1412 1413 1414 1415
1416 1417 1418 1419 1420 43 kDa 1421 1422 1423 1424 1425 1426 1427
1428 1429 1430 44 kDa 1431 1432 1433 1434 1435 1436 1437 1438 1439
1440 45 kDa 1441 1442 1443 1444 1445 1446 1447 1448 1449 1450 46
kDa 1451 1452 1453 1454 1455 1456 1457 1458 1459 1460 47 kDa 1461
1462 1463 1464 1465 1466 1467 1468 1469 1470 48 kDa 1471 1472 1473
1474 1475 1476 1477 1478 1479 1480 49 kDa 1481 1482 1483 1484 1485
1486 1487 1488 1489 1490 50 kDa 1491 1492 1493 1494 1495 1496 1497
1498 1499 1500 51 kDa 1501 1502 1503 1504 1505 1506 1507 1508 1509
1510 52 kDa 1511 1512 1513 1514 1515 1516 1517 1518 1519 1520 53
kDa 1521 1522 1523 1524 1525 1526 1527 1528 1529 1530 54 kDa 1531
1532 1533 1534 1535 1536 1537 1538 1539 1540 55 kDa 1541 1542 1543
1544 1545 1546 1547 1548 1549 1550 56 kDa 1551 1552 1553 1554 1555
1556 1557 1558 1559 1560 57 kDa 1561 1562 1563 1564 1565 1566 1567
1568 1569 1570 58 kDa 1571 1572 1573 1574 1575 1576 1577 1578 1579
1580 59 kDa 1581 1582 1583 1584 1585 1586 1587 1588 1589 1590 60
kDa 1591 1592 1593 1594 1595 1596 1597 1598 1599 1600 61 kDa 1601
1602 1603 1604 1605 1606 1607 1608 1609 1610 62 kDa 1611 1612 1613
1614 1615 1616 1617 1618 1619 1620 63 kDa 1621 1622 1623 1624 1625
1626 1627 1628 1629 1630 64 kDa 1631 1632 1633 1634 1635 1636 1637
1638 1639 1640 65 kDa 1641 1642 1643 1644 1645 1646 1647 1648 1649
1650 66 kDa 1651 1652 1653 1654 1655 1656 1657 1658 1659 1660 67
kDa 1661 1662 1663 1664 1665 1666 1667 1668 1669 1670 68 kDa 1671
1672 1673 1674 1675 1676 1677 1678 1679 1680 69 kDa 1681 1682 1683
1684 1685 1686 1687 1688 1689 1690 70 kDa 1691 1692 1693 1694 1695
1696 1697 1698 1699 1700 71 kDa 1701 1702 1703 1704 1705 1706 1707
1708 1709 1710 72 kDa 1711 1712 1713 1714 1715 1716 1717 1718 1719
1720 73 kDa 1721 1722 1723 1724 1725 1726 1727 1728 1729 1730 74
kDa 1731 1732 1733 1734 1735 1736 1737 1738 1739 1740 75 kDa 1741
1742 1743 1744 1745 1746 1747 1748 1749 1750 76 kDa 1751 1752 1753
1754 1755 1756 1757 1758 1759 1760 77 kDa 1761 1762 1763 1764 1765
1766 1767 1768 1769 1770 78 kDa 1771 1772 1773 1774 1775 1776 1777
1778 1779 1780 79 kDa 1781 1782 1783 1784 1785 1786 1787 1788 1789
1790 80 kDa 1791 1792 1793 1794 1795 1796 1797 1798 1799 1800 81
kDa 1801 1802 1803 1804 1805 1806 1807 1808 1809 1810 82 kDa 1811
1812 1813 1814 1815 1816 1817 1818 1819 1820 83 kDa 1821 1822 1823
1824 1825 1826 1827 1828 1829 1830 84 kDa 1831 1832 1833 1834 1835
1836 1837 1838 1839 1840 85 kDa 1841 1842 1843 1844 1845 1846 1847
1848 1849 1850 86 kDa 1851 1852 1853 1854 1855 1856 1857 1858 1859
1860 87 kDa 1861 1862 1863 1864 1865 1866 1867 1868 1869 1870 88
kDa 1871 1872 1873 1874 1875 1876 1877 1878 1879 1880 89 kDa 1881
1882 1883 1884 1885 1886 1887 1888 1889 1890 90 kDa 1891 1892 1893
1894 1895 1896 1897 1898 1899 1900 91 kDa 1901 1902 1903 1904 1905
1906 1907 1908 1909 1910 92 kDa 1911 1912 1913 1914 1915 1916 1917
1918 1919 1920 93 kDa 1921 1922 1923 1924 1925 1926 1927 1928 1929
1930 94 kDa 1931 1932 1933 1934 1935 1936 1937 1938 1939 1940 95
kDa 1941 1942 1943 1944 1945 1946 1947 1948 1949 1950 96 kDa 1951
1952 1953 1954 1955 1956 1957 1958 1959 1960 97 kDa 1961 1962 1963
1964 1965 1966 1967 1968 1969 1970 98 kDa 1971 1972 1973 1974 1975
1976 1977 1978 1979 1980 99 kDa 1981 1982 1983 1984 1985 1986 1987
1988 1989 1990 100 kDa 1991 1992 1993 1994 1995 1996 1997 1998 1999
2000 101 kDa 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 102
kDa 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 103 kDa 2021
2022 2023 2024 2025 2026 2027 2028 2029 2030 104 kDa 2031 2032 2033
2034 2035 2036 2037 2038 2039 2040 105 kDa 2041 2042 2043 2044 2045
2046 2047 2048 2049 2050 106 kDa 2051 2052 2053 2054 2055 2056 2057
2058 2059 2060 107 kDa 2061 2062 2063 2064 2065 2066 2067 2068 2069
2070 108 kDa 2071 2072 2073 2074 2075 2076 2077 2078 2079 2080 109
kDa 2081 2082 2083 2084 2085 2086 2087 2088 2089 2090 110 kDa 2091
2092 2093 2094 2095 2096 2097 2098 2099 2100 111 kDa 2101 2102 2103
2104 2105 2106 2107 2108 2109 2110 112 kDa 2111 2112 2113 2114 2115
2116 2117 2118 2119 2120 113 kDa 2121 2122 2123 2124 2125 2126 2127
2128 2129 2130 114 kDa 2131 2132 2133 2134 2135 2136 2137 2138 2139
2140 115 kDa 2141 2142 2143 2144 2145 2146 2147 2148 2149 2150 116
kDa 2151 2152 2153 2154 2155 2156 2157 2158 2159 2160 117 kDa 2161
2162 2163 2164 2165 2166 2167 2168 2169 2170 118 kDa 2171 2172 2173
2174 2175 2176 2177 2178 2179 2180 119 kDa 2181 2182 2183 2184 2185
2186 2187 2188 2189 2190 120 kDa 2191 2192 2193 2194 2195 2196 2197
2198 2199 2200 121 kDa 2201 2202 2203 2204 2205 2206 2207 2208 2209
2210 122 kDa 2211 2212 2213 2214 2215 2216 2217 2218 2219 2220 123
kDa 2221 2222 2223 2224 2225 2226 2227 2228 2229 2230 124 kDa 2231
2232 2233 2234 2235 2236 2237 2238 2239 2240 125 kDa 2241 2242 2243
2244 2245 2246 2247 2248 2249 2250 126 kDa 2251 2252 2253 2254 2255
2256 2257 2258 2259 2260 127 kDa 2261 2262 2263 2264 2265 2266 2267
2268 2269 2270 128 kDa 2271 2272 2273 2274 2275 2276 2277 2278 2279
2280 129 kDa 2281 2282 2283 2284 2285 2286 2287 2288 2289 2290 130
kDa 2291 2292 2293 2294 2295 2296 2297 2298 2299 2300 131 kDa 2301
2302 2303 2304 2305 2306 2307 2308 2309 2310 132 kDa 2311 2312 2313
2314 2315 2316 2317 2318 2319 2320 133 kDa 2321 2322 2323 2324 2325
2326 2327 2328 2329 2330 134 kDa 2331 2332 2333 2334 2335 2336 2337
2338 2339 2340 135 kDa 2341 2342 2343 2344 2345 2346 2347 2348 2349
2350 136 kDa 2351 2352 2353 2354 2355 2356 2357 2358 2359 2360 137
kDa 2361 2362 2363 2364 2365 2366 2367 2368 2369 2370 138 kDa 2371
2372 2373 2374 2375 2376 2377 2378 2379 2380 139 kDa 2381 2382 2383
2384 2385 2386 2387 2388 2389 2390 140 kDa 2391 2392 2393 2394 2395
2396 2397 2398 2399 2400 141 kDa 2401 2402 2403 2404 2405 2406 2407
2408 2409 2410 142 kDa 2411 2412 2413 2414 2415 2416 2417 2418 2419
2420 143 kDa 2421 2422 2423 2424 2425 2426 2427 2428 2429 2430 144
kDa 2431 2432 2433 2434 2435 2436 2437 2438 2439 2440 145 kDa 2441
2442 2443 2444 2445 2446 2447 2448 2449 2450
[0033] As used herein, "low molecular weight," "low MW," or
"low-MW" SPF may include SPF having a weight average molecular
weight, or average weight average molecular weight in a range of
about 5 kDa to about 30 kDa, about 14 kDa to about 30 kDa, or about
6 kDa to about 17 kDa. In some embodiments, a target low molecular
weight for certain SPF may be weight average molecular weight of
about 5 kDa, about 6 kDa, about 7 kDa, about 8 kDa, about 9 kDa,
about 10 kDa, about 11 kDa, about 12 kDa, about 13 kDa, about 14
kDa, about 15 kDa, about 16 kDa, about 17 kDa, about 18 kDa, about
19 kDa, about 20 kDa, about 21 kDa, about 22 kDa, about 23 kDa,
about 24 kDa, about 25 kDa, about 26 kDa, about 27 kDa, about 28
kDa, about 29 kDa, or about 30 kDa.
[0034] As used herein, "medium molecular weight," "medium MW," or
"mid-MW" SPF may include SPF having a weight average molecular
weight, or average weight average molecular weight in a range of
about 20 kDa to about 55 kDa, about 39 kDa to about 54 kDa, or
about 17 kDa to about 39 kDa. In some embodiments, a target medium
molecular weight for certain SPF may be weight average molecular
weight of about 17 kDa, about 18 kDa, about 19 kDa, about 20 kDa,
about 21 kDa, about 22 kDa, about 23 kDa, about 24 kDa, about 25
kDa, about 26 kDa, about 27 kDa, about 28 kDa, about 29 kDa, about
30 kDa, about 31 kDa, about 32 kDa, about 33 kDa, about 34 kDa,
about 35 kDa, about 36 kDa, about 37 kDa, about 38 kDa, about 39
kDa, about 40 kDa, about 41 kDa, about 42 kDa, about 43 kDa, about
44 kDa, about 45 kDa, about 46 kDa, about 47 kDa, about 48 kDa,
about 49 kDa, about 50 kDa, about 51 kDa, about 52 kDa, about 53
kDa, about 54 kDa, or about 55 kDa.
[0035] As used herein, "high molecular weight," "high MW," or
"high-MW" SPF may include SPF having a weight average molecular
weight, or average weight average molecular weight that is in a
range of about 55 kDa to about 150 kDa, or about 39 kDa to about 80
kDa. In some embodiments, a target high molecular weight for
certain SPF may be about 39 kDa, about 40 kDa, about 41 kDa, about
42 kDa, about 43 kDa, about 44 kDa, about 45 kDa, about 46 kDa,
about 47 kDa, about 48 kDa, about 49 kDa, about 50 kDa, about 51
kDa, about 52 kDa, about 53 kDa, about 54 kDa, about 55 kDa, about
56 kDa, about 57 kDa, about 58 kDa, about 59 kDa, about 60 kDa,
about 61 kDa, about 62 kDa, about 63 kDa, about 64 kDa, about 65
kDa, about 66 kDa, about 67 kDa, about 68 kDa, about 69 kDa, about
70 kDa, about 71 kDa, about 72 kDa, about 73 kDa, about 74 kDa,
about 75 kDa, about 76 kDa, about 77 kDa, about 78 kDa, about 79
kDa, or about 80 kDa.
[0036] In some embodiments, the molecular weights described herein
(e.g., low molecular weight silk, medium molecular weight silk,
high molecular weight silk) may be converted to the approximate
number of amino acids contained within the respective SPF, as would
be understood by a person having ordinary skill in the art. For
example, the average weight of an amino acid may be about 110
daltons (i.e., 110 g/mol). Therefore, in some embodiments, dividing
the molecular weight of a linear protein by 110 daltons may be used
to approximate the number of amino acid residues contained
therein.
[0037] In an embodiment, SPF in a composition of the present
disclosure have a polydispersity ranging from 1 to about 5.0,
including, without limitation, a polydispersity of 1. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity ranging from about 1.5 to about 3.0. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity ranging from 1 to about 1.5, including, without
limitation, a polydispersity of 1. In an embodiment, SPF in a
composition of the present disclosure have a polydispersity ranging
from about 1.5 to about 2.0. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity ranging from about
2.0 to about 2.5. In an embodiment, SPF in a composition of the
present disclosure have a polydispersity ranging from about 2.5 to
about 3.0. In an embodiment, SPF in a composition of the present
disclosure have a polydispersity ranging from about 3.0 to about
3.5. In an embodiment, SPF in a composition of the present
disclosure have a polydispersity ranging from about 3.5 to about
4.0. In an embodiment, SPF in a composition of the present
disclosure have a polydispersity ranging from about 4.0 to about
4.5. In an embodiment, SPF in a composition of the present
disclosure have a polydispersity ranging from about 4.5 to about
5.0.
[0038] In an embodiment, SPF in a composition of the present
disclosure have a polydispersity of 1. In an embodiment, SPF in a
composition of the present disclosure have a polydispersity of
about 1.1. In an embodiment, SPF in a composition of the present
disclosure have a polydispersity of about 1.2. In an embodiment,
SPF in a composition of the present disclosure have a
polydispersity of about 1.3. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 1.4. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 1.5. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 1.6. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 1.7. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 1.8. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 1.9. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 2.0. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 2.1. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 2.2. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 2.3. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 2.4. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 2.5. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 2.6. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 2.7. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 2.8. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 2.9. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 3.0. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 3.1. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 3.2. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 3.3. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 3.4. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 3.5. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 3.6. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 3.7. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 3.8. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 3.9. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 4.0. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 4.1. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 4.2. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 4.3. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 4.4. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 4.5. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 4.6. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 4.7. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 4.8. In an
embodiment, SPF in a composition of the present disclosure have a
polydispersity of about 4.9. In an embodiment, SPF in a composition
of the present disclosure have a polydispersity of about 5.0.
[0039] In some embodiments, in compositions described herein having
combinations of low, medium, and/or high molecular weight SPF, such
low, medium, and/or high molecular weight SPF may have the same or
different polydispersities.
[0040] Silk Fibroin Fragments
[0041] Methods of making silk fibroin or silk fibroin protein
fragments and their applications in various fields are known and
are described for example in U.S. Pat. Nos. 9,187,538, 9,511,012,
9,517,191, 9,522,107, 9,522,108, 9,545,369, and 10,166,177,
10,287,728 and 10,301,768, all of which are incorporated herein in
their entireties. Raw silk from silkworm Bombyx mori is composed of
two primary proteins: silk fibroin (approximately 75%) and sericin
(approximately 25%). Silk fibroin is a fibrous protein with a
semi-crystalline structure that provides stiffness and strength. As
used herein, the term "silk fibroin" means the fibers of the cocoon
of Bombyx mori having a weight average molecular weight of about
370,000 Da. The crude silkworm fiber consists of a double thread of
fibroin. The adhesive substance holding these double fibers
together is sericin. The silk fibroin is composed of a heavy chain
having a weight average molecular weight of about 350,000 Da (H
chain), and a light chain having a weight average molecular weight
about 25,000 Da (L chain). Silk fibroin is an amphiphilic polymer
with large hydrophobic domains occupying the major component of the
polymer, which has a high molecular weight. The hydrophobic regions
are interrupted by small hydrophilic spacers, and the N- and
C-termini of the chains are also highly hydrophilic. The
hydrophobic domains of the H-chain contain a repetitive hexapeptide
sequence of Gly-Ala-Gly-Ala-Gly-Ser and repeats of Gly-Ala/Ser/Tyr
dipeptides, which can form stable anti-parallel-sheet crystallites.
The amino acid sequence of the L-chain is non-repetitive, so the
L-chain is more hydrophilic and relatively elastic. The hydrophilic
(Tyr, Ser) and hydrophobic (Gly, Ala) chain segments in silk
fibroin molecules are arranged alternatively such that allows
self-assembling of silk fibroin molecules.
[0042] Provided herein are methods for producing pure and highly
scalable silk fibroin-protein fragment mixture solutions that may
be used across multiple industries for a variety of applications.
Without wishing to be bound by any particular theory, it is
believed that these methods are equally applicable to fragmentation
of any SPF described herein, including without limitation
recombinant silk proteins, and fragmentation of silk-like or
fibroin-like proteins.
[0043] As used herein, the term "fibroin" includes silk worm
fibroin and insect or spider silk protein. In an embodiment,
fibroin is obtained from Bombyx mori. Raw silk from Bombyx mori is
composed of two primary proteins: silk fibroin (approximately 75%)
and sericin (approximately 25%). Silk fibroin is a fibrous protein
with a semi-crystalline structure that provides stiffness and
strength. As used herein, the term "silk fibroin" means the fibers
of the cocoon of Bombyx mori having a weight average molecular
weight of about 370,000 Da. Conversion of these insoluble silk
fibroin fibrils into water-soluble silk fibroin protein fragments
requires the addition of a concentrated neutral salt (e.g., 8-10 M
lithium bromide), which interferes with inter- and intramolecular
ionic and hydrogen bonding that would otherwise render the fibroin
protein insoluble in water. Methods of making silk fibroin protein
fragments, and/or compositions thereof, are known and are described
for example in U.S. Pat. Nos. 9,187,538, 9,511,012, 9,517,191,
9,522,107, 9,522,108, 9,545,369, and 10,166,177.
[0044] The raw silk cocoons from the silkworm Bombyx mori was cut
into pieces. The pieces silk cocoons were processed in an aqueous
solution of Na.sub.2CO.sub.3 at about 100.degree. C. for about 60
minutes to remove sericin (degumming). The volume of the water used
equals about 0.4.times.raw silk weight and the amount of
Na.sub.2CO.sub.3 is about 0.848.times.the weight of the raw silk
cocoon pieces. The resulting degummed silk cocoon pieces were
rinsed with deionized water three times at about 60.degree. C. (20
minutes per rinse). The volume of rinse water for each cycle was
0.2 L.times.the weight of the raw silk cocoon pieces. The excess
water from the degummed silk cocoon pieces was removed. After the
DI water washing step, the wet degummed silk cocoon pieces were
dried at room temperature. The degummed silk cocoon pieces were
mixed with a LiBr solution, and the mixture was heated to about
100.degree. C. The warmed mixture was placed in a dry oven and was
heated at about 100.degree. C. for about 60 minutes to achieve
complete dissolution of the native silk protein. The resulting silk
fibroin solution was filtered and dialyzed using Tangential Flow
Filtration (TFF) and a 10 kDa membrane against deionized water for
72 hours. The resulting silk fibroin aqueous solution has a
concentration of about 8.5 wt. %. Then, 8.5% silk solution was
diluted with water to result in a 1.0% w/v silk solution. TFF can
then be used to further concentrate the pure silk solution to a
concentration of 20.0% w/w silk to water.
[0045] Dialyzing the silk through a series of water changes is a
manual and time intensive process, which could be accelerated by
changing certain parameters, for example diluting the silk solution
prior to dialysis. The dialysis process could be scaled for
manufacturing by using semi-automated equipment, for example a
tangential flow filtration system.
[0046] In some embodiments, the silk solutions are prepared under
various preparation condition parameters such as: 90.degree. C. 30
min, 90.degree. C. 60 min, 100.degree. C. 30 min, and 100.degree.
C. 60 min. Briefly, 9.3 M LiBr was prepared and allowed to sit at
room temperature for at least 30 minutes. 5 mL of LiBr solution was
added to 1.25 g of silk and placed in the 60.degree. C. oven.
Samples from each set were removed at 4, 6, 8, 12, 24, 168 and 192
hours.
[0047] In some embodiments, the silk solutions are prepared under
various preparation condition parameters such as: 90.degree. C. 30
min, 90.degree. C. 60 min, 100.degree. C. 30 min, and 100.degree.
C. 60 min. Briefly, 9.3 M LiBr solution was heated to one of four
temperatures: 60.degree. C., 80.degree. C., 100.degree. C. or
boiling. 5 mL of hot LiBr solution was added to 1.25 g of silk and
placed in the 60.degree. C. oven. Samples from each set were
removed at 1, 4 and 6 hours.
[0048] In some embodiments, the silk solutions are prepared under
various preparation condition parameters such as: Four different
silk extraction combinations were used: 90 .degree. C. 30 min,
90.degree. C. 60 min, 100.degree. C. 30 min, and 100.degree. C. 60
min. Briefly, 9.3 M LiBr solution was heated to one of four
temperatures: 60.degree. C., 80.degree. C., 100.degree. C. or
boiling. 5 mL of hot LiBr solution was added to 1.25 g of silk and
placed in the oven at the same temperature of the LiBr. Samples
from each set were removed at 1, 4 and 6 hours. 1 mL of each sample
was added to 7.5 mL of 9.3 M LiBr and refrigerated for viscosity
testing.
[0049] In some embodiments, SPF are obtained by dissolving raw
unscoured, partially scoured, or scoured silkworm fibers with a
neutral lithium bromide salt. The raw silkworm silks are processed
under selected temperature and other conditions in order to remove
any sericin and achieve the desired weight average molecular weight
(Mw) and polydispersity (PD) of the fragment mixture. Selection of
process parameters may be altered to achieve distinct final silk
protein fragment characteristics depending upon the intended use.
The resulting final fragment solution is silk fibroin protein
fragments and water with parts per million (ppm) to non-detectable
levels of process contaminants, levels acceptable in the
pharmaceutical, medical and consumer eye care markets. The
concentration, size and polydispersity of SPF may further be
altered depending upon the desired use and performance
requirements.
[0050] FIG. 18 is a flow chart showing various embodiments for
producing pure silk fibroin protein fragments (SPFs) of the present
disclosure. It should be understood that not all of the steps
illustrated are necessarily required to fabricate all silk
solutions of the present disclosure. As illustrated in FIG. 18,
step A, cocoons (heat-treated or non-heat-treated), silk fibers,
silk powder, spider silk or recombinant spider silk can be used as
the silk source. If starting from raw silk cocoons from Bombyx
mori, the cocoons can be cut into small pieces, for example pieces
of approximately equal size, step B1. The raw silk is then
extracted and rinsed to remove any sericin, step C1a. This results
in substantially sericin free raw silk. In an embodiment, water is
heated to a temperature between 84.degree. C. and 100.degree. C.
(ideally boiling) and then Na.sub.2CO.sub.3 (sodium carbonate) is
added to the boiling water until the Na.sub.2CO.sub.3 is completely
dissolved. The raw silk is added to the boiling
water/Na.sub.2CO.sub.3 (100.degree. C.) and submerged for
approximately 15-90 minutes, where boiling for a longer time
results in smaller silk protein fragments. In an embodiment, the
water volume equals about 0.4.times.raw silk weight and the
Na.sub.2CO.sub.3 volume equals about 0.848.times.raw silk weight.
In an embodiment, the water volume equals 0.1.times.raw silk weight
and the Na.sub.2CO.sub.3 volume is maintained at 2.12 g/L.
[0051] Subsequently, the water dissolved Na.sub.2CO.sub.3 solution
is drained and excess water/Na.sub.2CO.sub.3 is removed from the
silk fibroin fibers (e.g., ring out the fibroin extract by hand,
spin cycle using a machine, etc.). The resulting silk fibroin
extract is rinsed with warm to hot water to remove any remaining
adsorbed sericin or contaminate, typically at a temperature range
of about 40.degree. C. to about 80.degree. C., changing the volume
of water at least once (repeated for as many times as required).
The resulting silk fibroin extract is a substantially
sericin-depleted silk fibroin. In an embodiment, the resulting silk
fibroin extract is rinsed with water at a temperature of about
60.degree. C. In an embodiment, the volume of rinse water for each
cycle equals 0.1 L to 0.2 L.times.raw silk weight. It may be
advantageous to agitate, turn or circulate the rinse water to
maximize the rinse effect. After rinsing, excess water is removed
from the extracted silk fibroin fibers (e.g., ring out fibroin
extract by hand or using a machine). Alternatively, methods known
to one skilled in the art such as pressure, temperature, or other
reagents or combinations thereof may be used for the purpose of
sericin extraction. Alternatively, the silk gland (100% sericin
free silk protein) can be removed directly from a worm. This would
result in liquid silk protein, without any alteration of the
protein structure, free of sericin.
[0052] The extracted fibroin fibers are then allowed to dry
completely. Once dry, the extracted silk fibroin is dissolved using
a solvent added to the silk fibroin at a temperature between
ambient and boiling, step C1b. In an embodiment, the solvent is a
solution of Lithium bromide (LiBr) (boiling for LiBr is 140.degree.
C.). Alternatively, the extracted fibroin fibers are not dried but
wet and placed in the solvent; solvent concentration can then be
varied to achieve similar concentrations as to when adding dried
silk to the solvent. The final concentration of LiBr solvent can
range from 0.1 M to 9.3 M. Complete dissolution of the extracted
fibroin fibers can be achieved by varying the treatment time and
temperature along with the concentration of dissolving solvent.
Other solvents may be used including, but not limited to, phosphate
phosphoric acid, calcium nitrate, calcium chloride solution or
other concentrated aqueous solutions of inorganic salts. To ensure
complete dissolution, the silk fibers should be fully immersed
within the already heated solvent solution and then maintained at a
temperature ranging from about 60.degree. C. to about 140.degree.
C. for 1-168 hrs. In an embodiment, the silk fibers should be fully
immersed within the solvent solution and then placed into a dry
oven at a temperature of about 100.degree. C. for about 1 hour.
[0053] The temperature at which the silk fibroin extract is added
to the LiBr solution (or vice versa) has an effect on the time
required to completely dissolve the fibroin and on the resulting
molecular weight and polydispersity of the final SPF mixture
solution. In an embodiment, silk solvent solution concentration is
less than or equal to 20% w/v. In addition, agitation during
introduction or dissolution may be used to facilitate dissolution
at varying temperatures and concentrations. The temperature of the
LiBr solution will provide control over the silk protein fragment
mixture molecular weight and polydispersity created. In an
embodiment, a higher temperature will more quickly dissolve the
silk offering enhanced process scalability and mass production of
silk solution. In an embodiment, using a LiBr solution heated to a
temperature between 80.degree. C.-140.degree. C. reduces the time
required in an oven in order to achieve full dissolution. Varying
time and temperature at or above 60.degree. C. of the dissolution
solvent will alter and control the MW and polydispersity of the SPF
mixture solutions formed from the original molecular weight of the
native silk fibroin protein.
[0054] Alternatively, whole cocoons may be placed directly into a
solvent, such as LiBr, bypassing extraction, step B2. This requires
subsequent filtration of silk worm particles from the silk and
solvent solution and sericin removal using methods know in the art
for separating hydrophobic and hydrophilic proteins such as a
column separation and/or chromatography, ion exchange, chemical
precipitation with salt and/or pH, and or enzymatic digestion and
filtration or extraction, all methods are common examples and
without limitation for standard protein separation methods, step
C2. Non-heat treated cocoons with the silkworm removed, may
alternatively be placed into a solvent such as LiBr, bypassing
extraction. The methods described above may be used for sericin
separation, with the advantage that non-heat treated cocoons will
contain significantly less worm debris.
[0055] Dialysis may be used to remove the dissolution solvent from
the resulting dissolved fibroin protein fragment solution by
dialyzing the solution against a volume of water, step E1.
Pre-filtration prior to dialysis is helpful to remove any debris
(i.e., silk worm remnants) from the silk and LiBr solution, step D.
In one example, a 3 .mu.m or 5 .mu.m filter is used with a
flow-rate of 200-300 mL/min to filter a 0.1% to 1.0% silk-LiBr
solution prior to dialysis and potential concentration if desired.
A method disclosed herein, as described above, is to use time
and/or temperature to decrease the concentration from 9.3 M LiBr to
a range from 0.1 M to 9.3 M to facilitate filtration and downstream
dialysis, particularly when considering creating a scalable process
method. Alternatively, without the use of additional time or
temperate, a 9.3 M LiBr-silk protein fragment solution may be
diluted with water to facilitate debris filtration and dialysis.
The result of dissolution at the desired time and temperate
filtration is a translucent particle-free room temperature
shelf-stable silk protein fragment-LiBr solution of a known MW and
polydispersity. It is advantageous to change the dialysis water
regularly until the solvent has been removed (e.g., change water
after 1 hour, 4 hours, and then every 12 hours for a total of 6
water changes). The total number of water volume changes may be
varied based on the resulting concentration of solvent used for
silk protein dissolution and fragmentation. After dialysis, the
final silk solution maybe further filtered to remove any remaining
debris (i.e., silk worm remnants).
[0056] Alternatively, Tangential Flow Filtration (TFF), which is a
rapid and efficient method for the separation and purification of
biomolecules, may be used to remove the solvent from the resulting
dissolved fibroin solution, step E2. TFF offers a highly pure
aqueous silk protein fragment solution and enables scalability of
the process in order to produce large volumes of the solution in a
controlled and repeatable manner. The silk and LiBr solution may be
diluted prior to TFF (20% down to 0.1% silk in either water or
LiBr). Pre-filtration as described above prior to TFF processing
may maintain filter efficiency and potentially avoids the creation
of silk gel boundary layers on the filter's surface as the result
of the presence of debris particles. Pre-filtration prior to TFF is
also helpful to remove any remaining debris (i.e., silk worm
remnants) from the silk and LiBr solution that may cause
spontaneous or long-term gelation of the resulting water only
solution, step D. TFF, recirculating or single pass, may be used
for the creation of water-silk protein fragment solutions ranging
from 0.1% silk to 30.0% silk (more preferably, 0.1%-6.0% silk).
Different cutoff size TFF membranes may be required based upon the
desired concentration, molecular weight and polydispersity of the
silk protein fragment mixture in solution. Membranes ranging from
1-100 kDa may be necessary for varying molecular weight silk
solutions created for example by varying the length of extraction
boil time or the time and temperate in dissolution solvent (e.g.,
LiBr). In an embodiment, a TFF 5 or 10 kDa membrane is used to
purify the silk protein fragment mixture solution and to create the
final desired silk-to-water ratio. As well, TFF single pass, TFF,
and other methods known in the art, such as a falling film
evaporator, may be used to concentrate the solution following
removal of the dissolution solvent (e.g., LiBr) (with resulting
desired concentration ranging from 0.1% to 30% silk). This can be
used as an alternative to standard HFIP concentration methods known
in the art to create a water-based solution. A larger pore membrane
could also be utilized to filter out small silk protein fragments
and to create a solution of higher molecular weight silk with
and/or without tighter polydispersity values.
[0057] An assay for LiBr and Na.sub.2CO.sub.3 detection can be
performed using an HPLC system equipped with evaporative light
scattering detector (ELSD). The calculation was performed by linear
regression of the resulting peak areas for the analyte plotted
against concentration. More than one sample of a number of
formulations of the present disclosure was used for sample
preparation and analysis. Generally, four samples of different
formulations were weighed directly in a 10 mL volumetric flask. The
samples were suspended in 5 mL of 20 mM ammonium formate (pH 3.0)
and kept at 2-8.degree. C. for 2 hours with occasional shaking to
extract analytes from the film. After 2 hours the solution was
diluted with 20 mM ammonium formate (pH 3.0). The sample solution
from the volumetric flask was transferred into HPLC vials and
injected into the HPLC-ELSD system for the estimation of sodium
carbonate and lithium bromide.
[0058] The analytical method developed for the quantitation of
Na.sub.2CO.sub.3 and LiBr in silk protein formulations was found to
be linear in the range 10-165 .mu.g/mL, with RSD for injection
precision as 2% and 1% for area and 0.38% and 0.19% for retention
time for sodium carbonate and lithium bromide respectively. The
analytical method can be applied for the quantitative determination
of sodium carbonate and lithium bromide in silk protein
formulations.
[0059] FIG. 19 is a flow chart showing various parameters that can
be modified during the process of producing a silk protein fragment
solution of the present disclosure during the extraction and the
dissolution steps. Select method parameters may be altered to
achieve distinct final solution characteristics depending upon the
intended use, e.g., molecular weight and polydispersity. It should
be understood that not all of the steps illustrated are necessarily
required to fabricate all silk solutions of the present
disclosure.
[0060] In an embodiment, silk protein fragment solutions useful for
a wide variety of applications are prepared according to the
following steps: forming pieces of silk cocoons from the Bombyx
mori silkworm; extracting the pieces at about 100.degree. C. in a
Na.sub.2CO.sub.3 water solution for about 60 minutes, wherein a
volume of the water equals about 0.4.times.raw silk weight and the
amount of Na.sub.2CO.sub.3 is about 0.848.times.the weight of the
pieces to form a silk fibroin extract; triple rinsing the silk
fibroin extract at about 60.degree. C. for about 20 minutes per
rinse in a volume of rinse water, wherein the rinse water for each
cycle equals about 0.2 L.times.the weight of the pieces; removing
excess water from the silk fibroin extract; drying the silk fibroin
extract; dissolving the dry silk fibroin extract in a LiBr
solution, wherein the LiBr solution is first heated to about
100.degree. C. to create a silk and LiBr solution and maintained;
placing the silk and LiBr solution in a dry oven at about
100.degree. C. for about 60 minutes to achieve complete dissolution
and further fragmentation of the native silk protein structure into
mixture with desired molecular weight and polydispersity; filtering
the solution to remove any remaining debris from the silkworm;
diluting the solution with water to result in a 1.0 wt. % silk
solution; and removing solvent from the solution using Tangential
Flow Filtration (TFF). In an embodiment, a 10 kDa membrane is
utilized to purify the silk solution and create the final desired
silk-to-water ratio. TFF can then be used to further concentrate
the silk solution to a concentration of 2.0 wt. % silk in
water.
[0061] Without wishing to be bound by any particular theory,
varying extraction (i.e., time and temperature), LiBr (i.e.,
temperature of LiBr solution when added to silk fibroin extract or
vice versa) and dissolution (i.e., time and temperature) parameters
results in solvent and silk solutions with different viscosities,
homogeneities, and colors. Also without wishing to be bound by any
particular theory, increasing the temperature for extraction,
lengthening the extraction time, using a higher temperature LiBr
solution at emersion and over time when dissolving the silk and
increasing the time at temperature (e.g., in an oven as shown here,
or an alternative heat source) all resulted in less viscous and
more homogeneous solvent and silk solutions.
[0062] The extraction step could be completed in a larger vessel,
for example an industrial washing machine where temperatures at or
in between 60.degree. C. to 100.degree. C. can be maintained. The
rinsing step could also be completed in the industrial washing
machine, eliminating the manual rinse cycles. Dissolution of the
silk in LiBr solution could occur in a vessel other than a
convection oven, for example a stirred tank reactor. Dialyzing the
silk through a series of water changes is a manual and time
intensive process, which could be accelerated by changing certain
parameters, for example diluting the silk solution prior to
dialysis. The dialysis process could be scaled for manufacturing by
using semi-automated equipment, for example a tangential flow
filtration system.
[0063] Varying extraction (i.e., time and temperature), LiBr (i.e.,
temperature of LiBr solution when added to silk fibroin extract or
vice versa) and dissolution (i.e., time and temperature) parameters
results in solvent and silk solutions with different viscosities,
homogeneities, and colors. Increasing the temperature for
extraction, lengthening the extraction time, using a higher
temperature LiBr solution at emersion and over time when dissolving
the silk and increasing the time at temperature (e.g., in an oven
as shown here, or an alternative heat source) all resulted in less
viscous and more homogeneous solvent and silk solutions. While
almost all parameters resulted in a viable silk solution, methods
that allow complete dissolution to be achieved in fewer than 4 to 6
hours are preferred for process scalability.
[0064] In an embodiment, solutions of silk fibroin protein
fragments having a weight average ranging from about 6 kDa to about
17 kDa are prepared according to following steps: degumming a silk
source by adding the silk source to a boiling (100.degree. C.)
aqueous solution of sodium carbonate for a treatment time of
between about 30 minutes to about 60 minutes; removing sericin from
the solution to produce a silk fibroin extract comprising non-
detectable levels of sericin; draining the solution from the silk
fibroin extract; dissolving the silk fibroin extract in a solution
of lithium bromide having a starting temperature upon placement of
the silk fibroin extract in the lithium bromide solution that
ranges from about 60.degree. C. to about 140.degree. C.;
maintaining the solution of silk fibroin-lithium bromide in an oven
having a temperature of about 140.degree. C. for a period of at
most 1 hour; removing the lithium bromide from the silk fibroin
extract; and producing an aqueous solution of silk protein
fragments, the aqueous solution comprising: fragments having a
weight average molecular weight ranging from about 6 kDa to about
17 kDa, and a polydispersity of between 1 and about 5, or between
about 1.5 and about 3.0. The method may further comprise drying the
silk fibroin extract prior to the dissolving step. The aqueous
solution of silk fibroin protein fragments may comprise lithium
bromide residuals of less than 300 ppm as measured using a
high-performance liquid chromatography lithium bromide assay. The
aqueous solution of silk fibroin protein fragments may comprise
sodium carbonate residuals of less than 100 ppm as measured using a
high-performance liquid chromatography sodium carbonate assay. The
aqueous solution of silk fibroin protein fragments may be
lyophilized. In some embodiments, the silk fibroin protein fragment
solution may be further processed into various forms including gel,
powder, and nanofiber.
[0065] In an embodiment, solutions of silk fibroin protein
fragments having a weight average molecular weight ranging from
about 17 kDa to about 39 kDa are prepared according to the
following steps: adding a silk source to a boiling (100.degree. C.)
aqueous solution of sodium carbonate for a treatment time of
between about 30 minutes to about 60 minutes so as to result in
degumming; removing sericin from the solution to produce a silk
fibroin extract comprising non-detectable levels of sericin;
draining the solution from the silk fibroin extract; dissolving the
silk fibroin extract in a solution of lithium bromide having a
starting temperature upon placement of the silk fibroin extract in
the lithium bromide solution that ranges from about 80.degree. C.
to about 140.degree. C.; maintaining the solution of silk
fibroin-lithium bromide in a dry oven having a temperature in the
range between about 60.degree. C. to about 100.degree. C. for a
period of at most 1 hour; removing the lithium bromide from the
silk fibroin extract; and producing an aqueous solution of silk
fibroin protein fragments, wherein the aqueous solution of silk
fibroin protein fragments comprises lithium bromide residuals of
between about 10 ppm and about 300 ppm, wherein the aqueous
solution of silk protein fragments comprises sodium carbonate
residuals of between about 10 ppm and about 100 ppm, wherein the
aqueous solution of silk fibroin protein fragments comprises
fragments having a weight average molecular weight ranging from
about 17 kDa to about 39 kDa, and a polydispersity of between 1 and
about 5, or between about 1.5 and about 3.0. The method may further
comprise drying the silk fibroin extract prior to the dissolving
step. The aqueous solution of silk fibroin protein fragments may
comprise lithium bromide residuals of less than 300 ppm as measured
using a high-performance liquid chromatography lithium bromide
assay. The aqueous solution of silk fibroin protein fragments may
comprise sodium carbonate residuals of less than 100 ppm as
measured using a high-performance liquid chromatography sodium
carbonate assay.
[0066] In some embodiments, a method for preparing an aqueous
solution of silk fibroin protein fragments having an average weight
average molecular weight ranging from about 6 kDa to about 17 kDa
includes the steps of: degumming a silk source by adding the silk
source to a boiling (100.degree. C.) aqueous solution of sodium
carbonate for a treatment time of between about 30 minutes to about
60 minutes; removing sericin from the solution to produce a silk
fibroin extract comprising non-detectable levels of sericin;
draining the solution from the silk fibroin extract; dissolving the
silk fibroin extract in a solution of lithium bromide having a
starting temperature upon placement of the silk fibroin extract in
the lithium bromide solution that ranges from about 60.degree. C.
to about 140.degree. C.; maintaining the solution of silk
fibroin-lithium bromide in an oven having a temperature of about
140.degree. C. for a period of at least 1 hour; removing the
lithium bromide from the silk fibroin extract; and producing an
aqueous solution of silk protein fragments, the aqueous solution
comprising: fragments having an average weight average molecular
weight ranging from about 6 kDa to about 17 kDa, and a
polydispersity of between 1 and about 5, or between about 1.5 and
about 3.0. The method may further comprise drying the silk fibroin
extract prior to the dissolving step. The aqueous solution of pure
silk fibroin protein fragments may comprise lithium bromide
residuals of less than 300 ppm as measured using a high-performance
liquid chromatography lithium bromide assay . The aqueous solution
of pure silk fibroin protein fragments may comprise sodium
carbonate residuals of less than 100 ppm as measured using a
high-performance liquid chromatography sodium carbonate assay. The
method may further comprise adding a therapeutic agent to the
aqueous solution of pure silk fibroin protein fragments. The method
may further comprise adding a molecule selected from one of an
antioxidant or an enzyme to the aqueous solution of pure silk
fibroin protein fragments. The method may further comprise adding a
vitamin to the aqueous solution of pure silk fibroin protein
fragments. The vitamin may be vitamin C or a derivative thereof.
The aqueous solution of pure silk fibroin protein fragments may be
lyophilized. The method may further comprise adding an alpha
hydroxy acid to the aqueous solution of pure silk fibroin protein
fragments. The alpha hydroxy acid may be selected from the group
consisting of glycolic acid, lactic acid, tartaric acid and citric
acid. The method may further comprise adding hyaluronic acid or its
salt form at a concentration of about 0.5% to about 10.0% to the
aqueous solution of pure silk fibroin protein fragments. The method
may further comprise adding at least one of zinc oxide or titanium
dioxide. A film may be fabricated from the aqueous solution of pure
silk fibroin protein fragments produced by this method. The film
may comprise from about 1.0 wt. % to about 50,0 wt. % of vitamin C
or a derivative thereof. The film may have a water content ranging
from about 2.0 wt. % to about 20.0 wt. %. The film may comprise
from about 30.0 wt. % to about 99.5 wt. % of pure silk fibroin
protein fragments. A gel may be fabricated from the aqueous
solution of pure silk fibroin protein fragments produced by this
method. The gel may comprise from about 0.5 wt. % to about 20.0 wt.
% of vitamin C or a derivative thereof. The gel may have a silk
content of at least 2% and a vitamin content of at least 20%.
[0067] In some embodiments, a method for preparing an aqueous
solution of silk fibroin protein fragments having an average weight
average molecular weight ranging from about 17 kDa to about 39 kDa
includes the steps of: adding a silk source to a boiling
(100.degree. C.) aqueous solution of sodium carbonate for a
treatment time of between about 30 minutes to about 60 minutes so
as to result in degumming; removing sericin from the solution to
produce a silk fibroin extract comprising non-detectable levels of
sericin; draining the solution from the silk fibroin extract;
dissolving the silk fibroin extract in a solution of lithium
bromide having a starting temperature upon placement of the silk
fibroin extract in the lithium bromide solution that ranges from
about 80.degree. C. to about 140.degree. C.; maintaining the
solution of silk fibroin-lithium bromide in a dry oven having a
temperature in the range between about 60.degree. C. to about
100.degree. C. for a period of at least 1 hour; removing the
lithium bromide from the silk fibroin extract; and producing an
aqueous solution of pure silk fibroin protein fragments, wherein
the aqueous solution of pure silk fibroin protein fragments
comprises lithium bromide residuals of between about 10 ppm and
about 300 ppm, wherein the aqueous solution of silk protein
fragments comprises sodium carbonate residuals of between about 10
ppm and about 100 ppm, wherein the aqueous solution of pure silk
fibroin protein fragments comprises fragments having an average
weight average molecular weight ranging from about 17 kDa to about
39 kDa, and a polydispersity of between 1 and about 5, or between
about 1.5 and about 3.0. The method may further comprise drying the
silk fibroin extract prior to the dissolving step. The aqueous
solution of pure silk fibroin protein fragments may comprise
lithium bromide residuals of less than 300 ppm as measured using a
high-performance liquid chromatography lithium bromide assay. The
aqueous solution of pure silk fibroin protein fragments may
comprise sodium carbonate residuals of less than 100 ppm as
measured using a high-performance liquid chromatography sodium
carbonate assay. The method may further comprise adding a
therapeutic agent to the aqueous solution of pure silk fibroin
protein fragments. The method may further comprise adding a
molecule selected from one of an antioxidant or an enzyme to the
aqueous solution of pure silk fibroin protein fragments. The method
may further comprise adding a vitamin to the aqueous solution of
pure silk fibroin protein fragments. The vitamin may be vitamin C
or a derivative thereof. The aqueous solution of pure silk fibroin
protein fragments may be lyophilized. The method may further
comprise adding an alpha hydroxy acid to the aqueous solution of
pure silk fibroin protein fragments. The alpha hydroxy acid may be
selected from the group consisting of glycolic acid, lactic acid,
tartaric acid and citric acid. The method may further comprise
adding hyaluronic acid or its salt form at a concentration of about
0.5% to about 10.0% to the aqueous solution of pure silk fibroin
protein fragments. The method may further comprise adding at least
one of zinc oxide or titanium dioxide. A film may be fabricated
from the aqueous solution of pure silk fibroin protein fragments
produced by this method. The film may comprise from about 1.0 wt. %
to about 50.0 wt. % of vitamin C or a derivative thereof. The film
may have a water content ranging from about 2.0 wt. % to about 20.0
wt. %. The film may comprise from about 30.0 wt. % to about 99.5
wt. % of pure silk fibroin protein fragments. A gel may be
fabricated from the aqueous solution of pure silk fibroin protein
fragments produced by this method. The gel may comprise from about
0.5 wt. % to about 20.0 wt. % of vitamin C or a derivative thereof.
The gel may have a silk content of at least 2% and a vitamin
content of at least 20%.
[0068] In an embodiment, solutions of silk fibroin protein
fragments having a weight average molecular weight ranging from
about 39 kDa to about 80 kDa are prepared according to the
following steps: adding a silk source to a boiling (100.degree. C.)
aqueous solution of sodium carbonate for a treatment time of about
30 minutes so as to result in degumming; removing sericin from the
solution to produce a silk fibroin extract comprising
non-detectable levels of sericin; draining the solution from the
silk fibroin extract; dissolving the silk fibroin extract in a
solution of lithium bromide having a starting temperature upon
placement of the silk fibroin extract in the lithium bromide
solution that ranges from about 80.degree. C. to about 140.degree.
C.; maintaining the solution of silk fibroin-lithium bromide in a
dry oven having a temperature in the range between about 60.degree.
C. to about 100.degree. C. for a period of at most 1 hour; removing
the lithium bromide from the silk fibroin extract; and producing an
aqueous solution of silk fibroin protein fragments, wherein the
aqueous solution of silk fibroin protein fragments comprises
lithium bromide residuals of between about 10 ppm and about 300
ppm, sodium carbonate residuals of between about 10 ppm and about
100 ppm, fragments having a weight average molecular weight ranging
from about 39 kDa to about 80 kDa, and a polydispersity of between
1 and about 5, or between about 1.5 and about 3.0. The method may
further comprise drying the silk fibroin extract prior to the
dissolving step. The aqueous solution of silk fibroin protein
fragments may comprise lithium bromide residuals of less than 300
ppm as measured using a high-performance liquid chromatography
lithium bromide assay. The aqueous solution of silk fibroin protein
fragments may comprise sodium carbonate residuals of less than 100
ppm as measured using a high-performance liquid chromatography
sodium carbonate assay. In some embodiments, the method may further
comprise adding an active agent (e.g., therapeutic agent) to the
aqueous solution of pure silk fibroin protein fragments. The method
may further comprise adding an active agent selected from one of an
antioxidant or an enzyme to the aqueous solution of pure silk
fibroin protein fragments. The method may further comprise adding a
vitamin to the aqueous solution of pure silk fibroin protein
fragments. The vitamin may be vitamin C or a derivative thereof.
The aqueous solution of pure silk fibroin protein fragments may be
lyophilized. The method may further comprise adding an
alpha-hydroxy acid to the aqueous solution of pure silk fibroin
protein fragments. The alpha hydroxy acid may be selected from the
group consisting of glycolic acid, lactic acid, tartaric acid and
citric acid. The method may further comprise adding hyaluronic acid
or its salt form at a concentration of about 0.5% to about 10.0% to
the aqueous solution of pure silk fibroin protein fragments. A film
may be fabricated from the aqueous solution of pure silk fibroin
protein fragments produced by this method. The film may comprise
from about 1.0 wt. % to about 50.0 wt. % of vitamin C or a
derivative thereof. The film may have a water content ranging from
about 2.0 wt. % to about 20.0 wt. %. The film may comprise from
about 30.0 wt. % to about 99.5 wt. % of pure silk fibroin protein
fragments. A gel may be fabricated from the aqueous solution of
pure silk fibroin protein fragments produced by this method. The
gel may comprise from about 0.5 wt. % to about 20.0 wt. % of
vitamin C or a derivative thereof. The gel may have a silk content
of at least 2 wt. % and a vitamin content of at least 20 wt. %.
[0069] Molecular weight of the silk protein fragments may be
controlled based upon the specific parameters utilized during the
extraction step, including extraction time and temperature;
specific parameters utilized during the dissolution step, including
the LiBr temperature at the time of submersion of the silk in to
the lithium bromide and time that the solution is maintained at
specific temperatures; and specific parameters utilized during the
filtration step. By controlling process parameters using the
disclosed methods, it is possible to create silk fibroin protein
fragment solutions with polydispersity equal to or lower than 2.5
at a variety of different molecular weight ranging from 5 kDa to
200 kDa, or between 10 kDa and 80 kDa. By altering process
parameters to achieve silk solutions with different molecular
weights, a range of fragment mixture end products, with desired
polydispersity of equal to or less than 2.5 may be targeted based
upon the desired performance requirements. For example, a higher
molecular weight silk film containing an ophthalmic drug may have a
controlled slow release rate compared to a lower molecular weight
film making it ideal for a delivery vehicle in eye care products.
Additionally, the silk fibroin protein fragment solutions with a
polydispersity of greater than 2.5 can be achieved. Further, two
solutions with different average molecular weights and
polydispersity can be mixed to create combination solutions.
Alternatively, a liquid silk gland (100% sericin free silk protein)
that has been removed directly from a worm could be used in
combination with any of the silk fibroin protein fragment solutions
of the present disclosure. Molecular weight of the pure silk
fibroin protein fragment composition was determined using High
Pressure Liquid Chromatography (HPLC) with a Refractive Index
Detector (RID). Polydispersity was calculated using Cirrus GPC
Online GPC/SEC Software Version 3.3 (Agilent).
[0070] Differences in the processing parameters can result in
regenerated silk fibroins that vary in molecular weight, and
peptide chain size distribution (polydispersity, PD). This, in
turn, influences the regenerated silk fibroin performance,
including mechanical strength, water solubility etc.
[0071] Parameters were varied during the processing of raw silk
cocoons into the silk solution. Varying these parameters affected
the MW of the resulting silk solution. Parameters manipulated
included (i) time and temperature of extraction, (ii) temperature
of LiBr, (iii) temperature of dissolution oven, and (iv)
dissolution time. Experiments were carried out to determine the
effect of varying the extraction time. Tables A-F summarize the
results. Below is a summary: [0072] A sericin extraction time of 30
minutes resulted in larger molecular weight than a sericin
extraction time of 60 minutes [0073] Molecular weight decreases
with time in the oven [0074] 140.degree. C. LiBr and oven resulted
in the low end of the confidence interval to be below a molecular
weight of 9500 Da [0075] 30 min extraction at the 1 hour and 4 hour
time points have undigested silk [0076] 30 min extraction at the 1
hour time point resulted in a significantly high molecular weight
with the low end of the confidence interval being 35,000 Da [0077]
The range of molecular weight reached for the high end of the
confidence interval was 18000 to 216000 Da (important for offering
solutions with specified upper limit).
TABLE-US-00002 [0077] TABLE A The effect of extraction time (30 min
vs 60 min) on molecular weight of silk processed under the
conditions of 100.degree. C. Extraction Temperature, 100.degree. C.
Lithium Bromide (LiBr) and 100.degree. C. Oven Dissolution
(Oven/Dissolution Time was varied). Boil Oven Average Std
Confidence Time Time Mw dev Interval PD 30 1 57247 12780 35093
93387 1.63 60 1 31520 1387 11633 85407 2.71 30 4 40973 2632 14268
117658 2.87 60 4 25082 1248 10520 59803 2.38 30 6 25604 1405 10252
63943 2.50 60 6 20980 1262 10073 43695 2.08
TABLE-US-00003 TABLE B The effect of extraction time (30 min vs 60
min) on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, boiling Lithium Bromide
(LiBr) and 60.degree. C. Oven Dissolution for 4 hr. Boil Average
Std Confidence Sample Time Mw dev Interval PD 30 min, 4 hr 30 49656
4580 17306 142478 2.87 60 min, 4 hr 60 30042 1536 11183 80705
2.69
TABLE-US-00004 TABLE C The effect of extraction time (30 min vs 60
min) on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 60.degree. C. Lithium
Bromide (LiBr) and 60.degree. C. Oven Dissolution (Oven/Dissolution
Time was varied). Oven Average Std Confidence Sample Boil Time Time
Mw dev Interval PD 30 min, 1 hr 30 1 58436 22201 153809 2.63 60
min, 1 hr 60 1 31700 11931 84224 2.66 30 min, 4 hr 30 4 61956.5
13337 21463 178847 2.89 60 min, 4 hr 60 4 25578.5 2446 9979 65564
2.56
TABLE-US-00005 TABLE D The effect of extraction time (30 min vs 60
min) on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 80.degree. C. Lithium
Bromide (LiBr) and 80.degree. C. Oven Dissolution for 6 hr. Average
Std Confidence Sample Boil Time Mw dev Interval PD 30 min, 6 hr 30
63510 18693 215775 3.40 60 min, 6 hr 60 25164 238 9637 65706
2.61
TABLE-US-00006 TABLE E The effect of extraction time (30 min vs 60
min) on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 80.degree. C. Lithium
Bromide (LiBr) and 60.degree. C. Oven Dissolution (Oven/Dissolution
Time was varied). Oven Average Std Confidence Sample Boil Time Time
Mw dev Interval PD 30 min, 4 hr 30 4 59202 14028 19073 183760 3.10
60 min, 4 hr 60 4 26312.5 637 10266 67442 2.56 30 min, 6 hr 30 6
46824 18076 121293 2.59 60 min, 6 hr 60 6 26353 10168 68302
2.59
TABLE-US-00007 TABLE F The effect of extraction time (30 min vs 60
min) on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 140.degree. C. Lithium
Bromide (LiBr) and 140.degree. C. Oven Dissolution
(Oven/Dissolution Time was varied). Oven Average Std Confidence
Sample Boil Time Time Mw dev Interval PD 30 min, 4 hr 30 4 9024.5
1102 4493 18127 2.00865 60 min, 4 hr 60 4 15548 6954 34762 2.2358
30 min, 6 hr 30 6 13021 5987 28319 2.1749 60 min, 6 hr 60 6 10888
5364 22100 2.0298
[0078] Experiments were carried out to determine the effect of
varying the extraction temperature. Table G summarizes the results.
Below is a summary: [0079] Sericin extraction at 90.degree. C.
resulted in higher MW than sericin extraction at 100.degree. C.
extraction [0080] Both 90.degree. C. and 100.degree. C. show
decreasing MW over time in the oven
TABLE-US-00008 [0080] TABLE G The effect of extraction temperature
(90.degree. C. vs. 100.degree. C.) on molecular weight of silk
processed under the conditions of 60 min. Extraction Temperature,
100.degree. C. Lithium Bromide (LiBr) and 100.degree. C. Oven
Dissolution (Oven/Dissolution Time was varied). Boil Oven Average
Std Confidence Sample Time Time Mw dev Interval PD 90.degree. C., 4
hr 60 4 37308 4204 13368 104119 2.79 100.degree. C., 4 hr 60 4
25082 1248 10520 59804 2.38 90.degree. C., 6 hr 60 6 34224 1135
12717 92100 2.69 100.degree. C., 6 hr 60 6 20980 1262 10073 43694
2.08
[0081] Experiments were carried out to determine the effect of
varying the Lithium Bromide (LiBr) temperature when added to silk.
Tables H-I summarize the results. Below is a summary: [0082] No
impact on molecular weight or confidence interval (all CI
10500-6500 Da) [0083] Studies illustrated that the temperature of
LiBr-silk dissolution, as LiBr is added and begins dissolving,
rapidly drops below the original LiBr temperature due to the
majority of the mass being silk at room temperature
TABLE-US-00009 [0083] TABLE H The effect of Lithium Bromide (LiBr)
temperature on molecular weight of silk processed under the
conditions of 60 min. Extraction Time, 100.degree. C. Extraction
Temperature and 60.degree. C. Oven Dissolution (Oven/Dissolution
Time was varied). LiBr Temp Oven Average Std Confidence Sample
(.degree. C.) Time Mw dev Interval PD 60.degree. C. LiBr, 60 1
31700 11931 84223 2.66 1 hr 100.degree. C. LiBr, 100 1 27907 200
10735 72552 2.60 1 hr RT LiBr, RT 4 29217 1082 10789 79119 2.71 4
hr 60.degree. C. LiBr, 60 4 25578 2445 9978 65564 2.56 4 hr
80.degree. C. LiBr, 80 4 26312 637 10265 67441 2.56 4 hr
100.degree. C. LiBr, 100 4 27681 1729 11279 67931 2.45 4 hr Boil
LiBr, Boil 4 30042 1535 11183 80704 2.69 4 hr RT LiBr, RT 6 26543
1893 10783 65332 2.46 6 hr 80.degree. C. LiBr, 80 6 26353 10167
68301 2.59 6 hr 100.degree. C. LiBr, 100 6 27150 916 11020 66889
2.46 6 hr
TABLE-US-00010 TABLE I The effect of Lithium Bromide (LiBr)
temperature on molecular weight of silk processed under the
conditions of 30 min. Extraction Time, 100.degree. C. Extraction
Temperature and 60.degree. C. Oven Dissolution (Oven/Dissolution
Time was varied). LiBr Temp Oven Average Std Confidence Sample
(.degree. C.) Time Mw dev Interval PD 60.degree. C. LiBr, 60 4
61956 13336 21463 178847 2.89 4 hr 80.degree. C. LiBr, 80 4 59202
14027 19073 183760 3.10 4 hr 100.degree. C. LiBr, 100 4 47853 19757
115899 2.42 4 hr 80.degree. C. LiBr, 80 6 46824 18075 121292 2.59 6
hr 100.degree. C. LiBr, 100 6 55421 8991 19152 160366 2.89 6 hr
[0084] Experiments were carried out to determine the effect of v
oven/dissolution temperature. Tables J-N summarize the results.
Below is a summary: [0085] Oven temperature has less of an effect
on 60 min extracted silk than 30 min extracted silk. Without
wishing to be bound by theory, it is believed that the 30 min silk
is less degraded during extraction and therefore the oven
temperature has more of an effect on the larger MW, less degraded
portion of the silk. [0086] For 60.degree. C. vs. 140.degree. C.
oven the 30 min extracted silk showed a very significant effect of
lower MW at higher oven temp, while 60 min extracted silk had an
effect but much less [0087] The 140.degree. C. oven resulted in a
low end in the confidence interval at 6000 Da.
TABLE-US-00011 [0087] TABLE J The effect of oven/dissolution
temperature on molecular weight of silk processed under the
conditions of 100.degree. C. Extraction Temperature, 30 min.
Extraction Time, and 100.degree. C. Lithium Bromide (LiBr)
(Oven/Dissolution Time was varied). Boil Oven Temp Oven Average Std
Confidence Time (.degree. C.) Time Mw dev Interval PD 30 60 4 47853
19758 115900 2.42 30 100 4 40973 2632 14268 117658 2.87 30 60 6
55421 8992 19153 160366 2.89 30 100 6 25604 1405 10252 63943
2.50
TABLE-US-00012 TABLE K The effect of oven/dissolution temperature
on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 60 min. Extraction Time, and
100.degree. C. Lithium Bromide (LiBr) (Oven/Dissolution Time was
varied). Boil Time Oven Average Std Confidence (minutes) Oven Temp
Time Mw dev Interval PD 60 60 1 27908 200 10735 72552 2.60 60 100 1
31520 1387 11633 85407 2.71 60 60 4 27681 1730 11279 72552 2.62 60
100 4 25082 1248 10520 59803 2.38 60 60 6 27150 916 11020 66889
2.46 60 100 6 20980 1262 10073 43695 2.08
TABLE-US-00013 TABLE L The effect of oven/dissolution temperature
on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 60 min. Extraction Time, and
140.degree. C. Lithium Bromide (LiBr) (Oven/Dissolution Time was
varied). Boil Time Oven Oven Std Confidence (minutes) Temp(.degree.
C.) Time Average dev Interval PD 60 60 4 30042 1536 11183 80705
2.69 60 140 4 15548 7255 33322 2.14
TABLE-US-00014 TABLE M The effect of oven/dissolution temperature
on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 30 min. Extraction Time, and
140.degree. C. Lithium Bromide (LiBr) (Oven/Dissolution Time was
varied). Oven Boil Time Temp Oven Average Std Confidence (minutes)
(.degree. C.) Time Mw dev Interval PD 30 60 4 49656 4580 17306
142478 2.87 30 140 4 9025 1102 4493 18127 2.01 30 60 6 59383 11640
17641 199889 3.37 30 140 6 13021 5987 28319 2.17
TABLE-US-00015 TABLE N The effect of oven/dissolution temperature
on molecular weight of silk processed under the conditions of
100.degree. C. Extraction Temperature, 60 min. Extraction Time, and
80.degree. C. Lithium Bromide (LiBr) (Oven/Dissolution Time was
varied). Boil Time Oven Temp Oven Average Std Confidence (minutes)
(.degree. C.) Time Mw dev Interval PD 60 60 4 26313 637 10266 67442
2.56 60 80 4 30308 4293 12279 74806 2.47 60 60 6 26353 10168 68302
2.59 60 80 6 25164 238 9637 65706 2.61
[0088] The raw silk cocoons from the silkworm Bombyx mori was cut
into pieces. The pieces of raw silk cocoons were boiled in an
aqueous solution of Na.sub.2CO.sub.3 (about 100.degree. C.) for a
period of time between about 30 minutes to about 60 minutes to
remove sericin (degumming). The volume of the water used equals
about 0.4.times.raw silk weight and the amount of Na.sub.2CO.sub.3
is about 0.848.times.the weight of the raw silk cocoon pieces. The
resulting degummed silk cocoon pieces were rinsed with deionized
water three times at about 60.degree. C. (20 minutes per rinse).
The volume of rinse water for each cycle was 0.2 L.times.the weight
of the raw silk cocoon pieces. The excess water from the degummed
silk cocoon pieces was removed. After the DI water washing step,
the wet degummed silk cocoon pieces were dried at room temperature.
The degummed silk cocoon pieces were mixed with a LiBr solution,
and the mixture was heated to about 100.degree. C. The warmed
mixture was placed in a dry oven and was heated at a temperature
ranging from about 60.degree. C. to about 140.degree. C. for about
60 minutes to achieve complete dissolution of the native silk
protein. The resulting solution was allowed to cool to room
temperature and then was dialyzed to remove LiBr salts using a
3,500 Da MWCO membrane. Multiple exchanges were performed in Di
water until Br.sup.- ions were less than 1 ppm as determined in the
hydrolyzed fibroin solution read on an Oakton Bromide (Br.sup.-)
double-junction ion-selective electrode.
[0089] The resulting silk fibroin aqueous solution has a
concentration of about 8.0% w/v containing pure silk fibroin
protein fragments having an average weight average molecular weight
ranging from about 6 kDa to about 16 kDa, about 17 kDa to about 39
kDa, and about 39 kDa to about 80 kDa and a polydispersity of
between about 1.5 and about 3.0. The 8.0% w/v was diluted with DI
water to provide a 1.0% w/v, 2.0% w/v, 3.0% w/v, 4.0% w/v, 5.0% w/v
by the coating solution.
[0090] A variety of % silk concentrations have been produced
through the use of Tangential Flow Filtration (TFF). In all cases a
1% silk solution was used as the input feed. A range of 750-18,000
mL of 1% silk solution was used as the starting volume. Solution is
diafiltered in the TFF to remove lithium bromide. Once below a
specified level of residual LiBr, solution undergoes
ultrafiltration to increase the concentration through removal of
water. See examples below.
[0091] Six (6) silk solutions were utilized in standard silk
structures with the following results:
[0092] Solution #1 is a silk concentration of 5.9 wt. %, average MW
of 19.8 kDa and 2.2 PDI (made with a 60 min boil extraction,
100.degree. C. LiBr dissolution for 1 hour).
[0093] Solution #2 is a silk concentration of 6.4 wt. % (made with
a 30 min boil extraction, 60.degree. C. LiBr dissolution for 4
hrs).
[0094] Solution #3 is a silk concentration of 6.17 wt. % (made with
a 30 min boil extraction 100.degree. C. LiBr dissolution for 1
hour).
[0095] Solution #4 is a silk concentration of 7.30 wt. %: A 7.30%
silk solution was produced beginning with 30 minute extraction
batches of 100 g silk cocoons per batch. Extracted silk fibers were
then dissolved using 100.degree. C. 9.3 M LiBr in a 100.degree. C.
oven for 1 hour. 100 g of silk fibers were dissolved per batch to
create 20% silk in LiBr. Dissolved silk in LiBr was then diluted to
1% silk and filtered through a 5 .mu.m filter to remove large
debris. 15,500 mL of 1%, filtered silk solution was used as the
starting volume/diafiltration volume for TFF. Once LiBr was
removed, the solution was ultrafiltered to a volume around 1300 mL.
1262 mL of 7.30% silk was then collected. Water was added to the
feed to help remove the remaining solution and 547 mL of 3.91% silk
was then collected.
[0096] Solution #5 is a silk concentration of 6.44 wt. %: A 6.44
wt. % silk solution was produced beginning with 60 minute
extraction batches of a mix of 25, 33, 50, 75 and 100 g silk
cocoons per batch. Extracted silk fibers were then dissolved using
100.degree. C. 9.3 M LiBr in a 100.degree. C. oven for 1 hour. 35,
42, 50 and 71 g per batch of silk fibers were dissolved to create
20% silk in LiBr and combined. Dissolved silk in LiBr was then
diluted to 1% silk and filtered through a 5 .mu.m filter to remove
large debris. 17,000 mL of 1%, filtered silk solution was used as
the starting volume/diafiltration volume for TFF. Once LiBr was
removed, the solution was ultrafiltered to a volume around 3000 mL.
1490 mL of 6.44% silk was then collected. Water was added to the
feed to help remove the remaining solution and 1454 mL of 4.88%
silk was then collected.
[0097] Solution #6 is a silk concentration of 2.70 wt. %: A 2.70%
silk solution was produced beginning with 60-minute extraction
batches of 25 g silk cocoons per batch. Extracted silk fibers were
then dissolved using 100.degree. C. 9.3 M LiBr in a 100.degree. C.
oven for 1 hour. 35.48 g of silk fibers were dissolved per batch to
create 20% silk in LiBr. Dissolved silk in LiBr was then diluted to
1% silk and filtered through a 5 .mu.m filter to remove large
debris. 1000 mL of 1%, filtered silk solution was used as the
starting volume/diafiltration volume for TFF. Once LiBr was
removed, the solution was ultrafiltered to a volume around 300 mL.
312 mL of 2.7% silk was then collected.
[0098] The preparation of silk fibroin solutions with higher
molecular weights is given in Table O.
TABLE-US-00016 TABLE O Preparation and properties of silk fibroin
solutions. Average weight average Extraction Extraction LiBr Oven/
molecular Average Sample Time Temp Temp Sol'n weight poly- Name
(mins) (.degree. C.) (.degree. C.) Temp (kDa) dispersity Group A 60
100 100 100.degree. C. 34.7 2.94 TFF oven Group A 60 100 100
100.degree. C. 44.7 3.17 DIS oven Group B 60 100 100 100.degree. C.
41.6 3.07 TFF sol'n Group B 60 100 100 100.degree. C. 44.0 3.12 DIS
sol'n Group D 30 90 60 60.degree. C. 129.7 2.56 DIS sol'n Group D
30 90 60 60.degree. C. 144.2 2.73 FIL sol'n Group E 15 100 RT
60.degree. C. 108.8 2.78 DIS sol'n Group E 15 100 RT 60.degree. C.
94.8 2.62 FIL sol'n
[0099] Silk aqueous coating composition for application to fabrics
are given in Tables P and Q below.
TABLE-US-00017 TABLE P Silk Solution Characteristics Molecular
Weight: 57 kDa Polydispersity: 1.6 % Silk 5.0% 3.0% 1.0% 0.5%
Process Parameters Extraction Boil Time: 30 minutes Boil
Temperature: 100.degree. C. Rinse Temperature: 60.degree. C.
Dissolution LiBr Temperature: 100 Oven Temperature: 100.degree. C.
Oven Time: 60 minutes
TABLE-US-00018 TABLE Q Silk Solution Characteristics Molecular
Weight: 25 kDa Polydispersity: 2.4 % Silk 5.0% 3.0% 1.0% 0.5%
Process Parameters Extraction Boil Time: 60 minutes Boil
Temperature: 100.degree. C. Rinse Temperature: 60.degree. C.
Dissolution LiBr Temperature: 100.degree. C. Oven Temperature:
100.degree. C. Oven Time: 60 minutes
[0100] Three (3) silk solutions were utilized in film making with
the following results:
[0101] Solution #1 is a silk concentration of 5.9%, average MW of
19.8 kDa and 2.2 PD (made with a 60 min boil extraction,
100.degree. C. LiBr dissolution for 1 hr).
[0102] Solution #2 is a silk concentration of 6.4% (made with a 30
min boil extraction, 60.degree. C. LiBr dissolution for 4 hrs).
[0103] Solution #3 is a silk concentration of 6.17% (made with a 30
min boil extraction, 100.degree. C. LiBr dissolution for 1
hour).
[0104] Films were made in accordance with Rockwood et al. (Nature
Protocols; Vol. 6; No. 10; published on-line Sep. 22, 2011;
doi:10.1038/nprot.2011.379). 4 mL of 1% or 2% (wt/vol) aqueous silk
solution was added into 100 mm Petri dish (Volume of silk can be
varied for thicker or thinner films and is not critical) and
allowed to dry overnight uncovered. The bottom of a vacuum
desiccator was filled with water. Dry films were placed in the
desiccator and vacuum applied, allowing the films to water anneal
for 4 hours prior to removal from the dish. Films cast from
solution #1 did not result in a structurally continuous film; the
film was cracked in several pieces. These pieces of film dissolved
in water in spite of the water annealing treatment.
[0105] Silk solutions of various molecular weights and/or
combinations of molecular weights can be optimized for gel
applications. The following provides an example of this process but
it not intended to be limiting in application or formulation. Three
(3) silk solutions were utilized in gel making with the following
results:
[0106] Solution #1 is a silk concentration of 5.9%, average MW of
19.8 kDa and 2.2 PD (made with a 60 min boil extraction,
100.degree. C. LiBr dissolution for 1 hr).
[0107] Solution #2 is a silk concentration of 6.4% (made with a 30
min boil extraction, 60.degree. C. LiBr dissolution for 4 hrs).
[0108] Solution #3 is a silk concentration of 6.17% (made with a 30
min boil extraction, 100.degree. C. LiBr dissolution for 1
hour).
[0109] "Egel" is an electrogelation process as described in
Rockwood of al. Briefly, 10 ml of aqueous silk solution is added to
a 50 ml conical tube and a pair of platinum wire electrodes
immersed into the silk solution. A 20 volt potential was applied to
the platinum electrodes for 5 minutes, the power supply turned off
and the gel collected. Solution #1 did not form an EGEL over the 5
minutes of applied electric current.
[0110] Solutions #2 and #3 were gelled in accordance with the
published horseradish peroxidase (HRP) protocol. Behavior seemed
typical of published solutions.
[0111] Materials and Methods: the following equipment and material
are used in determination of Silk Molecular weight: Agilent 1100
with chemstation software ver. 10.01; Refractive Index Detector
(RID); analytical balance; volumetric flasks (1000 mL, 10 mL and 5
mL); HPLC grade water; ACS grade sodium chloride; ACS grade sodium
phosphate dibasic heptahydrate; phosphoric acid; dextran MW
Standards-Nominal Molecular Weights of 5 kDa, 11.6 kDa, 23.8 kDa,
48.6 kDa, and 148 kDa; 50 mL PET or polypropylene disposable
centrifuge tubes; graduated pipettes; amber glass HPLC vials with
Teflon caps; Phenomenex PolySep GFC P-4000 column (size: 7.8 mm x
300 mm).
[0112] Procedural Steps: [0113] A) Preparation of 1 L Mobile Phase
(0.1 M Sodium Chloride solution in 0.0125 M Sodium phosphate
buffer)
[0114] Take a 250 mL clean and dry beaker, place it on the balance
and tare the weight. Add about 3.3509 g of sodium phosphate dibasic
heptahydrate to the beaker. Note down the exact weight of sodium
phosphate dibasic weighed. Dissolve the weighed sodium phosphate by
adding 100 mL of HPLC water into the beaker. Take care not to spill
any of the content of the beaker. Transfer the solution carefully
into a clean and dry 1000 mL volumetric flask. Rinse the beaker and
transfer the rinse into the volumetric flask. Repeat the rinse 4-5
times. In a separate clean and dry 250 mL beaker weigh exactly
about 5.8440 g of sodium chloride. Dissolve the weighed sodium
chloride in 50 mL of water and transfer the solution to the sodium
phosphate solution in the volumetric flask. Rinse the beaker and
transfer the rinse into the volumetric flask. Adjust the pH of the
solution to 7.0.+-.0.2 with phosphoric acid. Make up the volume in
volumetric flask with HPLC water to 1000 mL and shake it vigorously
to homogeneously mix the solution. Filter the solution through 0.45
.mu.m polyamide membrane filter. Transfer the solution to a clean
and dry solvent bottle and label the bottle. The volume of the
solution can be varied to the requirement by correspondingly
varying the amount of sodium phosphate dibasic heptahydrate and
sodium chloride. [0115] B) Preparation of Dextran Molecular Weight
Standard solutions
[0116] At least five different molecular weight standards are used
for each batch of samples that are run so that the expected value
of the sample to be tested is bracketed by the value of the
standard used. Label six 20 mL scintillation glass vials respective
to the molecular weight standards. Weigh accurately about 5 mg of
each of dextran molecular weight standards and record the weights.
Dissolve the dextran molecular weight standards in 5 mL of mobile
phase to make a 1 mg/mL standard solution. [0117] C) Preparation of
Sample solutions
[0118] When preparing sample solutions, if there are limitations on
how much sample is available, the preparations may be scaled as
long as the ratios are maintained. Depending on sample type and
silk protein content in sample weigh enough sample in a 50 mL
disposable centrifuge tube on an analytical balance to make a 1
mg/mL sample solution for analysis. Dissolve the sample in
equivalent volume of mobile phase make a 1 mg/mL solution. Tightly
cap the tubes and mix the samples (in solution). Leave the sample
solution for 30 minutes at room temperature. Gently mix the sample
solution again for 1 minute and centrifuge at 4000 RPM for 10
minutes. [0119] D) HPLC analysis of the samples
[0120] Transfer 1.0 mL of all the standards and sample solutions
into individual HPLC vials. Inject the molecular weight standards
(one injection each) and each sample in duplicate. Analyze all the
standards and sample solutions using the following HPLC
conditions:
TABLE-US-00019 Column Poly Sep GFC P-4000 (7.8 x 300 mm) Column
25.degree. C. Temperature Detector Refractive Index Detector
(Temperature @ 35.degree. C.) Injection Volume 25.0 .mu.L Mobile
Phase 0.1M Sodium Chloride solution in 0.0125M sodium phosphate
buffer Flow Rate 1.0 mL/min Run Time 20.0 min
[0121] E) Data analysis and calculations--Calculation of Average
Molecular Weight using Cirrus Software
[0122] Upload the chromatography data files of the standards and
the analytical samples into Cirrus SEC data collection and
molecular weight analysis software. Calculate the weight average
molecular weight (M.sub.w), number average molecular weight
(M.sub.n), peak average molecular weight (M.sub.p), and
polydispersity for each injection of the sample.
[0123] Spider Silk Fragments
[0124] Spider silks are natural polymers that consist of three
domains: a repetitive middle core domain that dominates the protein
chain, and non-repetitive N-terminal and C-terminal domains. The
large core domain is organized in a block copolymer-like
arrangement, in which two basic sequences, crystalline [poly(A) or
poly(GA)] and less crystalline (GGX or GPGXX) polypeptides
alternate. Dragline silk is the protein complex composed of major
ampullate dragline silk protein 1 (MaSp1) and major ampullate
dragline silk protein 2 (MaSp2). Both silks are approximately 3500
amino acid long. MaSp1 can be found in the fibre core and the
periphery, whereas MaSp2 forms clusters in certain core areas. The
large central domains of MaSp1 and MaSp2 are organized in block
copolymer-like arrangements, in which two basic sequences,
crystalline [poly(A) or poly(GA)] and less crystalline (GGX or
GPGXX) polypeptides alternate in core domain. Specific secondary
structures have been assigned to poly(A)/(GA), GGX and GPGXX motifs
including (.beta.-sheet, .alpha.-helix and .beta.-spiral
respectively. The primary sequence, composition and secondary
structural elements of the repetitive core domain are responsible
for mechanical properties of spider silks; whereas, non-repetitive
N- and C-terminal domains are essential for the storage of liquid
silk dope in a lumen and fibre formation in a spinning duct.
[0125] The main difference between MaSp1 and MaSp2 is the presence
of proline (P) residues accounting for 15% of the total amino acid
content in MaSp2, whereas MaSp1 is proline-free. By calculating the
number of proline residues in N. clavipes dragline silk, it is
possible to estimate the presence of the two proteins in fibres;
81% MaSp1 and 19% MaSp2. Different spiders have different ratios of
MaSp1 and MaSp2. For example, a dragline silk fibre from the orb
weaver Argiope aurantia contains 41% MaSp1 and 59% MaSp2. Such
changes in the ratios of major ampullate silks can dictate the
performance of the silk fibre.
[0126] At least seven different types of silk proteins are known
for one orb-weaver species of spider. Silks differ in primary
sequence, physical properties and functions. For example, dragline
silks used to build frames, radii and lifelines are known for
outstanding mechanical properties including strength, toughness and
elasticity. On an equal weight basis, spider silk has a higher
toughness than steel and Kevlar. Flageliform silk found in capture
spirals has extensibility of up to 500%. Minor ampullate silk,
which is found in auxiliary spirals of the orb-web and in prey
wrapping, possesses high toughness and strength almost similar to
major ampullate silks, but does not supercontract in water.
[0127] Spider silks are known for their high tensile strength and
toughness. The recombinant silk proteins also confer advantageous
properties to cosmetic or dermatological compositions, in
particular to be able to improve the hydrating or softening action,
good film forming property and low surface density. Diverse and
unique biomechanical properties together with biocompatibility and
a slow rate of degradation make spider silks excellent candidates
as biomaterials for tissue engineering, guided tissue repair and
drug delivery, for cosmetic products (e.g. nail and hair
strengthener, skin care products), and industrial materials (e.g.
nanowires, nanofibers, surface coatings).
[0128] In an embodiment, a silk protein may include a polypeptide
derived from natural spider silk proteins. The polypeptide is not
limited particularly as long as it is derived from natural spider
silk proteins, and examples of the polypeptide include natural
spider silk proteins and recombinant spider silk proteins such as
variants, analogs, derivatives or the like of the natural spider
silk proteins. In terms of excellent tenacity, the polypeptide may
be derived from major dragline silk proteins produced in major
ampullate glands of spiders. Examples of the major dragline silk
proteins include major ampullate spidroin MaSp1 and MaSp2 from
Nephila clavipes, and ADF3 and ADF4 from Araneus diadematus, etc.
Examples of the polypeptide derived from major dragline silk
proteins include variants, analogs, derivatives or the like of the
major dragline silk proteins. Further, the polypeptide may be
derived from flagelliform silk proteins produced in flagelliform
glands of spiders. Examples of the flagelliform silk proteins
include flagelliform silk proteins derived from Nephila clavipes,
etc.
[0129] Examples of the polypeptide derived from major dragline silk
proteins include a polypeptide containing two or more units of an
amino acid sequence represented by the formula 1: REP1-REP2 (1),
preferably a polypeptide containing five or more units thereof, and
more preferably a polypeptide containing ten or more units thereof.
Alternatively, the polypeptide derived from major dragline silk
proteins may be a polypeptide that contains units of the amino acid
sequence represented by the formula 1: REP1-REP2 (1) and that has,
at a C-terminal, an amino acid sequence represented by any of SEQ
ID NOS: 1 to 3 of U.S. Pat. No. 9,051,453 or an amino acid sequence
having a homology of 90% or more with the amino acid sequence
represented by any of SEQ ID NOS: 1 to 3 of U.S. Pat. No.
9,051,453. In the polypeptide derived from major dragline silk
proteins, units of the amino acid sequence represented by the
formula 1: REP1-REP2 (1) may be the same or may be different from
each other. In the case of producing a recombinant protein using a
microbe such as Escherichia coli as a host, the molecular weight of
the polypeptide derived from major dragline silk proteins is 500
kDa or less, or 300 kDa or less, or 200 kDa or less, in terms of
productivity.
[0130] In the formula (1), the REP1 indicates polyalanine. In the
REP1, the number of alanine residues arranged in succession is
preferably 2 or more, more preferably 3 or more, further preferably
4 or more, and particularly preferably 5 or more. Further, in the
REP1, the number of alanine residues arranged in succession is
preferably 20 or less, more preferably 16 or less, further
preferably 12 or less, and particularly preferably 10 or less. In
the formula (1), the REP2 is an amino acid sequence composed of 10
to 200 amino acid residues. The total number of glycine, serine,
glutamine and alanine residues contained in the amino acid sequence
is 40% or more, preferably 60% or more, and more preferably 70% or
more with respect to the total number of amino acid residues
contained therein.
[0131] In the major dragline silk, the REP1 corresponds to a
crystal region in a fiber where a crystal .beta. sheet is formed,
and the REP2 corresponds to an amorphous region in a fiber where
most of the parts lack regular configurations and that has more
flexibility. Further, the [REP1-REP2] corresponds to a repetitious
region (repetitive sequence) composed of the crystal region and the
amorphous region, which is a characteristic sequence of dragline
silk proteins.
[0132] Recombinant Silk Fragments
[0133] In some embodiments, the recombinant silk protein refers to
recombinant spider silk polypeptides, recombinant insect silk
polypeptides, or recombinant mussel silk polypeptides. In some
embodiments, the recombinant silk protein fragment disclosed herein
include recombinant spider silk polypeptides of Araneidae or
Araneoids, or recombinant insect silk polypeptides of Bombyx mori.
In some embodiments, the recombinant silk protein fragment
disclosed herein include recombinant spider silk polypeptides of
Araneidae or Araneoids. In some embodiments, the recombinant silk
protein fragment disclosed herein include block copolymer having
repetitive units derived from natural spider silk polypeptides of
Araneidae or Araneoids. In some embodiments, the recombinant silk
protein fragment disclosed herein include block copolymer having
synthetic repetitive units derived from spider silk polypeptides of
Araneidae or Araneoids and non-repetitive units derived from
natural repetitive units of spider silk polypeptides of Araneidae
or Araneoids.
[0134] Recent advances in genetic engineering have provided a route
to produce various types of recombinant silk proteins. Recombinant
DNA technology has been used to provide a more practical source of
silk proteins. As used herein "recombinant silk protein" refers to
synthetic proteins produced heterologously in prokaryotic or
eukaryotic expression systems using genetic engineering
methods.
[0135] Various methods for synthesizing recombinant silk peptides
are known and have been described by Ausubel et al., Current
Protocols in Molecular Biology .sctn. 8 (John Wiley & Sons
1987, (1990)), incorporated herein by reference. A gram-negative,
rod-shaped bacterium E. coli is a well-established host for
industrial scale production of proteins. Therefore, the majority of
recombinant silks have been produced in E. coli. E. coli which is
easy to manipulate, has a short generation time, is relatively low
cost and can be scaled up for larger amounts protein
production.
[0136] The recombinant silk proteins can be produced by transformed
prokaryotic or eukaryotic systems containing the cDNA coding for a
silk protein, for a fragment of this protein or for an analog of
such a protein. The recombinant DNA approach enables the production
of recombinant silks with programmed sequences, secondary
structures, architectures and precise molecular weight. There are
four main steps in the process: (i) design and assembly of
synthetic silk-like genes into genetic `cassettes`, (ii) insertion
of this segment into a DNA recombinant vector, (iii) transformation
of this recombinant DNA molecule into a host cell and (iv)
expression and purification of the selected clones.
[0137] The term "recombinant vectors", as used herein, includes any
vectors known to the skilled person including plasmid vectors,
cosmid vectors, phage vectors such as lambda phage, viral vectors
such as adenoviral or baculoviral vectors, or artificial chromosome
vectors such as bacterial artificial chromosomes (BAC), yeast
artificial chromosomes (YAC), or P1 artificial chromosomes (PAC).
Said vectors include expression as well as cloning vectors.
Expression vectors comprise plasmids as well as viral vectors and
generally contain a desired coding sequence and appropriate DNA
sequences necessary for the expression of the operably linked
coding sequence in a particular host organism (e.g., bacteria,
yeast, or plant) or in in vitro expression systems. Cloning vectors
are generally used to engineer and amplify a certain desired DNA
fragment and may lack functional sequences needed for expression of
the desired DNA fragments.
[0138] The prokaryotic systems include Gram-negative bacteria or
Gram-positive bacteria. The prokaryotic expression vectors can
include an origin of replication which can be recognized by the
host organism, a homologous or heterologous promoter which is
functional in the said host, the DNA sequence coding for the spider
silk protein, for a fragment of this protein or for an analogous
protein. Nonlimiting examples of prokaryotic expression organisms
are Escherichia coli, Bacillus subtilis, Bacillus megaterium,
Corynebacterium glutamicum, Anabaena, Caulobacter, Gluconobacter,
Rhodobacter, Pseudomonas, Para coccus, Bacillus (e.g. Bacillus
subtilis) Brevibacterium, Corynebacterium, Rhizobium
(Sinorhizobium), Flavobacterium, Klebsiella, Enterobacter,
Lactobacillus, Lactococcus, Methylobacterium, Propionibacterium,
Staphylococcus or Streptomyces cells.
[0139] The eukaryotic systems include yeasts and insect, mammalian
or plant cells. In this case, the expression vectors can include a
yeast plasmid origin of replication or an autonomous replication
sequence, a promoter, a DNA sequence coding for a spider silk
protein, for a fragment or for an analogous protein, a
polyadenylation sequence, a transcription termination site and,
lastly, a selection gene. Nonlimiting examples of eukaryotic
expression organisms include yeasts, such as Saccharomyces
cerevisiae, Pichia pastoris, basidiosporogenous, ascosporogenous,
filamentous fungi, such as Aspergillus niger, Aspergillus oryzae,
Aspergillus nidulans, Trichoderma reesei, Acremonium chrysogenum,
Candida, Hansenula, Kluyveromyces, Saccharomyces (e.g.
Saccharomyces cerevisiae), Schizosaccharomyces, Pichia (e.g. Pichia
pastoris) or Yarrowia cells etc., mammalian cells, such as HeLa
cells, COS cells, CHO cells etc., insect cells, such as Sf9 cells,
MEL cells, etc., "insect host cells" such as Spodoptera frugiperda
or Trichoplusia ni cells. SF9 cells, SF-21 cells or High-Five
cells, wherein SF-9 and SF-21 are ovarian cells from Spodoptera
frupperda, and High-Five cells are egg cells from Trichoplusia ni.,
"plant host cells", such as tobacco, potato or pea cells.
[0140] A variety of heterologous host systems have been explored to
produce different types of recombinant silks. Recombinant partial
spidroins as well as engineered silks have been cloned and
expressed in bacteria (Escherichia coli), yeast (Pichia pastoris),
insects (silkworm larvae), plants (tobacco, soybean, potato,
Arabidopsis), mammalian cell lines (BHT/hamster) and transgenic
animals (mice, goats). Most of the silk proteins are produced with
an N- or C-terminal His-tags to make purification simple and
produce enough amounts of the protein.
[0141] In some embodiments, the host suitable for expressing the
recombinant spider silk protein using heterogeneous system may
include transgenic animals and plants. In some embodiments, the
host suitable for expressing the recombinant spider silk protein
using heterogeneous system comprises bacteria, yeasts, mammalian
cell lines. In some embodiments, the host suitable for expressing
the recombinant spider silk protein using heterogeneous system
comprises E. coli. In some embodiments, the host suitable for
expressing the recombinant spider silk protein using heterogeneous
system comprises transgenic B. mori silkworm generated using genome
editing technologies (e.g. CRISPR).
[0142] The recombinant silk protein in this disclosure comprises
synthetic proteins which are based on repeat units of natural silk
proteins. Besides the synthetic repetitive silk protein sequences,
these can additionally comprise one or more natural nonrepetitive
silk protein sequences.
[0143] In some embodiments, "recombinant silk protein" refers to
recombinant silkworm silk protein or fragments thereof. The
recombinant production of silk fibroin and silk sericin has been
reported. A variety of hosts are used for the production including
E. coli, Sacchromyces cerevisiae, Pseudomonas sp., Rhodopseudomonas
sp., Bacillus sp., and Strepomyces. See EP 0230702, which is
incorporate by reference herein by its entirety.
[0144] Provided herein also include design and biological-synthesis
of silk fibroin protein-like multiblock polymer comprising GAGAGX
hexapeptide (X is A, Y, V or S) derived from the repetitive domain
of B. mori silk heavy chain (H chain)
[0145] In some embodiments, this disclosure provides silk
protein-like multiblock polymers derived from the repetitive domain
of B. mori silk heavy chain (H chain) comprising the GAGAGS
hexapeptide repeating units. The GAGAGS hexapeptide is the core
unit of H-chain and plays an important role in the formation of
crystalline domains. The silk protein-like multiblock polymers
containing the GAGAGS hexapeptide repeating units spontaneously
aggregate into .beta.-sheet structures, similar to natural silk
fibroin protein, where in the silk protein-like multiblock polymers
having any weight average molecular weight described herein.
[0146] In some embodiments, this disclosure provides silk-peptide
like multiblock copolymers composed of the GAGAGS hexapeptide
repetitive fragment derived from H chain of B. mori silk heavy
chain and mammalian elastin VPGVG motif produced by E. coli. In
some embodiments, this disclosure provides fusion silk fibroin
proteins composed of the GAGAGS hexapeptide repetitive fragment
derived from H chain of B. mori silk heavy chain and GVGVP produced
by E. coli, where in the silk protein-like multiblock polymers
having any weight average molecular weight described herein.
[0147] In some embodiments, this disclosure provides B. mori
silkworm recombinant proteins composed of the (GAGAGS).sub.16
repetitive fragment. In some embodiments, this disclosure provides
recombinant proteins composed of the (GAGAGS).sub.16 repetitive
fragment and the non-repetitive (GAGAGS).sub.16-F--COOH,
(GAGAGS).sub.16-F--F--COOH, (GAGAGS).sub.16-F--F--F--COOH,
(GAGAGS).sub.16-F--F--F--F--COOH,
(GAGAGS).sub.16-F--F--F--F--F--F--F--F--COOH,
(GAGAGS).sub.16-F--F--F--F--F--F--F--F--F--F--F--F--COOH produced
by E. coli, where F has the following amino acid sequence
SGFGPVANGGSGEASSESDFGSSGFGPVANASSGEASSESDFAG, and where in the silk
protein-like multiblock polymers having any weight average
molecular weight described herein.
[0148] In some embodiments, "recombinant silk protein" refers to
recombinant spider silk protein or fragments thereof. The
productions of recombinant spider silk proteins based on a partial
cDNA clone have been reported. The recombinant spider silk proteins
produced as such comprise a portion of the repetitive sequence
derived from a dragline spider silk protein, Spidroin 1, from the
spider Nephila clavipes. see Xu et al. (Proc. Natl. Acad. Sci.
U.S.A., 87:7120-7124 (1990). cDNA clone encoding a portion of the
repeating sequence of a second fibroin protein, Spidroin 2, from
dragline silk of Nephila clavipes and the recombinant synthesis
thereof is described in J. Biol. Chem., 1992, volume 267, pp.
19320-19324. The recombinant synthesis of spider silk proteins
including protein fragments and variants of Nephila clavipes from
transformed E. coli is described in U.S. Pat. Nos. 5,728,810 and
5,989,894. cDNA clones encoding minor ampullate spider silk
proteins and the expression thereof is described in U.S. Pat. Nos.
5,733,771 and 5,756,677. cDNA clone encoding the flagelliform silk
protein from an orb-web spinning spider is described in U.S. Pat.
No. 5,994,099. U.S. Pat. No. 6,268,169 describes the recombinant
synthesis of spider silk like proteins derived from the repeating
peptide sequence found in the natural spider dragline of Nephila
clavipes by E. coli, Bacillus subtilis, and Pichia pastoris
recombinant expression systems. WO 03/020916 describes the cDNA
clone encoding and recombinant production of spider spider silk
proteins having repeative sequences derived from the major
ampullate glands of Nephila madagascariensis, Nephila senegalensis,
Tetragnatha kauaiensis, Tetragnatha versicolor, Argiope aurantia,
Argiope trifasciata, Gasteracantha mammosa, and Latrodectus
geometricus, the flagelliform glands of Argiope trifasciata, the
ampullate glands of Dolomedes tenebrosus, two sets of silk glands
from Plectreurys tristis, and the silk glands of the mygalomorph
Euagrus chisoseus. Each of the above reference is incorporated
herein by reference in its entirety.
[0149] In some embodiments, the recombinant spider silk protein is
a hybrid protein of a spider silk protein and an insect silk
protein, a spider silk protein and collagen, a spider silk protein
and resilin, or a spider silk protein and keratin. The spider silk
repetitive unit comprises or consists of an amino acid sequence of
a region that comprises or consists of at least one peptide motif
that repetitively occurs within a naturally occurring major
ampullate gland polypeptide, such as a dragline spider silk
polypeptide, a minor ampullate gland polypeptide, a flagelliform
polypeptide, an aggregate spider silk polypeptide, an aciniform
spider silk polypeptide or a pyriform spider silk polypeptide.
[0150] In some embodiments, the recombinant spider silk protein in
this disclosure comprises synthetic spider silk proteins derived
from repetitive units of natural spider silk proteins, consensus
sequence, and optionally one or more natural non-repetitive spider
silk protein sequences. The repeated units of natural spider silk
polypeptide may include dragline spider silk polypeptides or
flagelliform spider silk polypeptides of Araneidae or
Araneoids.
[0151] As used herein, the spider silk "repetitive unit" comprises
or consists of at least one peptide motif that repetitively occurs
within a naturally occurring major ampullate gland polypeptide,
such as a dragline spider silk polypeptide, a minor ampullate gland
polypeptide, a flagelliform polypeptide, an aggregate spider silk
polypeptide, an aciniform spider silk polypeptide or a pyriform
spider silk polypeptide. A "repetitive unit" refers to a region
which corresponds in amino acid sequence to a region that comprises
or consists of at least one peptide motif (e.g. AAAAAA) or GPGQQ)
that repetitively occurs within a naturally occurring silk
polypeptide (e.g. MaSpI, ADF-3, ADF-4, or Flag) (i.e. identical
amino acid sequence) or to an amino acid sequence substantially
similar thereto (i.e. variational amino acid sequence). A
"repetitive unit" having an amino acid sequence which is
"substantially similar" to a corresponding amino acid sequence
within a naturally occurring silk polypeptide (i.e. wild-type
repetitive unit) is also similar with respect to its properties,
e.g. a silk protein comprising the "substantially similar
repetitive unit" is still insoluble and retains its insolubility. A
"repetitive unit" having an amino acid sequence which is
"identical" to the amino acid sequence of a naturally occurring
silk polypeptide, for example, can be a portion of a silk
polypeptide corresponding to one or more peptide motifs of MaSpI,
MaSpII, ADF-3 and/or ADF-4. A "repetitive unit" having an amino
acid sequence which is "substantially similar" to the amino acid
sequence of a naturally occurring silk polypeptide, for example,
can be a portion of a silk polypeptide corresponding to one or more
peptide motifs of MaSpI, MaSpII, ADF-3 and/or ADF-4, but having one
or more amino acid substitution at specific amino acid
positions.
[0152] As used herein, the term "consensus peptide sequence" refers
to an amino acid sequence which contains amino acids which
frequently occur in a certain position (e.g. "G") and wherein,
other amino acids which are not further determined are replaced by
the place holder "X". In some embodiments, the consensus sequence
is at least one of (i) GPGXX, wherein X is an amino acid selected
from A, S, G, Y, P and Q; (ii) GGX, wherein X is an amino acid
selected from Y, P, R, S, A, T, N and Q, preferably Y, P and Q;
(iii) A.sub.x, wherein x is an integer from 5 to 10.
[0153] The consensus peptide sequences GPGXX and GGX, i.e. glycine
rich motifs, provide flexibility to the silk polypeptide and thus,
to the thread formed from the silk protein containing said motifs.
In detail, the iterated GPGXX motif forms turn spiral structures,
which imparts elasticity to the silk polypeptide. Major ampullate
and flagelliform silks both have a GPGXX motif. The iterated GGX
motif is associated with a helical structure having three amino
acids per turn and is found in most spider silks. The GGX motif may
provide additional elastic properties to the silk. The iterated
polyalanine Ax (peptide) motif forms a crystalline .beta.-sheet
structure that provides strength to the silk polypeptide, as
described for example in WO 03/057727.
[0154] In some embodiments, the recombinant spider silk protein in
this disclosure comprises two identical repetitive units each
comprising at least one, preferably one, amino acid sequence
selected from the group consisting of: GGRPSDTYG and GGRPSSSYG
derived from Resilin. Resilin is an elastomeric protein found in
most arthropods that provides low stiffness and high strength.
[0155] As used herein, "non-repetitive units" refers to an amino
acid sequence which is "substantially similar" to a corresponding
non-repetitive (carboxy terminal) amino acid sequence within a
naturally occurring dragline polypeptide (i.e. wild-type
non-repetitive (carboxy terminal) unit), preferably within ADF-3
(SEQ ID NO:1), ADF-4 (SEQ ID NO:2), NR3 (SEQ ID NO:41), NR4 (SEQ ID
NO:42), ADF-4 of the spider Araneus diadematus as described in U.S.
Pat. No. 8,367,803, C16 peptide (spider silk protein eADF4,
molecular weight of 47.7 kDa, AMSilk) comprising the 16 repeats of
the sequence GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP, an amino acid
sequence adapted from the natural sequence of ADF4 from A.
diadematus. Non-repetitive ADF-4 and variants thereof display
efficient assembly behavior.
[0156] Among the synthetic spider silk proteins, the recombinant
silk protein in this disclosure comprises in some embodiments the
C16-protein having the polypeptide sequence SEQ ID NO: 1 as
described in U.S. Pat. No. 8,288,512. Besides the polypeptide
sequence shown in SEQ ID NO:1, particularly functional equivalents,
functional derivatives and salts of this sequence are also
included.
[0157] As used herein, "functional equivalents" refers to mutant
which, in at least one sequence position of the abovementioned
amino acid sequences, have an amino acid other than that
specifically mentioned.
[0158] In some embodiments, the recombinant spider silk protein in
this disclosure comprises, in an effective amount, at least one
natural or recombinant silk protein including spider silk protein,
corresponding to Spidroin major 1 described by Xu et al., PNAS,
USA, 87, 7120, (1990), Spidroin major 2 described by Hinman and
Lewis, J. Biol. Chem., 267, 19320, (1922), recombinant spider silk
protein as described in U.S. Patent Application No. 2016/0222174
and U.S. Pat. Nos. 9,051,453, 9,617,315, 9,689,089, 8,173,772,
8,642,734, 8,367,803 8,097,583, 8,030,024, 7,754,851, 7,148,039,
7,060,260, or alternatively the minor Spidroins described in patent
application WO 95/25165. Each of the above-cited references is
incorporated herein by reference in its entirety. Additional
recombinant spider silk proteins suitable for the recombinant RSPF
of this disclosure include ADF3 and ADF4 from the "Major Ampullate"
gland of Araneus diadematus.
[0159] Recombinant silk is also described in other patents and
patent applications, incorporated by reference herein: US
2004590196, U.S. Pat. No. 7,754,851, US 2007654470, U.S. Pat. No.
7,951,908, US 2010785960, U.S. Pat. No. 8,034,897, US 20090263430,
US 2008226854, US 20090123967, US 2005712095, US 2007991037, US
20090162896, US 200885266, U.S. Pat. No. 8,372,436, US 2007989907,
US 2009267596, US 2010319542, US 2009265344, US 2012684607, US
2004583227, U.S. Pat. No. 8,030,024, US 2006643569, U.S. Pat. No.
7,868,146, US 2007991916, U.S. Pat. No. 8,097,583, US 2006643200,
U.S. Pat. Nos. 8,729,238, 8,877,903, US 20190062557, US
20160280960, US 20110201783, US 2008991916, US 2011986662, US
2012697729, US 20150328363, U.S. Pat. No. 9,034,816, US
20130172478, U.S. Pat. No. 9,217,017, US 20170202995, U.S. Pat. No.
8,721,991, US 2008227498, U.S. Pat. Nos. 9,233,067, 8,288,512, US
2008161364, U.S. Pat. No. 7,148,039, US 1999247806, US 2001861597,
US 2004887100, U.S. Pat. Nos. 9,481,719, 8,765,688, US 200880705,
US 2010809102, U.S. Pat. No. 8,367,803, US 2010664902, U.S. Pat.
No. 7,569,660, US 1999138833, US 2000591632, US 20120065126, US
20100278882, US 2008161352, US 20100015070, US 2009513709, US
20090194317, US 2004559286, US 200589551, US 2008187824, US
20050266242, US 20050227322, and US 20044418.
[0160] Recombinant silk is also described in other patents and
patent applications, incorporated by reference herein: US
20190062557, US 20150284565, US 20130225476, US 20130172478, US
20130136779, US 20130109762, US 20120252294, US 20110230911, US
20110201783, US 20100298877, U.S. Pat. Nos. 10,478,520, 10,253,213,
10,072,152, 9,233,067, 9,217,017, 9,034,816, 8,877,903, 8,729,238,
8,721,991, 8,097,583, 8,034,897, 8,030,024, 7,951,908, 7,868,146,
and 7,754,851.
[0161] In some embodiments, the recombinant spider silk protein in
this disclosure comprises or consists of 2 to 80 repetitive units,
each independently selected from GPGXX, GGX and A.sub.x as defined
herein.
[0162] In some embodiments, the recombinant spider silk protein in
this disclosure comprises or consists of repetitive units each
independently selected from selected from the group consisting of
GPGAS, GPGSG, GPGGY, GPGGP, GPGGA, GPGQQ, GPGGG, GPGQG, GPGGS, GGY,
GGP, GGA, GGR, GGS, GGT, GGN, GGQ, AAAAA, AAAAAA, AAAAAAA,
AAAAAAAA, AAAAAAAAA, AAAAAAAAAA, GGRPSDTYG and GGRPSSSYG, (i)
GPYGPGASAAAAAAGGYGPGSGQQ, (ii) GS
SAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP, (iii) GPGQQGPGQQGPGQQGPGQQ: (iv)
GPGGAGGPYGPGGAGGPYGPGGAGGPY, (v) GGTTIIEDLDITIDGADGPITISEELTI, (vi)
PGS SAAAAAAAASGPGQGQGQGQGQGGRPSDTYG, (vii)
SAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG, (viii) GGAGGAGGAGGSGGAGGS
(SEQ ID NO: 27), (ix) GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY, (x)
GPYGPGASAAAAAAGGYGPGCGQQ, (xi) GPYGPGASAAAAAAGGYGPGKGQQ, (xii) GS
SAAAAAAAASGPGGYGPENQGPCGPGGYGPGGP, (xiii)
GSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP, (xiv) GS
SAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP, or variants thereof as described
in U.S. Pat. No. 8,877,903, for example, a synthetic spider peptide
having sequential order of GPGAS, GGY, GPGSG in the peptide chain,
or sequential order of AAAAAAAA, GPGGY, GPGGP in the peptide chain,
sequential order of AAAAAAAA, GPGQG, GGR in the peptide chain.
[0163] In some embodiments, this disclosure provides silk
protein-like multiblock peptides that imitate the repeating units
of amino acids derived from natural spider silk proteins such as
Spidroin major 1 domain, Spidroin major 2 domain or Spidroin minor
1 domain and the profile of variation between the repeating units
without modifying their three-dimensional conformation, wherein
these silk protein-like multiblock peptides comprise a repeating
unit of amino acids corresponding to one of the sequences (I),
(II), (III) and/or (IV) below.
[0164] [(XGG).sub.w(XGA)(GXG).sub.x(AGA).sub.y(G).sub.zAG].sub.p
Formula (I) in which: X corresponds to tyrosine or to glutamine, w
is an integer equal to 2 or 3, x is an integer from 1 to 3, y is an
integer from 5 to 7, z is an integer equal to 1 or 2, and p is an
integer and having any weight average molecular weight described
herein, and/or
[0165] [(GPG.sub.2YGPGQ.sub.2).sub.a(X').sub.2S(A).sub.b].sub.p
Formula (II) in which: X' corresponds to the amino acid sequence
GPS or GPG, a is equal to 2 or 3, b is an integer from 7 to 10, and
p is an integer and having any weight average molecular weight
described herein, and/or
[0166]
[(GR)(GA).sub.l(A).sub.m(GGX).sub.n(GA).sub.l(A).sub.m].sub.p
Formula (III) and/or [(GGX).sub.n(GA).sub.m(A).sub.l].sub.p Formula
(IV) in which: X'' corresponds to tyrosine, glutamine or alanine, 1
is an integer from 1 to 6, m is an integer from 0 to 4, n is an
integer from 1 to 4, and p is an integer.
[0167] In some embodiments, the recombinant spider silk protein or
an analog of a spider silk protein comprising an amino acid
repeating unit of sequence (V):
[0168] [(Xaa Gly Gly).sub.w(Xaa Gly Ala)(Gly Xaa Gly).sub.x(Ala Gly
Ala).sub.y(Gly).sub.zAla Gly].sub.p Formula (V), wherein Xaa is
tyrosine or glutamine, w is an integer equal to 2 or 3, x is an
integer from 1 to 3, y is an integer from 5 to 7, z is an integer
equal to 1 or 2, and p is an integer.
[0169] In some embodiments, the recombinant spider silk protein in
this disclosure is selected from the group consisting of ADF-3 or
variants thereof, ADF-4 or variants thereof, MaSpI (SEQ ID NO: 43)
or variants thereof, MaSpII (SEQ ID NO: 44) or variants thereof as
described in U.S. Pat. No. 8,367,803.
[0170] In some embodiments, this disclosure provides water soluble
recombinant spider silk proteins produced in mammalian cells. The
solubility of the spider silk proteins produced in mammalian cells
was attributed to the presence of the COOH-terminus in these
proteins, which makes them more hydrophilic. These COOH-terminal
amino acids are absent in spider silk proteins expressed in
microbial hosts.
[0171] In some embodiments, the recombinant spider silk protein in
this disclosure comprises water soluble recombinant spider silk
protein C16 modified with an amino or carboxyl terminal selected
from the amino acid sequences consisting of: GCGGGGGG, GKGGGGGG,
GCGGSGGGGSGGGG, GKGGGGGGSGGGG, and GCGGGGGGSGGGG. In some
embodiments, the recombinant spider silk protein in this disclosure
comprises C.sub.16NR4, C.sub.32NR4, C16, C32, NR4C.sub.16NR4,
NR4C.sub.32NR4, NR3C.sub.16NR3, or NR3C.sub.32NR3 such that the
molecular weight of the protein ranges as described herein.
[0172] In some embodiments, the recombinant spider silk protein in
this disclosure comprises recombinant spider silk protein having a
synthetic repetitive peptide segments and an amino acid sequence
adapted from the natural sequence of ADF4 from A. diadematus as
described in U.S. Pat. No. 8,877,903. In some embodiments, the RSPF
in this disclosure comprises the recombinant spider silk proteins
having repeating peptide units derived from natural spider silk
proteins such as Spidroin major 1 domain, Spidroin major 2 domain
or Spidroin minor 1 domain, wherein the repeating peptide sequence
is GS SAAAAAAAASGPGQGQGQGQGQGGRPSDTYG or
SAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG, as described in U.S. Pat.
No. 8,367,803.
[0173] In some embodiments, this disclosure provides recombinant
spider proteins composed of the GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY
repetitive fragment and having a molecular weight as described
herein.
[0174] As used herein, the term "recombinant silk" refers to
recombinant spider and/or silkworm silk protein or fragments
thereof. In an embodiment, the spider silk protein is selected from
the group consisting of swathing silk (Achniform gland silk), egg
sac silk (Cylindriform gland silk), egg case silk (Tubuliform
silk), non-sticky dragline silk (Ampullate gland silk), attaching
thread silk (Pyriform gland silk), sticky silk core fibers
(Flagelliform gland silk), and sticky silk outer fibers (Aggregate
gland silk). For example, recombinant spider silk protein, as
described herein, includes the proteins described in U.S. Patent
Application No. 2016/0222174 and U.S. Pat. Nos. 9,051,453,
9,617,315, 9,689,089, 8,173,772, and 8,642,734.
[0175] Some organisms make multiple silk fibers with unique
sequences, structural elements, and mechanical properties. For
example, orb weaving spiders have six unique types of glands that
produce different silk polypeptide sequences that are polymerized
into fibers tailored to fit an environmental or lifecycle niche.
The fibers are named for the gland they originate from and the
polypeptides are labeled with the gland abbreviation (e.g. "Ma")
and "Sp" for spidroin (short for spider fibroin). In orb weavers,
these types include Major Ampullate (MaSp, also called dragline),
Minor Ampullate (MiSp), Flagelliform (Flag), Aciniform (AcSp),
Tubuliform (TuSp), and Pyriform (PySp). This combination of
polypeptide sequences across fiber types, domains, and variation
amongst different genus and species of organisms leads to a vast
array of potential properties that can be harnessed by commercial
production of the recombinant fibers. To date, the vast majority of
the work with recombinant silks has focused on the Major Ampullate
Spidroins (MaSp).
[0176] Aciniform (AcSp) silks tend to have high toughness, a result
of moderately high strength coupled with moderately high
extensibility. AcSp silks are characterized by large block
("ensemble repeat") sizes that often incorporate motifs of poly
serine and GPX. Tubuliform (TuSp or Cylindrical) silks tend to have
large diameters, with modest strength and high extensibility. TuSp
silks are characterized by their poly serine and poly threonine
content, and short tracts of poly alanine. Major Ampullate (MaSp)
silks tend to have high strength and modest extensibility. MaSp
silks can be one of two subtypes: MaSp1 and MaSp2. MaSpl silks are
generally less extensible than MaSp2 silks, and are characterized
by poly alanine, GX, and GGX motifs. MaSp2 silks are characterized
by poly alanine, GGX, and GPX motifs. Minor Ampullate (MiSp) silks
tend to have modest strength and modest extensibility. MiSp silks
are characterized by GGX, GA, and poly A motifs, and often contain
spacer elements of approximately 100 amino acids. Flagelliform
(Flag) silks tend to have very high extensibility and modest
strength. Flag silks are usually characterized by GPG, GGX, and
short spacer motifs.
[0177] Silk polypeptides are characteristically composed of a
repeat domain (REP) flanked by non-repetitive regions (e.g.,
C-terminal and N-terminal domains). In an embodiment, both the
C-terminal and N-terminal domains are between 75-350 amino acids in
length. The repeat domain exhibits a hierarchical architecture. The
repeat domain comprises a series of blocks (also called repeat
units). The blocks are repeated, sometimes perfectly and sometimes
imperfectly (making up a quasi-repeat domain), throughout the silk
repeat domain. The length and composition of blocks varies among
different silk types and across different species. Table 1 of U.S.
Published Application No. 2016/0222174, the entirety of which is
incorporated herein, lists examples of block sequences from
selected species and silk types, with further examples presented in
Rising, A. et al., Spider silk proteins: recent advances in
recombinant production, structure-function relationships and
biomedical applications, Cell Mol. Life Sci., 68:2, pg 169-184
(2011); and Gatesy, J. et al., Extreme diversity, conservation, and
convergence of spider silk fibroin sequences, Science, 291:5513,
pg. 2603-2605 (2001). In some cases, blocks may be arranged in a
regular pattern, forming larger macro-repeats that appear multiple
times (usually 2-8) in the repeat domain of the silk sequence.
Repeated blocks inside a repeat domain or macro-repeat, and
repeated macro-repeats within the repeat domain, may be separated
by spacing elements.
[0178] The construction of certain spider silk block copolymer
polypeptides from the blocks and/or macro-repeat domains, according
to certain embodiments of the disclosure, is illustrated in U.S.
Published Patent Application No. 2016/0222174.
[0179] The recombinant block copolymer polypeptides based on spider
silk sequences produced by gene expression in a recombinant
prokaryotic or eukaryotic system can be purified according to
methods known in the art. In a preferred embodiment, a commercially
available expression/secretion system can be used, whereby the
recombinant polypeptide is expressed and thereafter secreted from
the host cell, to be easily purified from the surrounding medium.
If expression/secretion vectors are not used, an alternative
approach involves purifying the recombinant block copolymer
polypeptide from cell lysates (remains of cells following
disruption of cellular integrity) derived from prokaryotic or
eukaryotic cells in which a polypeptide was expressed. Methods for
generation of such cell lysates are known to those of skill in the
art. In some embodiments, recombinant block copolymer polypeptides
are isolated from cell culture supernatant.
[0180] Recombinant block copolymer polypeptide may be purified by
affinity separation, such as by immunological interaction with
antibodies that bind specifically to the recombinant polypeptide or
nickel columns for isolation of recombinant polypeptides tagged
with 6-8 histidine residues at their N-terminus or C-terminus
Alternative tags may comprise the FLAG epitope or the hemagglutinin
epitope. Such methods are commonly used by skilled
practitioners.
[0181] A solution of such polypeptides (i.e., recombinant silk
protein) may then be prepared and used as described herein.
[0182] In another embodiment, recombinant silk protein may be
prepared according to the methods described in U.S. Pat. No.
8,642,734, the entirety of which is incorporated herein, and used
as described herein.
[0183] In an embodiment, a recombinant spider silk protein is
provided. The spider silk protein typically consists of from 170 to
760 amino acid residues, such as from 170 to 600 amino acid
residues, preferably from 280 to 600 amino acid residues, such as
from 300 to 400 amino acid residues, more preferably from 340 to
380 amino acid residues. The small size is advantageous because
longer spider silk proteins tend to form amorphous aggregates,
which require use of harsh solvents for solubilization and
polymerization. The recombinant spider silk protein may contain
more than 760 residues, in particular in cases where the spider
silk protein contains more than two fragments derived from the
N-terminal part of a spider silk protein, The spider silk protein
comprises an N-terminal fragment consisting of at least one
fragment (NT) derived from the corresponding part of a spider silk
protein, and a repetitive fragment (REP) derived from the
corresponding internal fragment of a spider silk protein.
Optionally, the spider silk protein comprises a C-terminal fragment
(CT) derived from the corresponding fragment of a spider silk
protein. The spider silk protein comprises typically a single
fragment (NT) derived from the N-terminal part of a spider silk
protein, but in preferred embodiments, the N-terminal fragment
include at least two, such as two fragments (NT) derived from the
N-terminal part of a spider silk protein. Thus, the spidroin can
schematically be represented by the formula NT.sub.m-REP, and
alternatively NT.sub.m-REP-CT, where m is an integer that is 1 or
higher, such as 2 or higher, preferably in the ranges of 1-2, 1-4,
1-6, 2-4 or 2-6. Preferred spidroins can schematically be
represented by the formulas NT.sub.2-REP or NT-REP, and
alternatively NT.sub.2-REP-CT or NT-REP-CT. The protein fragments
are covalently coupled, typically via a peptide bond. In one
embodiment, the spider silk protein consists of the NT fragment(s)
coupled to the REP fragment, which REP fragment is optionally
coupled to the CT fragment.
[0184] In one embodiment, the first step of the method of producing
polymers of an isolated spider silk protein involves expression of
a polynucleic acid molecule which encodes the spider silk protein
in a suitable host, such as Escherichia coli. The thus obtained
protein is isolated using standard procedures. Optionally,
lipopolysaccharides and other pyrogens are actively removed at this
stage.
[0185] In the second step of the method of producing polymers of an
isolated spider silk protein, a solution of the spider silk protein
in a liquid medium is provided. By the terms "soluble" and "in
solution" is meant that the protein is not visibly aggregated and
does not precipitate from the solvent at 60,000.times.g. The liquid
medium can be any suitable medium, such as an aqueous medium,
preferably a physiological medium, typically a buffered aqueous
medium, such as a 10-50 mM Tris-HCl buffer or phosphate buffer. The
liquid medium has a pH of 6.4 or higher and/or an ion composition
that prevents polymerization of the spider silk protein. That is,
the liquid medium has either a pH of 6.4 or higher or an ion
composition that prevents polymerization of the spider silk
protein, or both.
[0186] Ion compositions that prevent polymerization of the spider
silk protein can readily be prepared by the skilled person
utilizing the methods disclosed herein. A preferred ion composition
that prevents polymerization of the spider silk protein has an
ionic strength of more than 300 mM. Specific examples of ion
compositions that prevent polymerization of the spider silk protein
include above 300 mM NaCl, 100 mM phosphate and combinations of
these ions having desired preventive effect on the polymerization
of the spider silk protein, e.g. a combination of 10 mM phosphate
and 300 mM NaCl.
[0187] The presence of an NT fragment improves the stability of the
solution and prevents polymer formation under these conditions.
This can be advantageous when immediate polymerization may be
undesirable, e.g. during protein purification, in preparation of
large batches, or when other conditions need to be optimized. It is
preferred that the pH of the liquid medium is adjusted to 6.7 or
higher, such as 7.0 or higher, or even 8.0 or higher, such as up to
10.5, to achieve high solubility of the spider silk protein. It can
also be advantageous that the pH of the liquid medium is adjusted
to the range of 6.4-6.8, which provides sufficient solubility of
the spider silk protein but facilitates subsequent pH adjustment to
6.3 or lower.
[0188] In the third step, the properties of the liquid medium are
adjusted to a pH of 6.3 or lower and ion composition that allows
polymerization. That is, if the liquid medium wherein the spider
silk protein is dissolved has a pH of 6.4 or higher, the pH is
decreased to 6.3 or lower. The skilled person is well aware of
various ways of achieving this, typically involving addition of a
strong or weak acid. If the liquid medium wherein the spider silk
protein is dissolved has an ion composition that prevents
polymerization, the ion composition is changed so as to allow
polymerization. The skilled person is well aware of various ways of
achieving this, e.g. dilution, dialysis or gel filtration. If
required, this step involves both decreasing the pH of the liquid
medium to 6.3 or lower and changing the ion composition so as to
allow polymerization. It is preferred that the pH of the liquid
medium is adjusted to 6.2 or lower, such as 6.0 or lower. In
particular, it may be advantageous from a practical point of view
to limit the pH drop from 6.4 or 6.4-6.8 in the preceding step to
6.3 or 6.0-6.3, e.g. 6.2 in this step. In a preferred embodiment,
the pH of the liquid medium of this step is 3 or higher, such as
4.2 or higher. The resulting pH range, e.g. 4.2-6.3 promotes rapid
polymerization,
[0189] In the fourth step, the spider silk protein is allowed to
polymerize in the liquid medium having pH of 6.3 or lower and an
ion composition that allows polymerization of the spider silk
protein. Although the presence of the NT fragment improves
solubility of the spider silk protein at a pH of 6.4 or higher
and/or an ion composition that prevents polymerization of the
spider silk protein, it accelerates polymer formation at a pH of
6.3 or lower when the ion composition allows polymerization of the
spider silk protein. The resulting polymers are preferably solid
and macroscopic, and they are formed in the liquid medium having a
pH of 6.3 or lower and an ion composition that allows
polymerization of the spider silk protein. In a preferred
embodiment, the pH of the liquid medium of this step is 3 or
higher, such as 4.2 or higher. The resulting pH range, e.g. 4.2-6.3
promotes rapid polymerization, Resulting polymer may be provided at
the molecular weights described herein and prepared as a solution
form that may be used as necessary for article coatings.
[0190] Ion compositions that allow polymerization of the spider
silk protein can readily be prepared by the skilled person
utilizing the methods disclosed herein. A preferred ion composition
that allows polymerization of the spider silk protein has an ionic
strength of less than 300 mM. Specific examples of ion compositions
that allow polymerization of the spider silk protein include 150 mM
NaCl, 10 mM phosphate, 20 mM phosphate and combinations of these
ions lacking preventive effect on the polymerization of the spider
silk protein, e.g. a combination of 10 mM phosphate or 20 mM
phosphate and 150 mM NaCl. It is preferred that the ionic strength
of this liquid medium is adjusted to the range of 1-250 mM.
[0191] Without desiring to be limited to any specific theory, it is
envisaged that the NT fragments have oppositely charged poles, and
that environmental changes in pH affects the charge balance on the
surface of the protein followed by polymerization, whereas salt
inhibits the same event.
[0192] At neutral pH, the energetic cost of burying the excess
negative charge of the acidic pole may be expected to prevent
polymerization. However, as the dimer approaches its isoelectric
point at lower pH, attractive electrostatic forces will eventually
become dominant, explaining the observed salt and pH-dependent
polymerization behavior of NT and NT-containing minispidroins. It
is proposed that, in some embodiments, pH-induced NT
polymerization, and increased efficiency of fiber assembly of
NT-minispidroins, are due to surface electrostatic potential
changes, and that clustering of acidic residues at one pole of NT
shifts its charge balance such that the polymerization transition
occurs at pH values of 6.3 or lower.
[0193] In a fifth step, the resulting, preferably solid spider silk
protein polymers are isolated from said liquid medium. Optionally,
this step involves actively removing lipopolysaccharides and other
pyrogens from the spidroin polymers.
[0194] Without desiring to be limited to any specific theory, it
has been observed that formation of spidroin polymers progresses
via formation of water-soluble spidroin dimers. The present
disclosure thus also provides a method of producing dimers of an
isolated spider silk protein, wherein the first two method steps
are as described above. The spider silk proteins are present as
dimers in a liquid medium at a pH of 6.4 or higher and/or an ion
composition that prevents polymerization of said spider silk
protein. The third step involves isolating the dimers obtained in
the second step, and optionally removal of lipopolysaccharides and
other pyrogens. In a preferred embodiment, the spider silk protein
polymer of the disclosure consists of polymerized protein dimers.
The present disclosure thus provides a novel use of a spider silk
protein, preferably those disclosed herein, for producing dimers of
the spider silk protein.
[0195] According to another aspect, the disclosure provides a
polymer of a spider silk protein as disclosed herein. In an
embodiment, the polymer of this protein is obtainable by any one of
the methods therefor according to the disclosure. Thus, the
disclosure provides various uses of recombinant spider silk
protein, preferably those disclosed herein, for producing polymers
of the spider silk protein as recombinant silk based coatings.
According to one embodiment, the present disclosure provides a
novel use of a dimer of a spider silk protein, preferably those
disclosed herein, for producing polymers of the isolated spider
silk protein as recombinant silk based coatings. In these uses, it
is preferred that the polymers are produced in a liquid medium
having a pH of 6.3 or lower and an ion composition that allows
polymerization of said spider silk protein. In an embodiment, the
pH of the liquid medium is 3 or higher, such as 4.2 or higher. The
resulting pH range, e.g. 4.2-6.3 promotes rapid polymerization,
[0196] Using the method(s) of the present disclosure, it is
possible to control the polymerization process, and this allows for
optimization of parameters for obtaining silk polymers with
desirable properties and shapes.
[0197] In an embodiment, the recombinant silk proteins described
herein, include those described in U.S. Pat. No. 8,642,734, the
entirety of which is incorporated by reference.
[0198] In another embodiment, the recombinant silk proteins
described herein may be prepared according to the methods described
in U.S. Pat. No. 9,051,453, the entirety of which is incorporated
herein by reference.
[0199] An amino acid sequence represented by SEQ ID NO: 1 of U.S.
Pat. No. 9,051,453 is identical to an amino acid sequence that is
composed of 50 amino acid residues of an amino acid sequence of
ADF3 at the C-terminal (NCBI Accession No.: AAC47010, GI: 1263287).
An amino acid sequence represented by SEQ ID NO: 2 of U.S. Pat. No.
9,051,453 is identical to an amino acid sequence represented by SEQ
ID NO: 1 of U.S. Pat. No. 9,051,453 from which 20 residues have
been removed from the C-terminal. An amino acid sequence
represented by SEQ ID NO: 3 of U.S. Pat. No. 9,051,453 is identical
to an amino acid sequence represented by SEQ ID NO: 1 from which 29
residues have been removed from the C-terminal.
[0200] An example of the polypeptide that contains units of the
amino acid sequence represented by the formula 1: REP1-REP2 (1) and
that has, at a C-terminal, an amino acid sequence represented by
any of SEQ ID NOS: 1 to 3 or an amino acid sequence having a
homology of 90% or more with the amino acid sequence represented by
any of SEQ ID NOS: 1 to 3 of U.S. Pat. No. 9,051,453 is a
polypeptide having an amino acid sequence represented by SEQ ID NO:
8 of U.S. Pat. No. 9,051,453. The polypeptide having the amino acid
sequence represented by SEQ ID NO: 8 of U.S. Pat. No. 9,051,453 is
obtained by the following mutation: in an amino acid sequence of
ADF3 (NCBI Accession No.: AAC47010, GI: 1263287) to the N-terminal
of which has been added an amino acid sequence (SEQ ID NO: 5 of
U.S. Pat. No. 9,051,453) composed of a start codon, His 10 tags and
an HRV3C Protease (Human rhinovirus 3C Protease) recognition site,
1.sup.st to 13.sup.th repetitive regions are about doubled and the
translation ends at the 1154.sup.th amino acid residue. In the
polypeptide having the amino acid sequence represented by SEQ ID
NO: 8 of U.S. Pat. No. 9,051,453, the C-terminal sequence is
identical to the amino acid sequence represented by SEQ ID NO:
3.
[0201] Further, the polypeptide that contains units of the amino
acid sequence represented by the formula 1: REP1-REP2 (1) and that
has, at a C-terminal, an amino acid sequence represented by any of
SEQ ID NOS: 1 to 3 of U.S. Pat. No. 9,051,453 or an amino acid
sequence having a homology of 90% or more with the amino acid
sequence represented by any of SEQ ID NOS: 1 to 3 of U.S. Pat. No.
9,051,453 may be a protein that has an amino acid sequence
represented by SEQ ID NO: 8 of U.S. Pat. No. 9,051,453 in which one
or a plurality of amino acids have been substituted, deleted,
inserted and/or added and that has a repetitious region composed of
a crystal region and an amorphous region.
[0202] Further, an example of the polypeptide containing two or
more units of the amino acid sequence represented by the formula 1:
REP1-REP2 (1) is a recombinant protein derived from ADF4 having an
amino acid sequence represented by SEQ ID NO: 15 of U.S. Pat. No.
9,051,453. The amino acid sequence represented by SEQ ID NO: 15 of
U.S. Pat. No. 9,051,453 is an amino acid sequence obtained by
adding the amino acid sequence (SEQ ID NO: 5 of U.S. Pat. No.
9,051,453) composed of a start codon, His 10 tags and an HRV3C
Protease (Human rhinovirus 3C Protease) recognition site, to the
N-terminal of a partial amino acid sequence of ADF4 obtained from
the NCBI database (NCBI Accession No.: AAC47011, GI: 1263289).
Further, the polypeptide containing two or more units of the amino
acid sequence represented by the formula 1: REP1-REP2 (1) may be a
polypeptide that has an amino acid sequence represented by SEQ ID
NO: 15 of U.S. Pat. No. 9,051,453 in which one or a plurality of
amino acids have been substituted, deleted, inserted and/or added
and that has a repetitious region composed of a crystal region and
an amorphous region. Further, an example of the polypeptide
containing two or more units of the amino acid sequence represented
by the formula 1: REP1-REP2 (1) is a recombinant protein derived
from MaSp2 that has an amino acid sequence represented by SEQ ID
NO: 17 of U.S. Pat. No. 9,051,453. The amino acid sequence
represented by SEQ ID NO: 17 of U.S. Pat. No. 9,051,453 is an amino
acid sequence obtained by adding the amino acid sequence (SEQ ID
NO: 5 of U.S. Pat. No. 9,051,453) composed of a start codon, His 10
tags and an HRV3C Protease (Human rhinovirus 3C Protease)
recognition site, to the N-terminal of a partial sequence of MaSp2
obtained from the NCBI web database (NCBI Accession No.: AAT75313,
GI: 50363147). Furthermore, the polypeptide containing two or more
units of the amino acid sequence represented by the formula 1:
REP1-REP2 (1) may be a polypeptide that has an amino acid sequence
represented by SEQ ID NO: 17 of U.S. Pat. No. 9,051,453 in which
one or a plurality of amino acids have been substituted, deleted,
inserted and/or added and that has a repetitious region composed of
a crystal region and an amorphous region.
[0203] Examples of the polypeptide derived from flagelliform silk
proteins include a polypeptide containing 10 or more units of an
amino acid sequence represented by the formula 2: REP3 (2),
preferably a polypeptide containing 20 or more units thereof, and
more preferably a polypeptide containing 30 or more units thereof.
In the case of producing a recombinant protein using a microbe such
as Escherichia coli as a host, the molecular weight of the
polypeptide derived from flagelliform silk proteins is preferably
500 kDa or less, more preferably 300 kDa or less, and further
preferably 200 kDa or less, in terms of productivity.
[0204] In the formula (2), the REP 3 indicates an amino acid
sequence composed of Gly-Pro-Gly-Gly-X, where X indicates an amino
acid selected from the group consisting of Ala, Ser, Tyr and
Val.
[0205] A major characteristic of the spider silk is that the
flagelliform silk does not have a crystal region, but has a
repetitious region composed of an amorphous region. Since the major
dragline silk and the like have a repetitious region composed of a
crystal region and an amorphous region, they are expected to have
both high stress and stretchability. Meanwhile, as to the
flagelliform silk, although the stress is inferior to that of the
major dragline silk, the stretchability is high. The reason for
this is considered to be that most of the flagelliform silk is
composed of amorphous regions.
[0206] An example of the polypeptide containing 10 or more units of
the amino acid sequence represented by the formula 2: REP3 (2) is a
recombinant protein derived from flagelliform silk proteins having
an amino acid sequence represented by SEQ ID NO: 19 of U.S. Pat.
No. 9,051,453. The amino acid sequence represented by SEQ ID NO: 19
of U.S. Pat. No. 9,051,453 is an amino acid sequence obtained by
combining a partial sequence of flagelliform silk protein of
Nephila clavipes obtained from the NCBI database (NCBI Accession
No.: AAF36090, GI: 7106224), specifically, an amino acid sequence
thereof from the 1220.sup.th residue to the 1659.sup.th residue
from the N-terminal that corresponds to repetitive sections and
motifs (referred to as a PR1 sequence), with a partial sequence of
flagelliform silk protein of Nephila clavipes obtained from the
NCBI database (NCBI Accession No.: AAC38847, GI: 2833649),
specifically, a C-terminal amino acid sequence thereof from the
816.sup.th residue to the 907.sup.th residue from the C-terminal,
and thereafter adding the amino acid sequence (SEQ ID NO: 5 of U.S.
Pat. No. 9,051,453) composed of a start codon, His 10 tags and an
HRV3C Protease recognition site, to the N-terminal of the combined
sequence. Further, the polypeptide containing 10 or more units of
the amino acid sequence represented by the formula 2: REP3 (2) may
be a polypeptide that has an amino acid sequence represented by SEQ
ID NO: 19 of U.S. Pat. No. 9,051,453 in which one or a plurality of
amino acids have been substituted, deleted, inserted and/or added
and that has a repetitious region composed of an amorphous
region.
[0207] The polypeptide can be produced using a host that has been
transformed by an expression vector containing a gene encoding a
polypeptide. A method for producing a gene is not limited
particularly, and it may be produced by amplifying a gene encoding
a natural spider silk protein from a cell derived from spiders by a
polymerase chain reaction (PCR), etc., and cloning it, or may be
synthesized chemically. Also, a method for chemically synthesizing
a gene is not limited particularly, and it can be synthesized as
follows, for example: based on information of amino acid sequences
of natural spider silk proteins obtained from the NCBI web
database, etc., oligonucleotides that have been synthesized
automatically with AKTA oligopilot plus 10/100 (GE Healthcare Japan
Corporation) are linked by PCR, etc. At this time, in order to
facilitate the purification and observation of protein, it is
possible to synthesize a gene that encodes a protein having an
amino acid sequence of the above-described amino acid sequence to
the N-terminal of which has been added an amino acid sequence
composed of a start codon and His 10 tags.
[0208] Examples of the expression vector include a plasmid, a
phage, a virus, and the like that can express protein based on a
DNA sequence. The plasmid-type expression vector is not limited
particularly as long as it allows a target gene to be expressed in
a host cell and it can amplify itself. For example, in the case of
using Escherichia coli Rosetta (DE3) as a host, a pET22b(+) plasmid
vector, a pCold plasmid vector, and the like can be used. Among
these, in terms of productivity of protein, it is preferable to use
the pET22b(+) plasmid vector. Examples of the host include animal
cells, plant cells, microbes, etc.
[0209] The polypeptide used in the present disclosure is preferably
a polypeptide derived from ADF3, which is one of two principal
dragline silk proteins of Araneus diadematus. This polypeptide has
advantages of basically having high strength-elongation and
toughness and of being synthesized easily.
[0210] Accordingly, the recombinant silk protein (e.g., the
recombinant spider silk-based protein) used in accordance with the
embodiments, articles, and/or methods described herein, may include
one or more recombinant silk proteins described above or recited in
U.S. Pat. Nos. 8,173,772, 8,278,416, 8,618,255, 8,642,734,
8,691,581, 8,729,235, 9,115,204, 9,157,070, 9,309,299, 9,644,012,
9,708,376, 9,051,453, 9,617,315, 9,968,682, 9,689,089, 9,732,125,
9,856,308, 9,926,348, 10,065,997, 10,316,069, and 10,329,332; and
U.S. Patent Publication Nos. 2009/0226969, 2011/0281273,
2012/0041177, 2013/0065278, 2013/0115698, 2013/0316376,
2014/0058066, 2014/0079674, 2014/0245923, 2015/0087046,
2015/0119554, 2015/0141618, 2015/0291673, 2015/0291674,
2015/0239587, 2015/0344542, 2015/0361144, 2015/0374833,
2015/0376247, 2016/0024464, 2017/0066804, 2017/0066805,
2015/0293076, 2016/0222174, 2017/0283474, 2017/0088675,
2019/0135880, 2015/0329587, 2019/0040109, 2019/0135881,
2019/0177363, 2019/0225646, 2019/0233481, 2019/0031842,
2018/0355120, 2019/0186050, 2019/0002644, 2020/0031887,
2018/0273590, 20191/094403, 2019/0031843, 2018/0251501,
2017/0066805, 2018/0127553, 2019/0329526, 2020/0031886,
2018/0080147, 2019/0352349, 2020/0043085, 2019/0144819,
2019/0228449, 2019/0340666, 2020/0000091, 2019/0194710,
2019/0151505, 2018/0265555, 2019/0352330, 2019/0248847, and
2019/0378191, the entirety of which are incorporated herein by
reference.
[0211] Silk Fibroin-Like Protein Fragments
[0212] The recombinant silk protein in this disclosure comprises
synthetic proteins which are based on repeat units of natural silk
proteins. Besides the synthetic repetitive silk protein sequences,
these can additionally comprise one or more natural nonrepetitive
silk protein sequences. As used herein, "silk fibroin-like protein
fragments" refer to protein fragments having a molecular weight and
polydispersity as defined herein, and a certain degree of homology
to a protein selected from native silk protein, fibroin heavy
chain, fibroin light chain, or any protein comprising one or more
GAGAGS hexa amino acid repeating units. In some embodiments, a
degree of homology is selected from about 99%, about 98%, about
97%, about 96%, about 95%, about 94%, about 93%, about 92%, about
91%, about 90%, about 89%, about 88%, about 87%, about 86%, about
85%, about 84%, about 83%, about 82%, about 81%, about 80%, about
79%, about 78%, about 77%, about 76%, about 75%, or less than
75%.
[0213] As described herein, a protein such as native silk protein,
fibroin heavy chain, fibroin light chain, or any protein comprising
one or more GAGAGS hexa amino acid repeating units includes between
about 9% and about 45% glycine, or about 9% glycine, or about 10%
glycine, about 43% glycine, about 44% glycine, about 45% glycine,
or about 46% glycine. As described herein, a protein such as native
silk protein, fibroin heavy chain, fibroin light chain, or any
protein comprising one or more GAGAGS hexa amino acid repeating
units includes between about 13% and about 30% alanine, or about
13% alanine, or about 28% alanine, or about 29% alanine, or about
30% alanine, or about 31% alanine. As described herein, a protein
such as native silk protein, fibroin heavy chain, fibroin light
chain, or any protein comprising one or more GAGAGS hexa amino acid
repeating units includes between 9% and about 12% serine, or about
9% serine, or about 10% serine, or about 11% serine, or about 12%
serine.
[0214] In some embodiments, a silk fibroin-like protein described
herein includes about 5%, about 6%, about 7%, about 8%, about 9%,
about 10%, about 11%, about 12%, about 13%, about 14%, about 15%,
about 16%, about 17%, about 18%, about 19%, about 20%, about 21%,
about 22%, about 23%, about 24%, about 25%, about 26%, about 27%,
about 28%, about 29%, about 30%, about 31%, about 32%, about 33%,
about 34%, about 35%, about 36%, about 37%, about 38%, about 39%,
about 40%, about 41%, about 42%, about 43%, about 44%, about 45%,
about 46%, about 47%, about 48%, about 49%, about 50%, about 51%,
about 52%, about 53%, about 54%, or about 55% glycine. In some
embodiments, a silk fibroin-like protein described herein includes
about 13%, about 14%, about 15%, about 16%, about 17%, about 18%,
about 19%, about 20%, about 21%, about 22%, about 23%, about 24%,
about 25%, about 26%, about 27%, about 28%, about 29%, about 30%,
about 31%, about 32%, about 33%, about 34%, about 35%, about 36%,
about 37%, about 38%, or about 39% alanine. In some embodiments, a
silk fibroin-like protein described herein includes about 2%, about
3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%,
about 10%, about 11%, about 12%, about 13%, about 14%, about 15%,
about 16%, about 17%, about 18%, about 19%, about 20%, about 21%,
or about 22% serine. In some embodiments, a silk fibroin-like
protein described herein may include independently any amino acid
known to be included in natural fibroin. In some embodiments, a
silk fibroin-like protein described herein may exclude
independently any amino acid known to be included in natural
fibroin. In some embodiments, on average 2 out of 6 amino acids, 3
out of 6 amino acids, or 4 out of 6 amino acids in a silk
fibroin-like protein described herein is glycine. In some
embodiments, on average 1 out of 6 amino acids, 2 out of 6 amino
acids, or 3 out of 6 amino acids in a silk fibroin-like protein
described herein is alanine. In some embodiments, on average none
out of 6 amino acids, 1 out of 6 amino acids, or 2 out of 6 amino
acids in a silk fibroin-like protein described herein is
serine.
[0215] Other Properties of SPF
[0216] Compositions of the present disclosure are "biocompatible"
or otherwise exhibit "biocompatibility" meaning that the
compositions are compatible with living tissue or a living system
by not being toxic, injurious, or physiologically reactive and not
causing immunological rejection or an inflammatory response. Such
biocompatibility can be evidenced by participants topically
applying compositions of the present disclosure on their skin for
an extended period of time. In an embodiment, the extended period
of time is about 3 days. In an embodiment, the extended period of
time is about 7 days. In an embodiment, the extended period of time
is about 14 days. In an embodiment, the extended period of time is
about 21 days. In an embodiment, the extended period of time is
about 30 days. In an embodiment, the extended period of time is
selected from the group consisting of about 1 month, about 2
months, about 3 months, about 4 months, about 5 months, about 6
months, about 7 months, about 8 months, about 9 months, about 10
months, about 11 months, about 12 months, and indefinitely. For
example, in some embodiments, the coatings described herein are
biocompatible coatings.
[0217] In some embodiments, compositions described herein, which
may be biocompatible compositions (e.g., biocompatible coatings
that include silk), may be evaluated and comply with International
Standard ISO 10993-1, titled the "Biological evaluation of medical
devices--Part 1: Evaluation and testing within a risk management
process." In some embodiments, compositions described herein, which
may be biocompatible compositions, may be evaluated under ISO
106993-1 for one or more of cytotoxicity, sensitization,
hemocompatibility, pyrogenicity, implantation, genotoxicity,
carcinogenicity, reproductive and developmental toxicity, and
degradation.
[0218] Compositions of the present disclosure are "hypoallergenic"
meaning that they are relatively unlikely to cause an allergic
reaction. Such hypoallergenicity can be evidenced by participants
topically applying compositions of the present disclosure on their
skin for an extended period of time. In an embodiment, the extended
period of time is about 3 days. In an embodiment, the extended
period of time is about 7 days. In an embodiment, the extended
period of time is about 14 days. In an embodiment, the extended
period of time is about 21 days. In an embodiment, the extended
period of time is about 30 days. In an embodiment, the extended
period of time is selected from the group consisting of about 1
month, about 2 months, about 3 months, about 4 months, about 5
months, about 6 months, about 7 months, about 8 months, about 9
months, about 10 months, about 11 months, about 12 months, and
indefinitely.
[0219] In an embodiment, the stability of a composition of the
present disclosure is about 1 day. In an embodiment, the stability
of a composition of the present disclosure is about 2 days. In an
embodiment, the stability of a composition of the present
disclosure is about 3 days. In an embodiment, the stability of a
composition of the present disclosure is about 4 days. In an
embodiment, the stability of a composition of the present
disclosure is about 5 days. In an embodiment, the stability of a
composition of the present disclosure is about 6 days. In an
embodiment, the stability of a composition of the present
disclosure is about 7 days. In an embodiment, the stability of a
composition of the present disclosure is about 8 days. In an
embodiment, the stability of a composition of the present
disclosure is about 9 days. In an embodiment, the stability of a
composition of the present disclosure is about 10 days.
[0220] In an embodiment, the stability of a composition of the
present disclosure is about 11 days, about 12 days, about 13 days,
about 14 days, about 15 days, about 16 days, about 17 days, about
18 days, about 19 days, about 20 days, about 21 days, about 22
days, about 23 days, about 24 days, about 25 days, about 26 days,
about 27 days, about 28 days, about 29 days, or about 30 days.
[0221] In an embodiment, the stability of a composition of the
present disclosure is 10 days to 6 months. In an embodiment, the
stability of a composition of the present disclosure is 6 months to
12 months. In an embodiment, the stability of a composition of the
present disclosure is 12 months to 18 months. In an embodiment, the
stability of a composition of the present disclosure is 18 months
to 24 months. In an embodiment, the stability of a composition of
the present disclosure is 24 months to 30 months. In an embodiment,
the stability of a composition of the present disclosure is 30
months to 36 months. In an embodiment, the stability of a
composition of the present disclosure is 36 months to 48 months. In
an embodiment, the stability of a composition of the present
disclosure is 48 months to 60 months.
[0222] In an embodiment, a SPF composition of the present
disclosure is not soluble in an aqueous solution due to the
crystallinity of the protein. In an embodiment, a SPF composition
of the present disclosure is soluble in an aqueous solution. In an
embodiment, the SPF of a composition of the present disclosure
include a crystalline portion of about two-thirds and an amorphous
region of about one-third. In an embodiment, the SPF of a
composition of the present disclosure include a crystalline portion
of about one-half and an amorphous region of about one-half. In an
embodiment, the SPF of a composition of the present disclosure
include a 99% crystalline portion and a 1% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 95% crystalline portion and a 5% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 90% crystalline portion and a 10% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 85% crystalline portion and a 15% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 80% crystalline portion and a 20% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 75% crystalline portion and a 25% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 70% crystalline portion and a 30% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 65% crystalline portion and a 35% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 60% crystalline portion and a 40% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 50% crystalline portion and a 50% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 40% crystalline portion and a 60% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 35% crystalline portion and a 65% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 30% crystalline portion and a 70% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 25% crystalline portion and a 75% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 20% crystalline portion and a 80% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 15% crystalline portion and a 85% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 10% crystalline portion and a 90% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 5% crystalline portion and a 90% amorphous region. In an
embodiment, the SPF of a composition of the present disclosure
include a 1% crystalline portion and a 99% amorphous region.
[0223] As used herein, the term "substantially free of inorganic
residuals" means that the composition exhibits residuals of 0.1%
(w/w) or less. In an embodiment, substantially free of inorganic
residuals refers to a composition that exhibits residuals of 0.05%
(w/w) or less. In an embodiment, substantially free of inorganic
residuals refers to a composition that exhibits residuals of 0.01%
(w/w) or less. In an embodiment, the amount of inorganic residuals
is between 0 ppm ("non-detectable" or "ND") and 1000 ppm. In an
embodiment, the amount of inorganic residuals is ND to about 500
ppm. In an embodiment, the amount of inorganic residuals is ND to
about 400 ppm. In an embodiment, the amount of inorganic residuals
is ND to about 300 ppm. In an embodiment, the amount of inorganic
residuals is ND to about 200 ppm. In an embodiment, the amount of
inorganic residuals is ND to about 100 ppm. In an embodiment, the
amount of inorganic residuals is between 10 ppm and 1000 ppm.
[0224] As used herein, the term "substantially free of organic
residuals" means that the composition exhibits residuals of 0.1%
(w/w) or less, in an embodiment, substantially free of organic
residuals refers to a composition that exhibits residuals of 0.05%
(w/w) or less. In an embodiment, substantially free of organic
residuals refers to a composition that exhibits residuals of 0.01%
(w/w) or less. In an embodiment, the amount of organic residuals is
between 0 ppm ("non-detectable" or "ND") and 1000 ppm. In an
embodiment, the amount of organic residuals is ND to about 500 ppm.
In an embodiment, the amount of organic residuals is ND to about
400 ppm. In an embodiment, the amount of organic residuals is ND to
about 300 ppm. In an embodiment, the amount of organic residuals is
ND to about 200 ppm. In an embodiment, the amount of organic
residuals is ND to about 100 ppm. In an embodiment, the amount of
organic residuals is between 10 ppm and 1000 ppm.
[0225] Compositions of the present disclosure exhibit
"biocompatibility" meaning that the compositions are compatible
with living tissue or a living system by not being toxic,
injurious, or physiologically reactive and not causing
immunological rejection. Such biocompatibility can be evidenced by
participants topically applying compositions of the present
disclosure on their skin for an extended period of time. In an
embodiment, the extended period of time is about 3 days. In an
embodiment, the extended period of time is about 7 days, in an
embodiment, the extended period of time is about 14 days, in an
embodiment, the extended period of time is about 21 days. In an
embodiment, the extended period of time is about 30 days. In an
embodiment, the extended period of time is selected from the group
consisting of about I month, about 2 months, about 3 months, about
4 months, about 5 months, about 6 months, about 7 months, about 8
months, about 9 months, about 10 months, about 11 months, about 12
months, and indefinitely.
[0226] Compositions of the present disclosure are "hypoallergenic"
meaning that they are relatively unlikely to cause an allergic
reaction. Such hypoallergenicity can be evidenced by participants
topically applying compositions of the present disclosure on their
skin for an extended period of time. In an embodiment, the extended
period of time is about 3 days. In an embodiment, the extended
period of time is about 7 days. In an embodiment, the extended
period of time is about 14 days. In an embodiment, the extended
period of time is about 21 days. In an embodiment, the extended
period of time is about 30 days. In an embodiment, the extended
period of time is selected from the group consisting of about 1
month, about 2 months, about 3 months, about 4 months, about 5
months, about 6 months, about 7 months, about 8 months, about 9
months, about 10 months, about 11 months, about 12 months, and
indefinitely.
[0227] Following are non-limiting examples of suitable ranges for
various parameters in and for preparation of the silk solutions of
the present disclosure. The silk solutions of the present
disclosure may include one or more, but not necessarily all, of
these parameters and may be prepared using various combinations of
ranges of such parameters.
[0228] In an embodiment, the percent SPF in the solution is less
than 30.0 wt. %. In an embodiment, the percent SPF in the solution
is less than 25.0 wt. %. In an embodiment, the percent SPF in the
solution is less than 20.0 wt. %. In an embodiment, the percent SPF
in the solution is less than 19.0 wt. %. In an embodiment, the
percent SPF in the solution is less than 18.0 wt. %. In an
embodiment, the percent SPF in the solution is less than 17.0 wt.
%. In an embodiment, the percent SPF in the solution is less than
16.0 wt. %. In an embodiment, the percent SPF in the solution is
less than 15.0 wt. %. In an embodiment, the percent SPF in the
solution is less than 14.0 wt. %. In an embodiment, the percent SPF
in the solution is less than 13.0 wt. %. In an embodiment, the
percent SPF in the solution is less than 12.0 wt. %. In an
embodiment, the percent SPF in the solution is less than 11.0 wt.
%. In an embodiment, the percent SPF in the solution is less than
10.0 wt. %. In an embodiment, the percent SPF in the solution is
less than 9.0 wt. %. In an embodiment, the percent SPF in the
solution is less than 8.0 wt. %. In an embodiment, the percent SPF
in the solution is less than 7.0 wt. %. In an embodiment, the
percent SPF in the solution is less than 6.0 wt. %. In an
embodiment, the percent SPF in the solution is less than 5.0 wt. %.
In an embodiment, the percent SPF in the solution is less than 4.0
wt. %. In an embodiment, the percent SPF in the solution is less
than 3.0 wt. %. In an embodiment, the percent SPF in the solution
is less than 2.0 wt. %. In an embodiment, the percent SPF in the
solution is less than 1.0 wt. %. In an embodiment, the percent SPF
in the solution is less than 0.9 wt. %. In an embodiment, the
percent SPF in the solution is less than 0.8 wt. %. In an
embodiment, the percent SPF in the solution is less than 0.7 wt. %.
In an embodiment, the percent SPF in the solution is less than 0.6
wt. %. In an embodiment, the percent SPF in the solution is less
than 0.5 wt. %. In an embodiment, the percent SPF in the solution
is less than 0.4 wt. %. In an embodiment, the percent SPF in the
solution is less than 0.3 wt. %. In an embodiment, the percent SPF
in the solution is less than 0.2 wt. %. In an embodiment, the
percent SPF in the solution is less than 0.1 wt. %.
[0229] In an embodiment, the percent SPF in the solution is greater
than 0.1 wt. %. In an embodiment, the percent SPF in the solution
is greater than 0.2 wt. %. In an embodiment, the percent SPF in the
solution is greater than 0.3 wt. %. In an embodiment, the percent
SPF in the solution is greater than 0.4 wt. %. In an embodiment,
the percent SPF in the solution is greater than 0.5 wt. %. In an
embodiment, the percent SPF in the solution is greater than 0.6 wt.
%. In an embodiment, the percent SPF in the solution is greater
than 0.7 wt. %. In an embodiment, the percent SPF in the solution
is greater than 0.8 wt. %. In an embodiment, the percent SPF in the
solution is greater than 0.9 wt. %. In an embodiment, the percent
SPF in the solution is greater than 1.0 wt. %. In an embodiment,
the percent SPF in the solution is greater than 2.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 3.0 wt.
%. In an embodiment, the percent SPF in the solution is greater
than 4.0 wt. %. In an embodiment, the percent SPF in the solution
is greater than 5.0 wt. %. In an embodiment, the percent SPF in the
solution is greater than 6.0 wt. %. In an embodiment, the percent
SPF in the solution is greater than 7.0 wt. %. In an embodiment,
the percent SPF in the solution is greater than 8.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 9.0 wt.
%. In an embodiment, the percent SPF in the solution is greater
than 10.0 wt. %. In an embodiment, the percent SPF in the solution
is greater than 11.0 wt. %. In an embodiment, the percent SPF in
the solution is greater than 12.0 wt. %. In an embodiment, the
percent SPF in the solution is greater than 13.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 14.0
wt. %. In an embodiment, the percent SPF in the solution is greater
than 15.0 wt. %. In an embodiment, the percent SPF in the solution
is greater than 16.0 wt. %. In an embodiment, the percent SPF in
the solution is greater than 17.0 wt. %. In an embodiment, the
percent SPF in the solution is greater than 18.0 wt. %. In an
embodiment, the percent SPF in the solution is greater than 19.0
wt. %. In an embodiment, the percent SPF in the solution is greater
than 20.0 wt. %. In an embodiment, the percent SPF in the solution
is greater than 25.0 wt. %.
[0230] In an embodiment, the percent SPF in the solution ranges
from about 0.1 wt. % to about 30.0 wt. %. In an embodiment, the
percent SPF in the solution ranges from about 0.1 wt. % to about
25.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 20.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 15.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 10.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 9.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 8.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 7.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 6.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 6.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 5.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 5.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 4.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 4.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 3.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 3.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 2.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.1 wt. % to
about 2.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 2.4 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.5 wt. % to
about 5.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.5 wt. % to about 4.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.5 wt. % to
about 4.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.5 wt. % to about 3.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 0.5 wt. % to
about 3.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.5 wt. % to about 2.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 1.0 wt. % to
about 4.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 1.0 wt. % to about 3.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 1.0 wt. % to
about 3.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 1.0 wt. % to about 2.5 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 1.0 wt. % to
about 2.4 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 1.0 wt. % to about 2.0 wt. %.
[0231] In an embodiment, the percent SPF in the solution ranges
from about 20.0 wt. % to about 30.0 wt. %. In an embodiment, the
percent SPF in the solution ranges from about 0.1 wt. % to about
10.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 1.0 wt. % to about 10.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 2 wt. % to about
10.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 0.1 wt. % to about 6.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 6.0 wt. % to
about 10.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 6.0 wt. % to about 8.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 6.0 wt. % to
about 9.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 10.0 wt. % to about 20.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 11.0 wt. % to
about 19.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 12.0 wt. % to about 18.0 wt. %. In an embodiment,
the percent SPF in the solution ranges from about 13.0 wt. % to
about 17.0 wt. %. In an embodiment, the percent SPF in the solution
ranges from about 14.0 wt. % to about 16.0 wt. %. In an embodiment,
the percent SPF in the solution is about 1.0 wt. %. In an
embodiment, the percent SPF in the solution is about 1.5 wt. %. In
an embodiment, the percent SPF in the solution is about 2.0 wt.%.
In an embodiment, the percent SPF in the solution is about 2.4 wt.
%. In an embodiment, the percent SPF in the solution is 3.0 wt. %.
In an embodiment, the percent SPF in the solution is 3.5 wt. %. In
an embodiment, the percent SPF in the solution is about 4.0 wt. %.
In an embodiment, the percent SPF in the solution is about 4.5 wt.
%. In an embodiment, the percent SPF in the solution is about 5.0
wt. %. In an embodiment, the percent SPF in the solution is about
5.5 wt. %. In an embodiment the percent SPF in the solution is
about 6.0 wt. %. In an embodiment, the percent SPF in the solution
is about 6.5 wt. %. In an embodiment, the percent SPF in the
solution is about 7.0 wt. %. In an embodiment, the percent SPF in
the solution is about 7.5 wt. %. In an embodiment, the percent SPF
in the solution is about 8.0 wt. %. In an embodiment, the percent
SPF in the solution is about 8.5 wt. %. In an embodiment, the
percent SPF in the solution is about 9.0 wt. %. In an embodiment,
the percent SPF in the solution is about 9.5 wt. %. In an
embodiment, the percent SPF in the solution is about 10.0 wt.
%.
[0232] In an embodiment, the percent sericin in the solution is
non-detectable to 25.0 wt. %. In an embodiment, the percent sericin
in the solution is non-detectable to 5.0 wt. %. In an embodiment,
the percent sericin in the solution is 1.0 wt. %. In an embodiment,
the percent sericin in the solution is 2.0 wt. %. In an embodiment,
the percent sericin in the solution is 3.0 wt. %. In an embodiment,
the percent sericin in the solution is 4.0 wt. %. In an embodiment,
the percent sericin in the solution is 5.0 wt. %. In an embodiment,
the percent sericin in the solution is 10.0 wt. %. In an
embodiment, the percent sericin in the solution is 25.0 wt. %.
[0233] In some embodiments, the silk fibroin protein fragments of
the present disclosure are shelf stable (they will not slowly or
spontaneously gel when stored in an aqueous solution and there is
no aggregation of fragments and therefore no increase in molecular
weight over time), from 10 days to 3 years depending on storage
conditions, percent SPF, and number of shipments and shipment
conditions. Additionally, pH may be altered to extend shelf life
and/or support shipping conditions by preventing premature folding
and aggregation of the silk. In an embodiment, the stability of the
LiBr-silk fragment solution is 0 to 1 year. In an embodiment, the
stability of the LiBr-silk fragment solution is 0 to 2 years. In an
embodiment, the stability of the LiBr-silk fragment solution is 0
to 3 years. In an embodiment, the stability of the LiBr-silk
fragment solution is 0 to 4 years. In an embodiment, the stability
of the LiBr-silk fragment solution is 0 to 5 years. In an
embodiment, the stability of the LiBr-silk fragment solution is 1
to 2 years. In an embodiment, the stability of the LiBr-silk
fragment solution is 1 to 3 years. In an embodiment, the stability
of the LiBr-silk fragment solution is 1 to 4 years. In an
embodiment, the stability of the LiBr-silk fragment solution is 1
to 5 years. In an embodiment, the stability of the LiBr-silk
fragment solution is 2 to 3 years. In an embodiment, the stability
of the LiBr-silk fragment solution is 2 to 4 years. In an
embodiment, the stability of the LiBr-silk fragment solution is 2
to 5 years. In an embodiment, the stability of the LiBr-silk
fragment solution is 3 to 4 years. In an embodiment, the stability
of the LiBr-silk fragment solution is 3 to 5 years. In an
embodiment, the stability of the LiBr-silk fragment solution is 4
to 5 years.
[0234] In an embodiment, the stability of a composition of the
present disclosure is 10 days to 6 months. In an embodiment, the
stability of a composition of the present disclosure is 6 months to
12 months. In an embodiment, the stability of a composition of the
present disclosure is 12 months to 18 months. In an embodiment, the
stability of a composition of the present disclosure is 18 months
to 24 months. In an embodiment, the stability of a composition of
the present disclosure is 24 months to 30 months. In an embodiment,
the stability of a composition of the present disclosure is 30
months to 36 months. In an embodiment, the stability of a
composition of the present disclosure is 36 months to 48 months. In
an embodiment, the stability of a composition of the present
disclosure is 48 months to 60 months.
[0235] In an embodiment, a composition of the present disclosure
having SPF has non-detectable levels of LiBr residuals. In an
embodiment, the amount of the LiBr residuals in a composition of
the present disclosure is between 10 ppm and 1000 ppm. In an
embodiment, the amount of the LiBr residuals in a composition of
the present disclosure is between 10 ppm and 300 ppm. In an
embodiment, the amount of the LiBr residuals in a composition of
the present disclosure is less than 25 ppm. In an embodiment, the
amount of the Li Br residuals in a composition of the present
disclosure is less than 50 ppm. In an embodiment, the amount of the
LiBr residuals in a composition of the present disclosure is less
than 75 ppm. In an embodiment, the amount of the LiBr residuals in
a composition of the present disclosure is less than 100 ppm. In an
embodiment, the amount of the LiBr residuals in a composition of
the present disclosure is less than 200 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is less than 300 ppm. In an embodiment, the amount of
the LiBr residuals in a composition of the present disclosure is
less than 400 ppm. In an embodiment, the amount of the LiBr
residuals in a composition of the present disclosure is less than
500 ppm. In an embodiment, the amount of the LiBr residuals in a
composition of the present disclosure is less than 600 ppm. In an
embodiment, the amount of the LiBr residuals in a composition of
the present disclosure is less than 700 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is less than 800 ppm. In an embodiment, the amount of
the LiBr residuals in a composition of the present disclosure is
less than 900 ppm. In an embodiment, the amount of the LiBr
residuals in a composition of the present disclosure is less than
1000 ppm. In an embodiment, the amount of the LiBr residuals in a
composition of the present disclosure is non-detectable to 500 ppm.
In an embodiment, the amount of the LiBr residuals in a composition
of the present disclosure is non-detectable to 450 ppm. In an
embodiment, the amount of the LiBr residue in a composition of the
present disclosure is non-detectable to 400 ppm. In an embodiment,
the amount of the LiBr residuals in a composition of the present
disclosure is non-detectable to 350 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is non-detectable to 300 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is non-detectable to 250 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is non-detectable to 200 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is non-detectable to 150 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is non-detectable to 100 ppm. In an embodiment, the
amount of the LiBr residuals in a composition of the present
disclosure is 100 ppm to 200 ppm. In an embodiment, the amount of
the LiBr residuals in a composition of the present disclosure is
200 ppm to 300 ppm. In an embodiment, the amount of the LiBr
residuals in a composition of the present disclosure is 300 ppm to
400 ppm. In an embodiment, the amount of the LiBr residuals in a
composition of the present disclosure is 400 ppm to 500 ppm.
[0236] In an embodiment, a composition of the present disclosure
having SPF, has non-detectable levels of Na.sub.2CO.sub.3
residuals. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
100 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
200 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
300 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
400 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
500 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
600 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
700 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
800 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
900 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is less than
1000 ppm. In an embodiment, the amount of the Na.sub.2CO.sub.3
residuals in a composition of the present disclosure is
non-detectable to 500 ppm. In an embodiment, the amount of the
Na.sub.2CO.sub.3 residuals in a composition of the present
disclosure is non-detectable to 450 ppm. In an embodiment, the
amount of the Na.sub.2CO.sub.3 residuals in a composition of the
present disclosure is non-detectable to 400 ppm. In an embodiment,
the amount of the Na.sub.2CO.sub.3 residuals in a composition of
the present disclosure is non-detectable to 350 ppm. In an
embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is non-detectable to 300 ppm.
In an embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is non-detectable to 250 ppm.
In an embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is non-detectable to 200 ppm.
In an embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is non-detectable to 150 ppm.
In an embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is non-detectable to 100 ppm.
In an embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is 100 ppm to 200 ppm. In an
embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is 200 ppm to 300 ppm. In an
embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is 300 ppm to 400 ppm. In an
embodiment, the amount of the Na.sub.2CO.sub.3 residuals in a
composition of the present disclosure is 400 ppm to 500 ppm.
[0237] A unique feature of the SPF compositions of the present
disclosure are shelf stability (they will not slowly or
spontaneously gel when stored in an aqueous solution and there is
no aggregation of fragments and therefore no increase in molecular
weight over time), from 10 days to 3 years depending on storage
conditions, percent silk, and number of shipments and shipment
conditions. Additionally pH may be altered to extend shelf-life
and/or support shipping conditions by preventing premature folding
and aggregation of the silk. In an embodiment, a SPF solution
composition of the present disclosure has a shelf stability for up
to 2 weeks at room temperature (RT). In an embodiment, a SPF
solution composition of the present disclosure has a shelf
stability for up to 4 weeks at RT. In an embodiment, a SPF solution
composition of the present disclosure has a shelf stability for up
to 6 weeks at RT. In an embodiment, a SPF solution composition of
the present disclosure has a shelf stability for up to 8 weeks at
RT. In an embodiment, a SPF solution composition of the present
disclosure has a shelf stability for up to 10 weeks at RT. In an
embodiment, a SPF solution composition of the present disclosure
has a shelf stability for up to 12 weeks at RT. In an embodiment, a
SPF solution composition of the present disclosure has a shelf
stability ranging from about 4 weeks to about 52 weeks at RT. Table
R below shows shelf stability test results for embodiments of SPF
compositions of the present disclosure.
TABLE-US-00020 TABLE R Shelf Stability of SPF Compositions of the
Present Disclosure % Silk Temperature Time to Gelation 2 RT 4 weeks
2 4.degree. C. >9 weeks 4 RT 4 weeks 4 4.degree. C. >9 weeks
6 RT 2 weeks 6 4.degree. C. >9 weeks
[0238] In some embodiments, the water solubility of the silk film
derived from silk fibroin protein fragments as described herein can
be modified by solvent annealing (water annealing or methanol
annealing), chemical crosslinking, enzyme crosslinking and heat
treatment.
[0239] In some embodiments, the process of annealing may involve
inducing beta-sheet formation in the silk fibroin protein fragment
solutions used as a coating material. Techniques of annealing
(e.g., increase crystallinity) or otherwise promoting "molecular
packing" of silk fibroin-protein based fragments have been
described. In some embodiments, the amorphous silk film is annealed
to introduce beta-sheet in the presence of a solvent selected from
the group of water or organic solvent. In some embodiments, the
amorphous silk film is annealed to introduce beta-sheet in the
presence of water (water annealing process). In some embodiments,
the amorphous silk fibroin protein fragment film is annealed to
introduce beta-sheet in the presence of methanol. In some
embodiments, annealing (e.g., the beta sheet formation) is induced
by addition of an organic solvent. Suitable organic solvents
include, but are not limited to methanol, ethanol, acetone,
isopropanol, or combination thereof.
[0240] In some embodiments, annealing is carried out by so-called
"water-annealing" or "water vapor annealing" in which water vapor
is used as an intermediate plasticizing agent or catalyst to
promote the packing of beta-sheets. In some embodiments, the
process of water annealing may be performed under vacuum. Suitable
such methods have been described in Jin H-J et al. (2005),
Water-stable Silk Films with Reduced Beta-Sheet Content, Advanced
Functional Materials, 15: 1241-1247; Xiao H. et al. (2011),
Regulation of Silk Material Structure by Temperature-Controlled
Water Vapor Annealing, Biomacromolecules, 12(5): 1686-1696.
[0241] The important feature of the water annealing process is to
drive the formation of crystalline beta-sheet in the silk fibroin
protein fragment peptide chain to allow the silk fibroin
self-assembling into a continuous film. In some embodiments, the
crystallinity of the silk fibroin protein fragment film is
controlled by controlling the temperature of water vapor and
duration of the annealing. In some embodiments, the annealing is
performed at a temperature ranging from about 65.degree. C. to
about 110.degree. C. In some embodiments, the temperature of the
water is maintained at about 80.degree. C. In some embodiments,
annealing is performed at a temperature selected from the group of
about 65.degree. C., about 70.degree. C., about 75.degree. C.,
about 80.degree. C., about 85.degree. C., about 90.degree. C.,
about 95.degree. C., about 100.degree. C., about 105.degree. C.,
and about 110.degree. C.
[0242] In some embodiments, the annealing process lasts a period of
time selected from the group of about 1 minute to about 40 minutes,
about 1 minute to about 50 minutes, about 1 minute to about 60
minutes, about 1 minute to about 70 minutes, about 1 minute to
about 80 minutes, about 1 minute to about 90 minutes, about 1
minute to about 100 minutes, about 1 minute to about 110 minutes,
about 1 minute to about 120 minutes, about 1 minute to about 130
minutes, about 5 minutes to about 40 minutes, about 5 minutes to
about 50 minutes, about 5 minutes to about 60 minutes, about 5
minutes to about 70 minutes, about 5 minutes to about 80 minutes,
about 5 minutes to about 90 minutes, about 5 minutes to about 100
minutes, about 5 minutes to about 110 minutes, about 5 minutes to
about 120 minutes, about 5 minutes to about 130 minutes, about 10
minutes to about 40 minutes, about 10 minutes to about 50 minutes,
about 10 minutes to about 60 minutes, about 10 minutes to about 70
minutes, about 10 minutes to about 80 minutes, about 10 minutes to
about 90 minutes, about 10 minutes to about 100 minutes, about 10
minutes to about 110 minutes, about 10 minutes to about 120
minutes, about 10 minutes to about 130 minutes, about 15 minutes to
about 40 minutes, about 15 minutes to about 50 minutes, about 15
minutes to about 60 minutes, about 15 minutes to about 70 minutes,
about 15 minutes to about 80 minutes, about 15 minutes to about 90
minutes, about 15 minutes to about 100 minutes, about 15 minutes to
about 110 minutes, about 15 minutes to about 120 minutes, about 15
minutes to about 130 minutes, about 20 minutes to about 40 minutes,
about 20 minutes to about 50 minutes, about 20 minutes to about 60
minutes, about 20 minutes to about 70 minutes, about 20 minutes to
about 80 minutes, about 20 minutes to about 90 minutes, about 20
minutes to about 100 minutes, about 20 minutes to about 110
minutes, about 20 minutes to about 120 minutes, about 20 minutes to
about 130 minutes, about 25 minutes to about 40 minutes, about 25
minutes to about 50 minutes, about 25 minutes to about 60 minutes,
about 25 minutes to about 70 minutes, about 25 minutes to about 80
minutes, about 25 minutes to about 90 minutes, about 25 minutes to
about 100 minutes, about 25 minutes to about 110 minutes, about 25
minutes to about 120 minutes, about 25 minutes to about 130
minutes, about 30 minutes to about 40 minutes, about 30 minutes to
about 50 minutes, about 30 minutes to about 60 minutes, about 30
minutes to about 70 minutes, about 30 minutes to about 80 minutes,
about 30 minutes to about 90 minutes, about 30 minutes to about 100
minutes, about 30 minutes to about 110 minutes, about 30 minutes to
about 120 minutes, about 30 minutes to about 130 minutes, about 35
minutes to about 40 minutes, about 35 minutes to about 50 minutes,
about 35 minutes to about 60 minutes, about 35 minutes to about 70
minutes, about 35 minutes to about 80 minutes, about 35 minutes to
about 90 minutes, about 35 minutes to about 100 minutes, about 35
minutes to about 110 minutes, about 35 minutes to about 120
minutes, about 35 minutes to about 130 minutes, about 40 minutes to
about 50 minutes, about 40 minutes to about 60 minutes, about 40
minutes to about 70 minutes, about 40 minutes to about 80 minutes,
about 40 minutes to about 90 minutes, about 40 minutes to about 100
minutes, about 40 minutes to about 110 minutes, about 40 minutes to
about 120 minutes, about 40 minutes to about 130 minutes, about 45
minutes to about 50 minutes, about 45 minutes to about 60 minutes,
about 45 minutes to about 70 minutes, about 45 minutes to about 80
minutes, about 45 minutes to about 90 minutes, about 45 minutes to
about 100 minutes, about 45 minutes to about 110 minutes, about 45
minutes to about 120 minutes, and about 45 minutes to about 130
minutes. In some embodiments, the annealing process lasts a period
of time ranging from about 1 minute to about 60 minutes. In some
embodiments, the annealing process lasts a period of time ranging
from about 45 minutes to about 60 minutes. The longer water
annealing post-processing corresponded an increased crystallinity
of silk fibroin protein fragments.
[0243] In some embodiments, the annealed silk fibroin protein
fragment film is immersing the wet silk fibroin protein fragment
film in 100% methanol for 60 minutes at room temperature. The
methanol annealing changed the composition of silk fibroin protein
fragment film from predominantly amorphous random coil to
crystalline antiparallel beta-sheet structure.
[0244] In some embodiments, the SPF as described herein can be used
to prepare SPF microparticles by precipitation with methanol.
Alternative flash drying, fluid-bed drying, spray drying or vacuum
drying can be applied to remove water from the silk solution. The
SPF powder can then be stored and handled without refrigeration or
other special handling procedures. In some embodiments, the SPF
powders comprise low molecular weight silk fibroin protein
fragments. In some embodiments, the SPF powders comprise
mid-molecular weight silk fibroin protein fragments. In some
embodiments, the SPF powders comprise a mixture of low molecular
weight silk fibroin protein fragments and mid-molecular weight silk
fibroin protein fragment.
[0245] In an embodiment, the water solubility of pure silk fibroin
protein fragments of the present disclosure is 50 to 100%. In an
embodiment, the water solubility of pure silk fibroin protein
fragments of the present disclosure is 60 to 100%. In an
embodiment, the water solubility of pure silk fibroin protein
fragments of the present disclosure is 70 to 100%. In an
embodiment, the water solubility of pure silk fibroin protein
fragments of the present disclosure is 80 to 100%. In an
embodiment, the water solubility is 90 to 100%. In an embodiment,
the silk fibroin fragments of the present disclosure are
non-soluble in aqueous solutions.
[0246] In an embodiment, the solubility of pure silk fibroin
protein fragments of the present disclosure in organic solutions is
50 to 100%. In an embodiment, the solubility of pure silk fibroin
protein fragments of the present disclosure in organic solutions is
60 to 100%. In an embodiment, the solubility of pure silk fibroin
protein fragments of the present disclosure in organic solutions is
70 to 100%. In an embodiment, the solubility of pure silk fibroin
protein fragments of the present disclosure in organic solutions is
80 to 100%. In an embodiment, the solubility of pure silk fibroin
protein fragments of the present disclosure in organic solutions is
90 to 100%. In an embodiment, the silk fibroin fragments of the
present disclosure are non-soluble in organic solutions.
[0247] In some embodiments, the silk fibroin protein fragments
comprise cationic quaternized amino acid residue (cationic
quaternized silk fibroin) with fatty alkyl groups, wherein the silk
fibroin protein fragments having any weight average molecular
weight and polydispersity described herein. In some embodiments,
the fatty alkyl group for quaternization of amine groups of the
silk fibroin protein fragment is selected from the group of
cocodimonium hydroxypropyl, hydroxypropyltrimonium, lauryidimonium
hydroxypropyl, steardimonium hydroxypropyl, quaternium-79, and
combinations thereof.
Silk Fibroin-Based Protein Fragments and Solutions Thereof
[0248] Provided herein are methods for producing pure and highly
scalable SPF as defined herein, including without limitation silk
fibroin or silk fibroin fragments, mixture compositions, for
example solutions, that may be used to coat at least a portion of a
substrate, or may be formed into usable fibers for weaving into
yarn, in particular to be used with a chemical modifier, or a
physical modifier. Methods of making silk fibroin or silk fibroin
fragments are known and are described for example in U.S. Pat. Nos.
9,187,538, 9,511,012, 9,517,191, 9,522,107, 9,522,108, 9,545,369,
and 10,166,177, all of which are incorporated herein in their
entireties. Methods of using silk fibroin or silk fibroin fragments
in coating applications are known and are described for example in
U.S. Patent Application Publications Nos. 20160222579, and
20160281294.
[0249] In some embodiments, the SPF as defined herein, including
without limitation silk fibroin or silk fibroin fragments, have an
average weight average molecular weight from about 1 kDa to about 5
kDa, from about 5 kDa to about 10 kDa, from about 6 kDa to about 17
kDa, from about 10 kDa to about 15 kDa, from about 15 kDa to about
20 kDa, from about 17 kDa to about 39 kDa, from about 20 kDa to
about 25 kDa, from about 25 kDa to about 30 kDa, from about 30 kDa
to about 35 kDa, from about 35 kDa to about 40 kDa, from about 39
kDa to about 80 kDa, from about 40 kDa to about 45 kDa, from about
45 kDa to about 50 kDa, from about 60 kDa to about 100 kDa, or from
about 80 kDa to about 144 kDa, wherein the SPF and/or silk fibroin
or silk fibroin fragments are chemically modified with a precursor
linker to form a silk-conjugate, and wherein in some embodiments
the silk fibroin or silk fibroin fragments are chemically linked to
a substrate through the linker. In some embodiments, the SPF as
defined herein, including without limitation silk fibroin or silk
fibroin fragments, have a polydispersity between 1 and about 5.0,
wherein the SPF and/or silk fibroin or silk fibroin fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the SPF and/or silk
fibroin or silk fibroin fragments are chemically linked to a
substrate through the linker.
[0250] As used herein, "average weight average molecular weight"
refers to an average of two or more values of weight average
molecular weight of silk fibroin or fragments thereof of the same
compositions, the two or more values determined by two or more
separate experimental readings.
[0251] As used herein, the terms "substantially sericin free" or
"substantially devoid of sericin" refer to silk fibers in which a
majority of the sericin protein has been removed. In an embodiment,
silk fibroin that is substantially devoid of sericin refers to silk
fibroin having between about 0.01% (w/w) and about 10.0% (w/w)
sericin. In an embodiment, silk fibroin that is substantially
devoid of sericin refers to silk fibroin having between about 0.01%
(w/w) and about 9.0% (w/w) sericin. In an embodiment, silk fibroin
that is substantially devoid of sericin refers to silk fibroin
having between about 0.01% (w/w) and about 8.0% (w/w) sericin. In
an embodiment, silk fibroin that is substantially devoid of sericin
refers to silk fibroin having between about 0.01% (w/w) and about
7.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid of sericin refers to silk fibroin having
between about 0.01% (w/w) and about 6.0% (w/w) sericin. In an
embodiment, silk fibroin that is substantially devoid of sericin
refers to silk fibroin having between about 0.01% (w/w) and about
5.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid of sericin refers to silk fibroin having
between about 0% (w/w) and about 4.0% (w/w) sericin. In an
embodiment, silk fibroin that is substantially devoid of sericin
refers to silk fibroin having between about 0.05% (w/w) and about
4.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid of sericin refers to silk fibroin having
between about 0.1% (w/w) and about 4.0% (w/w) sericin. In an
embodiment, silk fibroin that is substantially devoid of sericin
refers to silk fibroin having between about 0.5% (w/w) and about
4.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid of sericin refers to silk fibroin having
between about 1.0% (w/w) and about 4.0% (w/w) sericin. In an
embodiment, silk fibroin that is substantially devoid of sericin
refers to silk fibroin having between about 1.5% (w/w) and about
4.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid of sericin refers to silk fibroin having
between about 2.0% (w/w) and about 4.0% (w/w) sericin. In an
embodiment, silk fibroin that is substantially devoid of sericin
refers to silk fibroin having between about 2.5% (w/w) and about
4.0% (w/w) sericin. In an embodiment, silk fibroin that is
substantially devoid of sericin refers to silk fibroin having a
sericin content between about 0.01% (w/w) and about 0.1% (w/w). In
an embodiment, silk fibroin that is substantially devoid of sericin
refers to silk fibroin having a sericin content below about 0.1%
(w/w). In an embodiment, silk fibroin that is substantially devoid
of sericin refers to silk fibroin having a sericin content below
about 0.05% (w/w). In an embodiment, when a silk source is added to
a boiling (100.degree. C.) aqueous solution of sodium carbonate for
a treatment time of between about 30 minutes to about 60 minutes, a
degumming loss of about 26 wt. % to about 31 wt.% is obtained.
[0252] As used herein, the term "substantially homogeneous" may
refer to pure silk fibroin-based protein fragments that are
distributed in a normal distribution about an identified molecular
weight. As used herein, the term "substantially homogeneous" may
refer to an even distribution of additive, for example vitamin C,
throughout a composition of the present disclosure.
Textiles and Leathers Coated with Silk Fibroin-Based Protein
Fragments
[0253] As used herein, the term "washable" and "exhibiting
washability" means that a silk coated fabric of the present
disclosure is capable of being washed without shrinking, fading, or
the like.
[0254] As used herein, the term "textile" refers to a flexible
woven or non-woven material consisting of a network of natural or
artificial fibers often referred to as fabric, thread, or yarn. In
an embodiment, textiles can be used to fabricate clothing, shoes
and bags. In an embodiment, textiles can be used to fabricate
carpeting, upholstered furnishings, window shades, towels, and
coverings for tables, beds, and other flat surfaces. In an
embodiment, textiles can be used to fabricate flags, backpacks,
tents, nets, handkerchiefs, balloons, kites, sails, and
parachutes.
[0255] As used herein, the term "leather" refers to natural leather
and synthetic leather. Natural leather includes chrome-tanned
leather (e.g., tanned using chromium sulfate and other chromium
salts), vegetable-tanned leather (e.g., tanned using tannins),
aldehyde-tanned leather (also known as wet-white leather, e.g.,
tanned using glutaraldehyde or oxazolidine compounds), brain-tanned
leather, formaldehyde-tanned leather, Chamois leather (e.g., tanned
using cod oils), rose-tanned leather (e.g., tanned using rose otto
oils), synthetic-tanned leather (e.g., tanned using aromatic
polymers), alum-tanned leather, patent leather, Vachetta leather,
nubuck leather, and rawhide leather. Natural leather also includes
split leather, full-grain leather, top-grain leather, and
corrected-grain leather, the properties and preparation of which
are known to those of skill in the art. Synthetic leather includes
poromeric imitation leathers (e.g., polyurethane on polyester),
vinyl and polyamide felt fibers, polyurethane, polyvinyl chloride,
polyethylene (PE), polypropylene (PP), vinyl acetate copolymer
(EVA), polyamide, polyester, recycled polyester, textile-polymer
composite microfibers, corfan, koskin, leatherette, BIOTHANE.RTM.,
BIRKIBUC.RTM., BIRKO-FLOR.RTM., CLARINO.RTM., ECOLORICA.RTM.,
KYDEX.RTM., LORICA.RTM., NAUGAHYDE.RTM., REXINE.RTM., VEGETAN.RTM.,
FABRIKOID.RTM., or combinations thereof.
[0256] As used herein, the term "hand" refers to the feel of a
fabric, which may be further described as the feeling of softness,
crispness, dryness, silkiness, and combinations thereof. Fabric
hand is also referred to as "drape." A fabric with a hard hand is
coarse, rough, and generally less comfortable for the wearer. A
fabric with a soft hand is fluid and smooth, such as fine silk or
wool, and generally more comfortable for the wearer. Fabric hand
can be determined by comparison to collections of fabric samples,
or by use of methods such as the Kawabata Evaluation System (KES)
or the Fabric Assurance by Simple Testing (FAST) methods. Behera
and Hari, Ind. J. Fibre & Textile Res., 1994, 19, 168-71.
[0257] As used herein, the term "yarn" refers to a single or
multi-fiber construct.
[0258] As used herein, the term "bath coating" encompasses coating
a fabric in a batch, immersing a fabric in a bath, and submerging a
fabric in a bath. Concepts of bath coating are set forth in U.S.
Pat. No. 4,521,458, the entirety of which is incorporated by
reference.
[0259] In an embodiment, the disclosure provides a textile or
leather product coated with silk fibroin-based proteins or
fragments thereof, in particular wherein the coating includes one
or more chemical modifiers and/or physical modifiers. Silk fibroin
coated articles have been described in U.S. Patent Application
Publications Nos. 20160222579, 20160281294, and 20190003113, all of
which are incorporated herein in their entireties.
[0260] In some embodiments, the article includes one or more
substrates, the substrates including one or more of a fiber, a
thread, a yarn, a fabric, a textile, a cloth, or a hide. In some
embodiments, the fabric, textile, or cloth is woven or nonwoven. In
some embodiments, the fiber, thread, or yarn includes one or more
of polyester, recycled polyester, Mylar, cotton, nylon, recycled
nylon, polyester-polyurethane copolymer, rayon, acetate, aramid
(aromatic polyamide), acrylic, ingeo (polylactide), lurex
(polyamide-polyester), olefin (polyethylene-polypropylene), and
combinations thereof. In some embodiments, the fiber, thread, or
yarn includes one or more of alpaca fiber, alpaca fleece, alpaca
wool, lama fiber, lama fleece, lama wool, cotton, cashmere, sheep
fiber, sheep fleece, sheep wool, byssus, chiengora, qiviut, yak,
rabbit, lambswool, mohair wool, camel hair, angora wool, silkworm
silk, abaca fiber, coir fiber, flax fiber, jute fiber, kapok fiber,
kenaf fiber, raffia fiber, bamboo fiber, hemp, modal fiber, pina,
ramie, sisal, and soy protein fiber. In some embodiments, the
fiber, thread, or yarn includes one or more of mineral wool,
mineral cotton, man-made mineral fiber, fiberglass, glass,
glasswool, stone wool, rock wool, slagwool, glass filaments,
asbestos fibers, and ceramic fibers.
[0261] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the SPF and/or silk based proteins or fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the fiber or
yarn through the linker, wherein the article is a fabric, wherein
the fabric exhibits an improved property, wherein the improved
property is an accumulative one-way moisture transport index
selected from the group consisting of greater than 40%, greater
than 60%, greater than 80%, greater than 100%, greater than 120%,
greater than 140%, greater than 160%, and greater than 180%. In an
embodiment, the foregoing improved property, or any other improved
property described herein, is determined after a period of machine
washing (e.g., by home laundering machine washing) cycles selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles,
4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0262] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the fabric
exhibits an improved property, wherein the improved property is an
accumulative one way transport capability increase relative to
uncoated fabric selected from the group consisting of 1.2 fold, 1.5
fold, 2.0 fold, 3.0 fold, 4.0 fold, 5.0 fold, and 10 fold. In an
embodiment, the foregoing improved property is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0263] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the fabric
exhibits an improved property, wherein the improved property is an
overall moisture management capability selected from the group
consisting of greater than 0.05, greater than 0.10, greater than
0.15, greater than 0.20, greater than 0.25, greater than 0.30,
greater than 0.35, greater than 0.40, greater than 0.50, greater
than 0.60, greater than 0.70, and greater than 0.80. In an
embodiment, the foregoing improved property is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0264] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the fabric
exhibits substantially no increase in microbial growth after a
number of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0265] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the fabric
exhibits substantially no increase in microbial growth after a
number of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles, and wherein the
microbial growth is microbial growth of a microbe selected from the
group consisting of Staphylococcus aureus, Klebisiella pneumoniae,
and combinations thereof. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0266] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the fabric
exhibits substantially no increase in microbial growth after a
number of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles, and wherein the
microbial growth is microbial growth of a microbe selected from the
group consisting of Staphylococcus aureus, Klebisiella pneumoniae,
and combinations thereof.
[0267] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the fabric
exhibits substantially no increase in microbial growth after a
number of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles, wherein the
microbial growth is microbial growth of a microbe selected from the
group consisting of Staphylococcus aureus, Klebisiella pneumoniae,
and combinations thereof, wherein the microbial growth is reduced
by a percentage selected from the group consisting of 50%, 100%,
500%, 1000%, 2000%, and 3000% compared to an uncoated fabric.
[0268] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the coating is
applied to the fabric at the fiber level prior to forming the
fabric.
[0269] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the coating is
applied to the fabric at the fabric level or garment level (e.g.,
after manufacture of a garment from fabrics, leathers, and/or other
materials).
[0270] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level or garment level, and
wherein the fabric is bath coated.
[0271] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level or garment level, and
wherein the fabric is spray coated.
[0272] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level or garment level, and
wherein the fabric is coated with a stencil.
[0273] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level or garment level, and
wherein the coating is applied to at least one side of the fabric
using a method selected from the group consisting of a bath coating
process, a spray coating process, a stencil (i.e., screen) process,
a silk-foam based process, a roller-based process, a magnetic
roller process, a knife process, a transfer process, a foam
process, a lacquering process, and a printing process.
[0274] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level, and wherein the coating
is applied to both sides of the fabric using a method selected from
the group consisting of a bath coating process, a spray coating
process, a stencil (i.e., screen) process, a silk-foam based
process, a roller-based process, a magnetic roller process, a knife
process, a transfer process, a foam process, a lacquering process,
and a printing process.
[0275] In any of the foregoing embodiment, the coating may be
applied at the fabric garment level by any of the methods disclosed
herein to recondition fabrics or garments. For example, such
reconditioning using a coating comprising silk based proteins or
fragments thereof may be performed as part of washing or cleaning a
fabric or garment.
[0276] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, and wherein the coating has a thickness of about one
nanolayer.
[0277] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, and wherein the coating has a thickness selected from the
group consisting of about 5 nm, about 10 nm, about 15 nm, about 20
nm, about 25 nm, about 50 nm, about 100 nm, about 200 nm, about 500
nm, about 1 .mu.m, about 5 .mu.m, about 10 .mu.m, and about 20
.mu.m.
[0278] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the coating is
adsorbed on the fabric.
[0279] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the coating is
attached to the fabric through chemical, enzymatic, thermal, or
irradiative cross-linking.
[0280] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level, and wherein the hand of
the coated fabric is improved relative to an uncoated fabric.
[0281] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level, and wherein the hand of
the coated fabric is improved relative to an uncoated fabric,
wherein the hand of the coated fabric that is improved is selected
from the group consisting of softness, crispness, dryness,
silkiness, and combinations thereof.
[0282] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
applied to the fabric at the fabric level, and wherein the pilling
of the fabric is improved relative to an uncoated fabric.
[0283] In an embodiment, the silk coating is applied using a bath
process, a screen (or stencil) process, a spray process, a
silk-foam based process, a roller based process, a tenter frame
process, or a pad-dry-cure process.
[0284] In an embodiment, a fiber or a yarn comprises a synthetic
fiber or yarn, including polyester, recycled polyester, Mylar,
cotton, nylon, recycled nylon, polyester-polyurethane copolymer,
rayon, acetate, aramid (aromatic polyamide), acrylic, ingeo
(polylactide), lurex (polyamide-polyester), olefin
(polyethylene-polypropylene), and combinations thereof.
[0285] In an embodiment, a fiber or a yarn comprises a natural
fiber or yarn (e.g., from animal or plant sources), including
alpaca fiber, alpaca fleece, alpaca wool, lama fiber, lama fleece,
lama wool, cotton, cashmere and sheep fiber, sheep fleece, sheep
wool, byssus, chiengora, qiviut, yak, rabbit, lambswool, mohair
wool, camel hair, angora wool, silkworm silk, abaca fiber, coir
fiber, flax fiber, jute fiber, kapok fiber, kenaf fiber, raffia
fiber, bamboo fiber, hemp, modal fiber, pina, ramie, sisal, and soy
protein fiber.
[0286] In an embodiment, a fiber or a yarn comprises a mineral
fiber, also known as mineral wool, mineral cotton, or man-made
mineral fiber, including fiberglass, glass, glasswool, stone wool,
rock wool, slagwool, glass filaments, asbestos fibers, and ceramic
fibers.
[0287] In an embodiment, a water-soluble silk coating may be used
as an adhesive or binder for binding particles to fabrics or for
binding fabrics, wherein the silk based proteins or fragments in
the water-soluble silk coating are chemically modified with a
precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk based proteins or fragments thereof are
chemically linked to the fiber or yarn through the linker. In an
embodiment, an article comprises a fabric bound to another fabric
using a silk coating. In an embodiment, an article comprises a
fabric with particles bound to the fabric using a silk
adhesive.
[0288] In an embodiment, the coating is applied to an article
including a fabric at the yarn level. In an embodiment, the coating
is applied at the fabric level. In an embodiment, the coating has a
thickness selected from the group consisting of about 5 nm, about
10 nm, about 15 nm, about 20 nm, about 25 nm, about 50 nm, about
100 nm, about 200 nm, about 500 nm, about 1 .mu.m, about 5 .mu.m,
about 10 .mu.m, and about 20 .mu.m. In an embodiment, the coating
has a thickness range selected from the group consisting of about 5
nm to about 100 nm, about 100 nm to about 200 nm, about 200 nm to
about 500 nm, about 1 .mu.m to about 2 .mu.m, about 2 .mu.m to
about 5 .mu.m, about 5 .mu.m to about 10 .mu.m, and about 10 .mu.m
to about 20 .mu.m.
[0289] In an embodiment, a fiber or a yarn is treated with a
polymer, such as polyglycolide (PGA), polyethylene glycols,
copolymers of glycolide, glycolide/L-lactide copolymers (PGA/PLLA),
glycolide/trimethylene carbonate copolymers (PGA/TMC), polylactides
(PLA), stereocopolymers of PLA, poly-L-lactide (PLLA),
poly-DL-lactide (PDLLA), L-lactide/DL-lactide copolymers,
co-polymers of PLA, lactide/tetramethylglycolide copolymers,
lactide/trimethylene carbonate copolymers,
lactide/.delta.-valerolactone copolymers,
lactide/.epsilon.-caprolactone copolymers, polydepsipeptides,
PLA/polyethylene oxide copolymers, unsymmetrically 3,6-substituted
poly-1,4-dioxane-2,5-diones, poly-.beta.-hydroxybutyrate (PHBA),
PHBA/.beta.-hydroxyvalerate copolymers (PHBA/HVA),
poly-.beta.-hydroxypropionate (PHPA), poly-p-dioxanone (PDS),
poly-.delta.-valerolactone, poly-.epsilon.-caprolactone,
methylmethacrylate-N-vinyl pyrrolidine copolymers, polyesteramides,
polyesters of oxalic acid, polydihydropyrans,
polyalkyl-2-cyanoacrylates, polyurethanes (PU), polyvinylalcohols
(PVA), polypeptides, poly-.beta.-malic acid (PMLA),
poly-.beta.-alkanoic acids, polyvinylalcohol (PVA),
polyethyleneoxide (PEO), chitine polymers, polyethylene,
polypropylene, polyasetal, polyamides, polyesters, recycled
polyesters, polysulphone, polyether ether ketone, polyethylene
terephthalate, polycarbonate, polyaryl ether ketone, and polyether
ketone ketone.
[0290] In an embodiment, the silk coating surface can be modified
silk crystals that range in size from nm to .mu.m.
[0291] The criterion for "visibility" is satisfied by any one of
the following: a change in the surface character of the textile;
the silk coating fills the interstices where the yarns intersect;
or the silk coating blurs or obscures the weave.
[0292] In an embodiment, a SPF as defined herein, for example, and
without limitation, silk based protein or fragment solution may be
utilized to coat at least a portion of a fabric which can be used
to create a textile. In an embodiment, a silk based protein or
fragment solution may be weaved into yarn that can be used as a
fabric in a textile. In an embodiment, a silk based protein or
fragment solution may be used to coat a fiber. In an embodiment,
the disclosure provides an article comprising a silk based protein
or fragment solution coating at least a portion of a fabric or a
textile. In an embodiment, the disclosure provides an article
comprising a silk based protein or fragment solution coating a
yarn. In an embodiment, the disclosure provides an article
comprising a silk based protein or fragment solution coating a
fiber, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker.
[0293] There is disclosed a textile that is at least partially
surface treated with an aqueous solution of SPF as defined herein,
for example, and without limitation, silk fibroin-based protein
fragments of the present disclosure so as to result in a silk
coating on the textile, wherein the silk based proteins or
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the fiber or
yarn through the linker. In an embodiment, the silk coating of the
present disclosure is available in a spray can and can be sprayed
on any textile by a consumer. In an embodiment, a textile
comprising a silk coating of the present disclosure is sold to a
consumer. In an embodiment, a textile of the present disclosure is
used in constructing action sportswear/apparel. In an embodiment, a
silk coating of the present disclosure is positioned on the
underlining of apparel. In an embodiment, a silk coating of the
present disclosure is positioned on the shell, the lining, or the
interlining of apparel. In an embodiment, apparel is partially made
from a silk coated textile of the present disclosure and partially
made from an uncoated textile. In an embodiment, apparel partially
made from a silk coated textile and partially made from an uncoated
textile combines an uncoated inert synthetic material with a silk
coated inert synthetic material. Examples of inert synthetic
material include, but are not limited to, polyester, recycled
polyester, polyamide, polyaramid, polytetrafluoroethylene,
polyethylene, polypropylene, polyurethane, silicone, mixtures of
polyurethane and polyethyleneglycol, ultrahigh molecular weight
polyethylene, high-performance polyethylene, and mixtures thereof.
In an embodiment, apparel partially made from a silk coated textile
and partially made from an uncoated textile combines an elastomeric
material at least partially covered with a silk coating of the
present disclosure. In an embodiment, the percentage of silk to
elastomeric material can be varied to achieve desired shrink or
wrinkle resistant properties.
[0294] In an embodiment, a silk coating of the present disclosure
is visible. In an embodiment, a silk coating of the present
disclosure positioned on apparel helps control skin temperature. In
an embodiment, a silk coating of the present disclosure positioned
on apparel helps control fluid transfer away from the skin. In an
embodiment, a silk coating of the present disclosure positioned on
apparel has a soft feel against the skin decreasing abrasions from
fabric on skin. In an embodiment, a silk coating of the present
disclosure positioned on a textile has properties that confer at
least one of wrinkle resistance, shrinkage resistance, or machine
washability to the textile. In an embodiment, a silk coated textile
of the present disclosure is 100% machine washable and dry
cleanable. In an embodiment, a silk coated textile of the present
disclosure is 100% waterproof. In an embodiment, a silk coated
textile of the present disclosure is wrinkle resistant. In an
embodiment, a silk coated textile of the present disclosure is
shrink resistant. In an embodiment, a silk coated textile of the
present disclosure has the qualities of being waterproof,
breathable, and elastic and possess a number of other qualities
which are highly desirable in action sportswear. In an embodiment,
a silk coated textile of the present disclosure manufactured from a
silk fabric of the present disclosure further includes LYCRA.RTM.
brand spandex fibers.
[0295] In an embodiment, a textile at least partially coated with
an aqueous solution of SPF as defined herein, for example, and
without limitation, silk fibroin-based protein fragments of the
present disclosure is a breathable fabric. In an embodiment, a
textile at least partially coated with an aqueous solution of SPF
as defined herein, for example, and without limitation, silk
fibroin-based protein fragments of the present disclosure is a
water-resistant fabric. In an embodiment, a textile at least
partially coated with an aqueous solution of SPF as defined herein,
for example, and without limitation, silk fibroin-based protein
fragments of the present disclosure is a shrink-resistant fabric.
In an embodiment, a textile at least partially coated with an
aqueous solution of SPF as defined herein, for example, and without
limitation, silk fibroin-based protein fragments of the present
disclosure is a machine-washable fabric. In an embodiment, a
textile at least partially coated with an aqueous solution of SPF
as defined herein, for example, and without limitation, silk
fibroin-based protein fragments of the present disclosure is a
wrinkle resistant fabric. In an embodiment, textile at least
partially coated with an aqueous solution of SPF as defined herein,
for example, and without limitation, silk fibroin-based protein
fragments of the present disclosure provides moisture and vitamins
to the skin.
[0296] In an embodiment, an aqueous solution of SPF as defined
herein, for example, and without limitation, silk fibroin-based
protein fragments of the present disclosure is used to coat a
textile or leather, wherein the silk based proteins or fragments
are chemically modified with a precursor linker to form a
silk-conjugate. In an embodiment, the concentration of silk in the
solution ranges from about 0.1% to about 20.0%. In an embodiment,
the concentration of silk in the solution ranges from about 0.1% to
about 15.0%. In an embodiment, the concentration of silk in the
solution ranges from about 0.5% to about 10.0%. In an embodiment,
the concentration of silk in the solution ranges from about 1.0% to
about 5.0%. In an embodiment, an aqueous solution of pure silk
fibroin-based protein fragments of the present disclosure is
applied directly to a fabric. Alternatively, silk microsphere and
any additives may be used for coating a fabric. In an embodiment,
additives can be added to an aqueous solution of pure silk
fibroin-based protein fragments of the present disclosure before
coating (e.g., alcohols) to further enhance material properties. In
an embodiment, a silk coating of the present disclosure can have a
pattern to optimize properties of the silk on the fabric. In an
embodiment, a coating is applied to a fabric under tension and/or
lax to vary penetration in to the fabric.
[0297] In an embodiment, a silk coating of the present disclosure
can be applied at the yarn level, followed by creation of a fabric
once the yarn is coated. In an embodiment, an aqueous solution of
pure silk fibroin-based protein fragments of the present disclosure
can be spun into fibers to make a silk fabric and/or silk fabric
blend with other materials known in the apparel industry.
Uses of Textiles and Leathers Coated with Silk Fibroin-Based
Protein Fragments in Apparel and Garment Applications
[0298] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article exhibits an improved color retention
property. Without being bound by any specific theory, it is
postulated that the coating prevents the article from color
degradation by separating the fiber or yarn from air or from
detergents during washing.
[0299] Methods of testing the color retention property of an
article are well within the knowledge of one skilled in the art. A
specific method of testing of the color retention property of a
fabric is described in U.S. Pat. No. 5,142,292, which is
incorporated herein by reference in its entirety.
[0300] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits an improved color retention property.
[0301] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
exhibits an improved color retention property.
[0302] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article exhibits an
improved color retention property.
[0303] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
exhibits an improved color retention property.
[0304] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article exhibits an improved color retention
property.
[0305] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article exhibits an improved color
retention property.
[0306] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
exhibits an improved color retention property.
[0307] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article exhibits an improved
color retention property.
[0308] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits an improved color retention property. In an embodiment,
the foregoing color retention property of the fabric is determined
after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an
embodiment, the foregoing improved property, or any other improved
property described herein, is determined after a period of machine
washing (e.g., by home laundering machine washing) cycles selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles,
4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0309] In an embodiment, a textile or leather of the present
disclosure exhibits an improved color retention property. In an
embodiment, the foregoing improved color retention property of the
textile is determined after a period of machine washing cycles
selected from the group consisting of 5 cycles, 10 cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0310] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is resistant to microbial (including
bacterial and fungal) growth.
[0311] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
resistant to microbial (including bacterial and fungal) growth.
[0312] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is resistant to microbial (including bacterial and fungal)
growth.
[0313] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article is resistant
to microbial (including bacterial and fungal) growth.
[0314] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
is resistant to microbial (including bacterial and fungal)
growth.
[0315] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article is resistant to microbial (including
bacterial and fungal) growth.
[0316] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article is resistant to microbial
(including bacterial and fungal) growth.
[0317] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
is resistant to microbial (including bacterial and fungal)
growth.
[0318] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article is resistant to
microbial (including bacterial and fungal) growth.
[0319] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
resistant to microbial (including bacterial and fungal) growth. In
an embodiment, the foregoing resistant to microbial (including
bacterial and fungal) growth property of the fabric is determined
after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an
embodiment, the foregoing improved property, or any other improved
property described herein, is determined after a period of machine
washing (e.g., by home laundering machine washing) cycles selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles,
4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0320] In an embodiment, a textile or leather of the present
disclosure exhibits resistant to microbial (including bacterial and
fungal) growth property. In an embodiment, the foregoing resistant
to microbial (including bacterial and fungal) growth property of
the textile is determined after a period of machine washing cycles
selected from the group consisting of 5 cycles, 10 cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0321] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is resistant to the buildup of static
electrical charge.
[0322] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
resistant to the buildup of static electrical charge.
[0323] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is resistant to the buildup of static electrical charge.
[0324] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article is resistant
to the buildup of static electrical charge.
[0325] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
is resistant to the buildup of static electrical charge.
[0326] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article is resistant to the buildup of static
electrical charge.
[0327] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article is resistant to the buildup of
static electrical charge.
[0328] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
is resistant to the buildup of static electrical charge.
[0329] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article is resistant to the
buildup of static electrical charge.
[0330] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
resistant to the buildup of static electrical charge. In an
embodiment, the foregoing resistant to the buildup of static
electrical charge property of the fabric is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles.
[0331] In an embodiment, a textile or leather of the present
disclosure exhibits resistant to the buildup of static electrical
charge property. In an embodiment, the foregoing resistant to the
buildup of static electrical charge property of the textile is
determined after a period of machine washing cycles selected from
the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an embodiment, the foregoing improved property, or any
other improved property described herein, is determined after a
period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14
cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40
cycles, 45 cycles, and 50 cycles.
[0332] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is mildew resistant.
[0333] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
mildew resistant.
[0334] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is mildew resistant.
[0335] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article is mildew
resistant.
[0336] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
is mildew resistant.
[0337] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article is mildew resistant.
[0338] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article is mildew resistant.
[0339] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
is mildew resistant.
[0340] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article is mildew
resistant.
[0341] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
mildew resistant. In an embodiment, the foregoing mildew resistant
property of the fabric is determined after a period of machine
washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing
improved property, or any other improved property described herein,
is determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0342] In an embodiment, a textile or leather of the present
disclosure exhibits mildew resistant property. In an embodiment,
the foregoing mildew resistant property of the textile is
determined after a period of machine washing cycles selected from
the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an embodiment, the foregoing improved property, or any
other improved property described herein, is determined after a
period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14
cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40
cycles, 45 cycles, and 50 cycles.
[0343] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the coating is transparent.
[0344] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the coating is transparent.
[0345] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the coating
is transparent.
[0346] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the coating is
transparent.
[0347] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the coating
is transparent.
[0348] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the coating is transparent.
[0349] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the coating is transparent.
[0350] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the coating
is transparent.
[0351] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the coating is transparent.
[0352] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating is
transparent. In an embodiment, the foregoing transparent property
of the coating is determined after a period of machine washing
cycles selected from the group consisting of 5 cycles, 10 cycles,
25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0353] In an embodiment, a textile or leather comprises a silk
coating of the present disclosure, wherein the silk coating is
transparent. In an embodiment, the foregoing transparent property
of the coating is determined after a period of machine washing
cycles selected from the group consisting of 5 cycles, 10 cycles,
25 cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0354] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is resistant to freeze-thaw cycle
damage.
[0355] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
resistant to freeze-thaw cycle damage.
[0356] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is resistant to freeze-thaw cycle damage.
[0357] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article is resistant
to freeze-thaw cycle damage.
[0358] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
is resistant to freeze-thaw cycle damage.
[0359] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article is resistant to freeze-thaw cycle
damage.
[0360] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article is resistant to freeze-thaw
cycle damage.
[0361] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
is resistant to freeze-thaw cycle damage.
[0362] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article is resistant to
freeze-thaw cycle damage.
[0363] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
resistant to freeze-thaw cycle damage. In an embodiment, the
foregoing resistant to freeze-thaw cycle damage property of the
fabric is determined after a period of machine washing cycles
selected from the group consisting of 5 cycles, 10 cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0364] In an embodiment, a textile or leather of the present
disclosure exhibits resistant to freeze-thaw cycle damage. In an
embodiment, the foregoing resistant to freeze-thaw cycle damage
property of the textile is determined after a period of machine
washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing
improved property, or any other improved property described herein,
is determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0365] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the coating provides protection from abrasion.
[0366] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating
provides protection from abrasion.
[0367] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the coating
provides protection from abrasion.
[0368] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the coating provides
protection from abrasion.
[0369] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the coating
provides protection from abrasion.
[0370] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the coating provides protection from abrasion.
[0371] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the coating provides protection from
abrasion.
[0372] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the coating
provides protection from abrasion.
[0373] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the coating provides protection
from abrasion.
[0374] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the coating
provides protection from abrasion. In an embodiment, the foregoing
abrasion resistant property of the fabric is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0375] In an embodiment, a textile or leather of the present
disclosure exhibits abrasion resistant. In an embodiment, the
foregoing abrasion resistant property of the textile is determined
after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an
embodiment, the foregoing improved property, or any other improved
property described herein, is determined after a period of machine
washing (e.g., by home laundering machine washing) cycles selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles,
4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0376] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article exhibits the property of blocking
ultraviolet (UV) radiation.
[0377] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits the property of blocking ultraviolet (UV) radiation.
[0378] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
exhibits the property of blocking ultraviolet (UV) radiation.
[0379] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article exhibits the
property of blocking ultraviolet (UV) radiation.
[0380] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
exhibits the property of blocking ultraviolet (UV) radiation.
[0381] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article exhibits the property of blocking
ultraviolet (UV) radiation.
[0382] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article exhibits the property of
blocking ultraviolet (UV) radiation.
[0383] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
exhibits the property of blocking ultraviolet (UV) radiation.
[0384] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article exhibits the property
of blocking ultraviolet (UV) radiation.
[0385] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits the property of blocking ultraviolet (UV) radiation. In an
embodiment, the foregoing UV blocking property of the fabric is
determined after a period of machine washing cycles selected from
the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an embodiment, the foregoing improved property, or any
other improved property described herein, is determined after a
period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14
cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40
cycles, 45 cycles, and 50 cycles.
[0386] In an embodiment, a textile or leather of the present
disclosure exhibits UV blocking property. In an embodiment, the
foregoing UV blocking property of the textile is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0387] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the garment regulates the body temperature of a
wearer.
[0388] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the garment
regulates the body temperature of a wearer.
[0389] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the garment
regulates the body temperature of a wearer.
[0390] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the garment regulates
the body temperature of a wearer.
[0391] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the garment
regulates the body temperature of a wearer.
[0392] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the garment regulates the body temperature of a
wearer.
[0393] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the garment regulates the body temperature
of a wearer.
[0394] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the garment
regulates the body temperature of a wearer.
[0395] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the garment regulates the body
temperature of a wearer.
[0396] In an embodiment, the disclosure provides a garment
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the garment
regulates the body temperature of a wearer. In an embodiment, the
foregoing temperature regulation property of the fabric is
determined after a period of machine washing cycles selected from
the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an embodiment, the foregoing improved property, or any
other improved property described herein, is determined after a
period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14
cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40
cycles, 45 cycles, and 50 cycles.
[0397] In an embodiment, a textile or leather of the present
disclosure exhibits a temperature regulation property. In an
embodiment, the foregoing temperature regulation property of the
textile is determined after a period of machine washing cycles
selected from the group consisting of 5 cycles, 10 cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0398] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, and wherein the article is tear resistant.
[0399] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the article is
tear resistant.
[0400] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, and wherein the
article is tear resistant.
[0401] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, and wherein the article is tear
resistant.
[0402] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, and wherein the
article is tear resistant.
[0403] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, and wherein the article is tear resistant.
[0404] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, and wherein the article is tear resistant.
[0405] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, and wherein the
article is tear resistant.
[0406] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, and wherein the article is tear
resistant.
[0407] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the article is
tear resistant. In an embodiment, the foregoing tear resistant
property of the fabric is determined after a period of machine
washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing
improved property, or any other improved property described herein,
is determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0408] In an embodiment, a textile or leather of the present
disclosure exhibits a tear resistant property. In an embodiment,
the foregoing tear resistant property of the textile is determined
after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an
embodiment, the foregoing improved property, or any other improved
property described herein, is determined after a period of machine
washing (e.g., by home laundering machine washing) cycles selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles,
4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0409] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the elasticity of the article is improved.
[0410] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the elasticity of the article is reduced.
[0411] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the
elasticity of the article is improved.
[0412] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the
elasticity of the article is reduced.
[0413] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article exhibits a rebound dampening property.
Without being bound by any specific theory, it is postulated that
the coating prevents the article from returning to the original
shape or orientation, and results in the rebound dampening
property.
[0414] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits a rebound dampening property.
[0415] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
exhibits a rebound dampening property.
[0416] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article exhibits a
rebound dampening property.
[0417] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
exhibits a rebound dampening property.
[0418] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article exhibits a rebound dampening
property.
[0419] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article exhibits a rebound dampening
property.
[0420] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
exhibits a rebound dampening property.
[0421] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article exhibits a rebound
dampening property.
[0422] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits a rebound dampening property. In an embodiment, the
foregoing rebound dampening property of the fabric is determined
after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an
embodiment, the foregoing improved property, or any other improved
property described herein, is determined after a period of machine
washing (e.g., by home laundering machine washing) cycles selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles,
4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0423] In an embodiment, a textile or leather of the present
disclosure exhibits a rebound dampening property. In an embodiment,
the foregoing rebound dampening property of the textile is
determined after a period of machine washing cycles selected from
the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an embodiment, the foregoing improved property, or any
other improved property described herein, is determined after a
period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14
cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40
cycles, 45 cycles, and 50 cycles.
[0424] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article exhibits an anti-itch property.
[0425] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits an anti-itch property.
[0426] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
exhibits an anti-itch property.
[0427] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article exhibits an
anti-itch property.
[0428] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
exhibits an anti-itch property.
[0429] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article exhibits an anti-itch property.
[0430] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article exhibits an anti-itch
property.
[0431] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
exhibits an anti-itch property.
[0432] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article exhibits an anti-itch
property.
[0433] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits an anti-itch property. In an embodiment, the foregoing
anti-itch property of the fabric is determined after a period of
machine washing cycles selected from the group consisting of 5
cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment, the
foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0434] In an embodiment, a textile or leather of the present
disclosure exhibits an anti-itch property. In an embodiment, the
foregoing anti-itch property of the textile is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0435] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article exhibits an improved insulation/warmth
property.
[0436] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits an improved insulation/warmth property.
[0437] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
exhibits an improved insulation/warmth property.
[0438] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article exhibits an
improved insulation/warmth property.
[0439] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
exhibits an improved insulation/warmth property.
[0440] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article exhibits an improved insulation/warmth
property.
[0441] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article
exhibits an improved insulation/warmth property. In an embodiment,
the foregoing improved insulation/warmth property of the fabric is
determined after a period of machine washing cycles selected from
the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an embodiment, the foregoing improved property, or any
other improved property described herein, is determined after a
period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14
cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40
cycles, 45 cycles, and 50 cycles.
[0442] In an embodiment, a textile or leather of the present
disclosure exhibits improved an insulation/warmth property. In an
embodiment, the foregoing improved insulation/warmth property of
the textile is determined after a period of machine washing cycles
selected from the group consisting of 5 cycles, 10 cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0443] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is wrinkle resistant.
[0444] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
wrinkle resistant.
[0445] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is wrinkle resistant.
[0446] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article is wrinkle
resistant.
[0447] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
is wrinkle resistant.
[0448] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article is wrinkle resistant.
[0449] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article is wrinkle resistant.
[0450] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
is wrinkle resistant.
[0451] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article is wrinkle
resistant.
[0452] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
wrinkle resistant. In an embodiment, the foregoing wrinkle
resistant property of the fabric is determined after a period of
machine washing cycles selected from the group consisting of 5
cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment, the
foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0453] In an embodiment, a textile or leather of the present
disclosure exhibits wrinkle resistant property. In an embodiment,
the foregoing wrinkle resistant property of the textile is
determined after a period of machine washing cycles selected from
the group consisting of 5 cycles, 10 cycles, 25 cycles, and 50
cycles. In an embodiment, the foregoing improved property, or any
other improved property described herein, is determined after a
period of machine washing (e.g., by home laundering machine
washing) cycles selected from the group consisting of 0 cycles, 1
cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles, 7 cycles,
8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14
cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40
cycles, 45 cycles, and 50 cycles.
[0454] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is stain resistant.
[0455] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
stain resistant.
[0456] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is stain resistant.
[0457] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article is stain
resistant.
[0458] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
is stain resistant.
[0459] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article is stain resistant.
[0460] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article is stain resistant.
[0461] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
is stain resistant.
[0462] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article is stain
resistant.
[0463] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
stain resistant. In an embodiment, the foregoing stain resistant
property of the fabric is determined after a period of machine
washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing
improved property, or any other improved property described herein,
is determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0464] In an embodiment, a textile or leather of the present
disclosure exhibits stain resistant property. In an embodiment, the
foregoing stain resistant property of the textile is determined
after a period of machine washing cycles selected from the group
consisting of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an
embodiment, the foregoing improved property, or any other improved
property described herein, is determined after a period of machine
washing (e.g., by home laundering machine washing) cycles selected
from the group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles,
4 cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0465] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is sticky. Without being bound to any
specific theory, it is postulated that the coating provides
stickiness and maintains stickiness.
[0466] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
sticky.
[0467] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is sticky.
[0468] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
sticky. In an embodiment, the foregoing sticky property of the
fabric is determined after a period of machine washing cycles
selected from the group consisting of 5 cycles, 10 cycles, 25
cycles, and 50 cycles. In an embodiment, the foregoing improved
property, or any other improved property described herein, is
determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0469] In an embodiment, a textile or leather of the present
disclosure exhibits sticky property. In an embodiment, the
foregoing sticky property of the textile is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0470] In an embodiment, the disclosure provides an article
comprising a textile or leather coated with silk fibroin-based
proteins or fragments thereof, wherein the silk based proteins or
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the fiber or
yarn through the linker, wherein the article exhibits improved
flame resistance relative to an uncoated textile. In an embodiment,
the disclosure provides an article comprising a textile or leather
coated with silk fibroin-based proteins or fragments thereof,
wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article exhibits equal flame resistance
relative to an uncoated textile or leather. In an embodiment, the
disclosure provides an article comprising a textile or leather
coated with silk fibroin-based proteins or fragments thereof,
wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article exhibits equal flame resistance
relative to an uncoated textile or leather, wherein an alternative
textile or leather coating exhibits reduced flame resistance. In an
embodiment, the disclosure provides an article comprising a textile
or leather coated with silk fibroin-based proteins or fragments
thereof, wherein the silk based proteins or fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the fiber or
yarn through the linker, wherein the article exhibits improved
resistance to fire relative to an uncoated textile or leather,
wherein the improved resistance to fire is determined by a
flammability test. In an embodiment, the flammability test measures
afterflame time, afterglow time, char length, and the observation
of fabric melting or dripping.
[0471] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is flame resistant.
[0472] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the article is
flame resistant.
[0473] In an embodiment, the disclosure provides an article
comprising a polyester having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is flame resistant.
[0474] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof
comprise silk fibroin-based proteins or protein fragments having
about 0.01% (w/w) to about 10% (w/w) sericin, wherein the article
is flame resistant.
[0475] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the article is flame
resistant.
[0476] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the article
is flame resistant.
[0477] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments thereof are
selected from the group consisting of natural silk based proteins
or fragments thereof, recombinant silk based proteins or fragments
thereof, and combinations thereof, wherein the silk based proteins
or fragments thereof are natural silk based proteins or fragments
thereof that are selected from the group consisting of spider silk
based proteins or fragments thereof, silkworm silk based proteins
or fragments thereof, and combinations thereof, wherein the natural
silk based proteins or fragments are silkworm silk based proteins
or fragments thereof, and the silkworm silk based proteins or
fragments thereof is Bombyx mori silk based proteins or fragments
thereof, wherein the article is flame resistant.
[0478] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the silk based proteins or fragments comprise silk
and a copolymer, wherein the article is flame resistant.
[0479] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is natural fiber or
yarn selected from the group consisting of cotton, alpaca fleece,
alpaca wool, lama fleece, lama wool, cotton, cashmere, sheep
fleece, sheep wool, and combinations thereof, wherein the article
is flame resistant.
[0480] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the fiber or yarn is selected from the group
consisting of natural fiber or yarn, synthetic fiber or yarn, or
combinations thereof, wherein the fiber or yarn is synthetic fiber
or yarn selected from the group consisting of polyester, recycled
polyester, nylon, recycled nylon, polyester-polyurethane copolymer,
and combinations thereof, wherein the article is flame
resistant.
[0481] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, wherein the fabric is
flame resistant. In an embodiment, the foregoing flame resistant
property of the fabric is determined after a period of machine
washing cycles selected from the group consisting of 5 cycles, 10
cycles, 25 cycles, and 50 cycles. In an embodiment, the foregoing
improved property, or any other improved property described herein,
is determined after a period of machine washing (e.g., by home
laundering machine washing) cycles selected from the group
consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5
cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11
cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25
cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50
cycles.
[0482] In an embodiment, a textile or leather of the present
disclosure is flame resistant. In an embodiment, the foregoing
flame resistant property of the textile is determined after a
period of machine washing cycles selected from the group consisting
of 5 cycles, 10 cycles, 25 cycles, and 50 cycles. In an embodiment,
the foregoing improved property, or any other improved property
described herein, is determined after a period of machine washing
(e.g., by home laundering machine washing) cycles selected from the
group consisting of 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4
cycles, 5 cycles, 6 cycles, 7 cycles, 8 cycles, 9 cycles, 10
cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20
cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and
50 cycles.
[0483] In an embodiment, the disclosure provides a leather coated
with coating, wherein the coating comprises SPF as defined herein,
for example, and without limitation, silk based proteins or
fragments thereof having a weight average molecular weight range of
about 5 kDa to about 144 kDa, wherein the silk based proteins or
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the fiber or
yarn through the linker, wherein the leather exhibits an property
selected from the group consisting of an improved color retention
property, improved mildew resistance, improved resistance to
freeze-thaw cycle damage, improved resistance to abrasion, improved
blocking of ultraviolet (UV) radiation, improved regulation of the
body temperature of a wearer, improved tear resistance, improved
elasticity, improved rebound dampening, improved anti-itch
properties, improved insulation, improved wrinkle resistance,
improved stain resistance, and improved stickiness. In an
embodiment, the disclosure provides a leather coated with coating,
wherein the coating comprises SPF as defined herein, for example,
and without limitation, silk based proteins or fragments thereof
having a weight average molecular weight range of about 5 kDa to
about 144 kDa, wherein the silk based proteins or fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the fiber or
yarn through the linker, wherein the coating is transparent.
[0484] In any of the foregoing embodiments, at least one property
of the article is improved, wherein the property that is improved
is selected from the group consisting of color retention,
resistance to microbial growth, resistance to bacterial growth,
resistance to fungal growth, resistance to the buildup of static
electrical charge, resistance to the growth of mildew, transparency
of the coating, resistance to freeze-thaw cycle damage, resistance
from abrasion, blocking of ultraviolet (UV) radiation, regulation
of the body temperature of a wearer, resistance to tearing,
elasticity of the article, rebound dampening, tendency to cause
itching in the wearer, thermal insulation of the wearer, wrinkle
resistance, stain resistance, stickiness to skin, and flame
resistance, and wherein the property is improved by an amount
relative to an uncoated article selected from the group consisting
of at least 5%, at least 10%, at least 15%, at least 20%, at least
25%, at least 30%, at least 35%, at least 40%, at least 45%, at
least 50%, at least 55%, at least 60%, at least 65%, at least 70%,
at least 75%, at least 80%, at least 85%, at least 90%, at least
95%, at least 100%, at least 125%, at least 150%, at least 200%, at
least 300%, at least 400%, and at least 500%.
[0485] In any of the foregoing embodiments, the silk based proteins
or protein fragments thereof have an average weight average
molecular weight range selected from the group consisting of about
5 to about 10 kDa, about 6 kDa to about 16 kDa, about 17 kDa to
about 38 kDa, about 39 kDa to about 80 kDa, about 60 to about 100
kDa, and about 80 kDa to about 144 kDa, wherein the silk based
proteins or fragments thereof have a polydispersity of between
about 1.5 and about 3.0, wherein the silk based proteins or
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to a fiber or
yarn through the linker, and optionally wherein the proteins or
protein fragments, prior to coating the fabric, do not
spontaneously or gradually gelate and do not visibly change in
color or turbidity when in a solution for at least 10 days.
Additional Agents for Use with Textiles Coated with Silk
Fibroin-Based Protein Fragments
[0486] In an embodiment, the disclosure provides an article
comprising a fiber or yarn having a coating, wherein the coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa, wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the fiber or yarn through the
linker, wherein the article is a fabric, and wherein the fabric is
pretreated with various additional agents. Additional agents are
described in U.S. Patent Application Publications Nos. 20160222579,
20160281294, and 20190003113, all of which are incorporated herein
in their entireties.
Other Materials Coated with Silk Fibroin-Based Protein
Fragments
[0487] In an embodiment, the disclosure provides a material coated
with silk fibroin-based proteins or fragments thereof. The material
may be any material suitable for coating, including plastics (e.g.,
vinyl), foams (e.g., for use in padding and cushioning), and
various natural or synthetic products.
[0488] In an embodiment, the disclosure provides an automobile
component coated with silk fibroin-based proteins or fragments
thereof having a weight average molecular weight range of about 5
kDa to about 144 kDa, wherein the silk based proteins or fragments
are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the
component through the linker. In an embodiment, the disclosure
provides an automobile component coated with silk fibroin-based
proteins or fragments thereof having a weight average molecular
weight range selected from the group consisting of about 5 to about
10 kDa, about 6 kDa to about 16 kDa, about 17 kDa to about 38 kDa,
about 39 kDa to about 80 kDa, about 60 to about 100 kDa, and about
80 kDa to about 144 kDa, wherein the silk based proteins or
fragments thereof have a polydispersity of between about 1.5 and
about 3.0, wherein the silk based proteins or fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the
component through the linker, and optionally wherein the proteins
or protein fragments, prior to coating the fabric, do not
spontaneously or gradually gelate and do not visibly change in
color or turbidity when in a solution for at least 10 days. In an
embodiment, the disclosure provides an automobile component coated
with silk fibroin-based proteins or fragments thereof, wherein the
silk based proteins or fragments are chemically modified with a
precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk based proteins or fragments thereof are
chemically linked to the component through the linker, wherein the
automobile component exhibits an improved property relative to an
uncoated automobile component. In an embodiment, the disclosure
provides an automobile component coated with silk fibroin-based
proteins or fragments thereof, wherein the silk based proteins or
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the
component through the linker, wherein the automobile component
exhibits an improved property relative to an uncoated automobile
component, and wherein the automobile component is selected from
the group consisting of an upholstery fabric, a headliner, a seat,
a headrest, a transmission control, a floor mat, a carpet fabric, a
dashboard, a steering wheel, a trim, a wiring harness, an airbag
cover, an airbag, a sunvisor, a seat belt, a headrest, an armrest,
and a children's car seat. In an embodiment, the disclosure
provides an electrical component insulated with a coating
comprising silk fibroin-based proteins or fragments thereof,
wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the component through the
linker.
[0489] In an embodiment, the disclosure provides a foam coated with
silk fibroin-based proteins or fragments thereof having a weight
average molecular weight range of about 5 kDa to about 144 kDa,
wherein the silk based proteins or fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk based proteins or fragments
thereof are chemically linked to the foam through the linker. In an
embodiment, the disclosure provides a foam coated with silk
fibroin-based proteins or fragments thereof having a weight average
molecular weight range selected from the group consisting of about
5 to about 10 kDa, about 6 kDa to about 16 kDa, about 17 kDa to
about 38 kDa, about 39 kDa to about 80 kDa, about 60 to about 100
kDa, and about 80 kDa to about 144 kDa, wherein the silk based
proteins or fragments thereof have a polydispersity of between
about 1.5 and about 3.0, wherein the silk based proteins or
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the foam
through the linker, and optionally wherein the proteins or protein
fragments, prior to coating the foam, do not spontaneously or
gradually gelate and do not visibly change in color or turbidity
when in a solution for at least 10 days. In an embodiment, the
disclosure provides a foam coated with silk fibroin-based proteins
or fragments thereof, wherein the silk based proteins or fragments
are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to the foam
through the linker, wherein the foam exhibits an improved property
relative to an uncoated foam, and wherein the foam is selected from
the group consisting of a polyurethane foam, an ethylene-vinyl
acetate copolymer foam, a low density polyethylene foam, a low
density polyethylene foam, a high density polyethylene foam, a
polypropylene copolymer foam, a linear low density polyethylene
foam, a natural rubber foam, a latex foam, and combinations
thereof.
[0490] In any of the foregoing embodiments, the material coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 5 kDa to about 144
kDa. In any of the foregoing embodiments, the material coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 6 kDa to about 16
kDa. In any of the foregoing embodiments, the material coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 17 kDa to about 38
kDa. In any of the foregoing embodiments, the material coating
comprises SPF as defined herein, for example, and without
limitation, silk based proteins or fragments thereof having a
weight average molecular weight range of about 39 kDa to about 80
kDa. In any of the foregoing embodiments, the silk based proteins
or fragments are chemically modified with a precursor linker to
form a silk-conjugate, and wherein in some embodiments the silk
based proteins or fragments thereof are chemically linked to a
substrate through the linker.
[0491] In any of the foregoing embodiments, the silk based proteins
or protein fragments thereof have an average weight average
molecular weight range selected from the group consisting of about
5 to about 10 kDa, about 6 kDa to about 16 kDa, about 17 kDa to
about 38 kDa, about 39 kDa to about 80 kDa, about 60 to about 100
kDa, and about 80 kDa to about 144 kDa, wherein the silk based
proteins or fragments thereof have a polydispersity of between
about 1.5 and about 3.0, the silk based proteins or fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk based
proteins or fragments thereof are chemically linked to a substrate
through the linker, and wherein the proteins or protein fragments,
prior to coating the fabric, do not spontaneously or gradually
gelate and do not visibly change in color or turbidity when in a
solution for at least 10 days.
Processes for Coating Textiles and Leathers with Silk Fibroin-Based
Protein Fragments
[0492] In an embodiment, a method for silk coating a textile,
leather, or other material (such as a foam) includes immersion of
the textile, leather, or other material in any of the aqueous
solutions of pure silk fibroin-based protein fragments of the
present disclosure. Such methods are described in U.S. Patent
Application Publications Nos. 20160222579, 20160281294, and
20190003113, all of which are incorporated herein in their
entireties. In some embodiments, the disclosure relates to such
methods including the use of chemical modifiers and/or physical
modifiers. In an embodiment, a method for silk coating a textile,
leather, or other material (such as a foam) includes chemically
modifying silk based proteins or fragments with a precursor linker
to form a silk-conjugate, and optionally chemically linking the
silk based proteins or fragments thereof to a substrate through the
linker.
Additives for Silk Fibroin-Based Protein Fragments and Solutions
Thereof
[0493] In an embodiment, a solution of the present disclosure is
contacted with an additive, such as a therapeutic agent and/or an
additive molecule. U.S. Patent Application Publications Nos.
20160222579, 20160281294, and 20190003113, all of which are
incorporated herein in their entireties. The present disclosure
relates in particular to the use of such solutions, therapeutic
agents, and/or additive molecules in conjunction with a chemical
modifier and/or physical modifier.
Processes for Production of Silk Fibroin-Based Protein Fragments
and Solutions Thereof
[0494] As used herein, the term "fibroin" includes silkworm fibroin
and insect or spider silk protein. In an embodiment, fibroin is
obtained from Bombyx mori. In an embodiment, the spider silk
protein is selected from the group consisting of swathing silk
(Achniform gland silk), egg sac silk (Cylindriform gland silk), egg
case silk (Tubuliform silk), non-sticky dragline silk (Ampullate
gland silk), attaching thread silk (Pyriform gland silk), sticky
silk core fibers (Flagelliform gland silk), and sticky silk outer
fibers (Aggregate gland silk). Methods of making silk fibroin or
silk fibroin fragments are known and are described for example in
U.S. Pat. Nos. 9,187,538, 9,511,012, 9,517,191, 9,522,107,
9,522,108, 9,545,369, and 10,166,177, and U.S. Patent Application
Publications Nos. 20160222579, 20160281294, and 20190003113, all of
which are incorporated herein in their entireties.
[0495] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 6 kDa to about
17 kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 17 kDa to about 39 kDa, wherein the silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form a silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 39 kDa to about 80 kDa, wherein the silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form a silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0496] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 1 kDa to about 5
kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 5 kDa to about 10 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 10 kDa to about 15 kDa, wherein the silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form a silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 15 kDa to about 20 kDa, wherein the silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form a silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 20 kDa to about 25 kDa, wherein the silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form a silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 25 kDa to about 30 kDa, wherein the silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form a silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 30 kDa to about 35 kDa, wherein the silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form a silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 35 to about 40 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 40 to about 45 kDa. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 45 to about 50 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0497] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 50 to about 55
kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 55 to about 60 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 60 to about 65 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 65 to about 70 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 70 to about 75 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 75 to about 80 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 80 to about 85 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 85 to about 90 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 90 to about 95 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 95 to about 100 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0498] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 100 to about 105
kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 105 to about 110 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 110 to about 115 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 115 to about 120 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 120 to about 125 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 125 to about 130 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 130 to about 135 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 135 to about 140 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 140 to about 145 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 145 to about 150 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0499] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 150 to about 155
kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 155 to about 160 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 160 to about 165 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 165 to about 170 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 170 to about 175 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 175 to about 180 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 180 to about 185 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 185 to about 190 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 190 to about 195 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 195 to about 200 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0500] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 200 to about 205
kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 205 to about 210 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 210 to about 215 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 215 to about 220 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 220 to about 225 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 225 to about 230 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 230 to about 235 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 235 to about 240 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 240 to about 245 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 245 to about 250 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0501] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 250 to about 255
kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 255 to about 260 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 260 to about 265 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 265 to about 270 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 270 to about 275 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 275 to about 280 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 280 to about 285 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 285 to about 290 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 290 to about 295 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 295 to about 300 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0502] In an embodiment, a coating of the present disclosure
includes silk fibroin-based protein fragments having an average
weight average molecular weight ranging from about 300 to about 305
kDa, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 305 to about 310 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 310 to about 315 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 315 to about 320 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 320 to about 325 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 325 to about 330 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 330 to about 335 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 335 to about 340 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 340 to about 345 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a coating of the
present disclosure includes silk fibroin-based protein fragments
having an average weight average molecular weight ranging from
about 345 to about 350 kDa, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
[0503] In an embodiment, a composition of the present disclosure,
for example a coating or a composition used to make such coating,
includes silk fibroin-based protein fragments having a
polydispersity ranging from about 1 to about 5.0, wherein the silk
fibroin-based protein fragments are chemically modified with a
precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk fibroin-based protein fragments are chemically
linked to a substrate through the linker. In an embodiment, a
composition of the present disclosure, for example a coating or a
composition used to make such coating, includes silk fibroin-based
protein fragments having a polydispersity ranging from about 1.5 to
about 3.0, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a composition of
the present disclosure, for example a coating or a composition used
to make such coating, includes silk fibroin-based protein fragments
having a polydispersity ranging from about 1 to about 1.5, wherein
the silk fibroin-based protein fragments are chemically modified
with a precursor linker to form a silk-conjugate, and wherein in
some embodiments the silk fibroin-based protein fragments are
chemically linked to a substrate through the linker. In an
embodiment, a composition of the present disclosure, for example a
coating or a composition used to make such coating, includes silk
fibroin-based protein fragments having a polydispersity ranging
from about 1.5 to about 2.0, wherein the silk fibroin-based protein
fragments are chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker. In an embodiment, a composition of
the present disclosure, for example a coating or a composition used
to make such coating, includes silk fibroin-based protein fragments
having a polydispersity ranging from about 2.0 to about 2.5,
wherein the silk fibroin-based protein fragments are chemically
modified with a precursor linker to form a silk-conjugate, and
wherein in some embodiments the silk fibroin-based protein
fragments are chemically linked to a substrate through the linker.
In an embodiment, a composition of the present disclosure, for
example a coating or a composition used to make such coating,
includes silk fibroin-based protein fragments having a
polydispersity ranging from about 2.0 to about 3.0, wherein the
silk fibroin-based protein fragments are chemically modified with a
precursor linker to form a silk-conjugate, and wherein in some
embodiments the silk fibroin-based protein fragments are chemically
linked to a substrate through the linker. In an embodiment, a
composition of the present disclosure, for example a coating or a
composition used to make such coating, includes silk fibroin-based
protein fragments having a polydispersity ranging from about 2.5 to
about 3.0, wherein the silk fibroin-based protein fragments are
chemically modified with a precursor linker to form a
silk-conjugate, and wherein in some embodiments the silk
fibroin-based protein fragments are chemically linked to a
substrate through the linker.
Chemical Modification of Silk Fibroin
[0504] The disclosure relates to articles including one or more
coated substrates, wherein the coatings include silk fibroin or
silk fibroin fragments and a chemical modifier or a physical
modifier. In some embodiments, the chemical modifier is chemically
linked to one or more of a silk fibroin side group and a silk
fibroin terminal group. In some embodiments, the silk fibroin side
group and the silk fibroin terminal group are independently
selected from an amine group, an amide group, a carboxyl group, a
hydroxyl group, a thiol group, and a sulfhydryl group. In some
embodiments, the chemical modifier is chemically linked to one or
more functional groups on the substrate. In some embodiments, the
functional group on the substrate is selected from an amine group,
an amide group, a carboxyl group, a hydroxyl group, a thiol group,
and a sulfhydryl group. In some embodiments, the chemical modifier
includes one or more of a chemically linked functional group, or
functional group residue, and a linker. In some embodiments, the
chemical modifier includes one or more of --CR.sup.a.sub.2--,
--CR.sup.a.dbd.CR.sup.a--, --C.ident.C--, -alkyl-, -alkenyl-,
-alkynyl-, -aryl-, -heteroaryl-, --O--, --S--, --OC(O)--,
--N(R.sup.a)--, --N.dbd.N--, .dbd.N--, --C(O)--, --C(O)O--,
--OC(O)N(R.sup.a)--, --C(O)N(R.sup.a)--, --N(R.sup.a)C(O)O--,
--N(R.sup.a)C(O)--, --N(R.sup.a)C(O)N(R.sup.a)--,
--N(R.sup.a)C(NR.sup.a)N(R.sup.a)--, --N(R.sup.a)S(O).sub.t--,
--S(O).sub.tO--, --S(O).sub.tN(R.sup.a)--,
--S(O).sub.tN(R.sup.a)C(O)--, --OP(O)(OR.sup.a)O--, wherein t is 1
or 2, and wherein at each independent occurrence R.sup.a is
selected from hydrogen, alkyl, alkenyl, fluoroalkyl, carbocyclyl,
carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl,
heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl.
[0505] In some embodiments, any SPF described herein, including
silk fibroin or silk fibroin-based protein fragments are chemically
modified with a precursor linker to form silk conjugates. Precursor
linkers can be selected from any of the following crosslinkers:
TABLE-US-00021 Example of chemical group Class of Crosslinker
reactivity Example Succinimidyl Amine ##STR00001##
Bis[Sulfosuccinimidyl] glutarate Carbodiimide Carboxyls
##STR00002## EDC 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide
.cndot. HCl MW 191.70 Spacer Arm 6.0 .ANG. Acyl chloride
Amines/Hydroxyls ##STR00003## 2,3-Dibromopropionyl chloride
Carbonyldiimidazole Amine/Hydroxyls ##STR00004##
N,N'-Carbonyldiimidazole NHS-maleimide crosslinking, Thiol
##STR00005## Succinimidyl-4-[N- maleimidomethyl]cyclohexane-1-
carboxylate Imidoester crosslinking Amine ##STR00006## DMP dimethyl
pimelimidate dicyclohexyl carbodiimide crosslinking Amines
##STR00007## NHS-haloacetyl crosslinking Sulfo-SIAB
(sulfosuccinimidyl (4-iodoacetyl)aminobenzoate) Amine ##STR00008##
Methacrylate Epoxide Hydroxyl/amines Silanes Hydroxyls ##STR00009##
TEOS Tetraethyl orthosilicate Alkyne-Click Chemistry Azide
Azide-click Chemistry Alkyne Aldehyde Amines Formaldehyde Amines
Thioester Thiols, mines, hydroxyls Photo-crosslinker Amines
##STR00010## N-Sulfosuccinimidyl-6-[4'-azido-2-
nitraphenylamino]hexanoate pyridyl thiol, sulfosuccinimidyl
6-[3'-(2- pyridyldithio)propionamido] hexanoate Amines and
sulfhydryl ##STR00011## hydrazide Aldehydes, carbohydrates
alkoxyamine Aldehydes reductive amination Amine aryl azide Alkyne
Diazirine, NHS diazirine, succinimidyl 4,4'- azipentanoate Amine
(through NHS group) to amine (UV 350 nm): ##STR00012##
azide-phosphine Aryl halide, 1,5-Difluoro-2,4- dinitrobenzene
Primary amines ##STR00013##
TABLE-US-00022 Chemical Structure ##STR00014## ##STR00015##
##STR00016## ##STR00017## ##STR00018## ##STR00019##
TABLE-US-00023 Structure ##STR00020## ##STR00021## ##STR00022##
##STR00023## ##STR00024## ##STR00025## ##STR00026##
TABLE-US-00024 Modified SPF Chemical Structure ##STR00027##
##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032##
TABLE-US-00025 Modified SPF Structure ##STR00033## ##STR00034##
##STR00035## ##STR00036## ##STR00037## ##STR00038##
##STR00039##
[0506] Precursor linkers can be selected from any of the following
natural crosslinkers: caffeic acid, tannic acid, genipin,
proanthocyanidin, and the like. Precursor crosslinking can be
selected from any of the following enzymatic crosslinking:
transglutaminase transferase crosslinking, hydrolase crosslinking,
peptidase crosslinking (e.g., sortase SrtA from Staphylococcus
aureus), oxidoreductase crosslinking, tyrosinase crosslinking,
laccase crosslinking, peroxidase crosslinking (e.g., horseradish
peroxidase), lysyl oxidase crosslinking, peptide ligases (e.g.,
butelase 1, peptiligase, subtiligase, etc.), and the like.
[0507] In some embodiments, silk fibroin or silk fibroin-based
protein fragments are chemically modified with a precursor linker
to form silk conjugates with a crosslinker or an activator
independently selected from a N-hydroxysuccinimide ester
crosslinker, an imidoester crosslinker, a sulfosuccinimidyl
aminobenzoate, a methacrylate, a silane, a silicate, an alkyne
compound, an azide compound, an aldehyde, a carbodiimide
crosslinker, a dicyclohexyl carbodiimide activator, a dicyclohexyl
carbodiimide crosslinker, a maleimide crosslinker, a haloacetyl
crosslinker, a pyridyl disulfide crosslinker, a hydrazide
crosslinker, an alkoxyamine crosslinker, a reductive amination
crosslinker, an aryl azide crosslinker, a diazirine crosslinker, an
azide-phosphine crosslinker, a transferase crosslinker, a hydrolase
crosslinker, a transglutaminase crosslinker, a peptidase
crosslinker, an oxidoreductase crosslinker, a tyrosinase
crosslinker, a laccase crosslinker, a peroxidase crosslinker, a
lysyl oxidase crosslinker, and any combinations thereof. Some
chemically modified silk fibroin has been described in J Mater
Chem. 2009, June 23, 19(36), 6443-6450, including cyanuric
chloride-activated coupling, carbodiimide coupling, arginine
masking, chlorosulfonic acid reaction, diazonium coupling,
tyrosinase-catalyzed grafting, and poly(methacrylate) grafting.
Compositions and Processes Including Silk Fibroin-Based
Coatings
[0508] In an embodiment, the disclosure may include textiles, such
as fibers, yarns, fabrics, or other materials and combinations
thereof, that may be coated with an SPF mixture solution (i.e.,
silk fibroin solution (SFS)) as described herein to produce a
coated article, wherein the silk fibroin is chemically modified
with a precursor linker to form a silk-conjugate, and wherein in
some embodiments the silk fibroin is chemically linked to a
substrate through the linker. In an embodiment, the coated articles
described herein may be treated with additional chemical agents
that may enhance the properties of the coated article. In an
embodiment, the SFS may include one or more chemical agents that
may enhance the properties of the coated article.
[0509] In an embodiment, textiles may be flexible materials (woven
or non-woven) that include a network of natural and/or man-made
fibers, thread, yarn, or a combination thereof. SFS may be applied
at any stage of textile processing from individual fibers, to yarn,
to fabric, to thread, or a combination thereof.
[0510] In an embodiment, fibers may be natural fibers that may
include a natural fiber cellulose base, wherein the natural fiber
cellulose base may include one or more of: (1) a baste such as
flax, hemp, kenaf, jute, linen, and/or ramie; (2) a leaf such as
flax, hemp, sisal, abaca, banana, henequen, ramie, sunn, and/or
coir; and (3) seed hair such as cotton and/or kapok. In an
embodiment, fibers may be natural fibers that may include a natural
fiber protein base, wherein the natural fiber protein base may
include one or more of: (1) hair such as alpaca, camel, cashmere,
llama, mohair, and/or vicuna; (2) wool such as sheep; (3) filament
such as silk. In an embodiment, fibers may be natural fibers that
may include a natural fiber mineral base, including asbestos. In an
embodiment, fibers may be man-made fibers that may include a
man-made fiber organic natural polymer base, which may include one
or more of: (1) a cellulose base such as bamboo, rayon, lyocell,
acetate, and/or triacetate; (2) a protein base such as azlon; (3)
an alginate; and (4) rubber. In an embodiment, fibers may be
man-made fibers that may include a man-made fiber organic synthetic
base, which may include one ore more of acrylic, anidex, aramid,
fluorocarbon, modacrylic, novoloid, nylon, recycled nylon, nytril,
olefin, PBI, polycarbonate, polyester, recycled polyester, rubber,
saran, spandex, vinal vinvon. In an embodiment, fibers may be
man-made fibers that may include a man-made fiber inorganic base,
which may include one ore more of a glass material, metallic
material, and carbon material.
[0511] In an embodiment, yarn may include natural fibers that may
include a natural fiber cellulose base, wherein the natural fiber
cellulose base may be from: (1) a baste such as flax, hemp, kenaf,
jute, linen, and/or ramie; (2) a leaf such as flax, hemp, sisal,
abaca, banana, henequen, ramie, sunn, and/or coir; or (3) seed hair
such as cotton and/or kapok. In an embodiment, yarn may include
natural fibers that may include a natural fiber protein base,
wherein the natural fiber protein base may be from: (1) hair such
as alpaca, camel, cashmere, llama, mohair, and/or vicuna; (2) wool
such as sheep; or (3) filament such as silk. In an embodiment, yarn
may include natural fibers that may include a natural fiber mineral
base, including asbestos. In an embodiment, yarn may include
man-made fibers that may include a man-made fiber organic natural
polymer base, which may include: (1) a cellulose base such as
bamboo, rayon, lyocell, acetate, and/or triacetate; (2) a protein
base such as azlon; (3) an alginate; or (4) rubber. In an
embodiment, yarn may include man-made fibers that may include a
man-made fiber organic synthetic base, which may include acrylic,
anidex, aramid, fluorocarbon, modacrylic, novoloid, nylon, recycled
nylon, nytril, olefin, PBI, polycarbonate, polyester, recycled
polyester, rubber, saran, spandex, vinal and/or vinvon. In an
embodiment, yarn may include man-made fibers that may include a
man-made fiber inorganic base, which may include a glass material,
metallic material, carbon material, and/or specialty material.
[0512] In an embodiment, fabrics may include natural fibers and/or
yarn that may include a natural fiber cellulose base, wherein the
natural fiber cellulose base may be from: (1) a baste such as flax,
hemp, kenaf, jute, linen, and/or ramie; (2) a leaf such as flax,
hemp, sisal, abaca, banana, henequen, ramie, sunn, and/or coir; or
(3) seed hair such as cotton and/or kapok. In an embodiment, fabric
may include natural fibers and/or yarn that may include a natural
fiber protein base, wherein the natural fiber protein base may be
from: (1) hair such as alpaca, camel, cashmere, llama, mohair,
and/or vicuna; (2) wool such as sheep; or (3) filament such as
silk. In an embodiment, fabric may include natural fibers and/or
yarn that may include a natural fiber mineral base, including
asbestos. In an embodiment, fabric may include man-made fibers
and/or yarn that may include a man-made fiber organic natural
polymer base, which may include: (1) a cellulose base such as
bamboo, rayon, lyocell, acetate, and/or triacetate; (2) a protein
base such as azlon; (3) an alginate; or (4) rubber. In an
embodiment, fabric may include man-made fibers and/or yarn that may
include a man-made fiber organic synthetic base, which may include
acrylic, anidex, aramid, fluorocarbon, modacrylic, novoloid, nylon,
recycled nylon, nytril, olefin, PBI, polycarbonate, polyester,
recycled polyester, rubber, saran, spandex, vinal and/or vinvon. In
an embodiment, fabric may include man-made fibers and/or yarn that
may include a man-made fiber inorganic base, which may include a
glass material, metallic material, carbon material, and/or
specialty material.
[0513] In an embodiment, textiles may be manufactured via one or
more of the following processes weaving processes, knitting
processes, and non-woven processes. In an embodiment, weaving
processes may include plain weaving, twill weaving, and/or satin
weaving. In an embodiment, knitting processes may include weft
knitting (e.g., circular, flat bed, and/or full fashioned) and/or
warp knitting (e.g., tricot, Raschel, and/or crochet). In an
embodiment, non-woven processes may include stable fiber (e.g., dry
laid and/or wet laid) and/or continuous filament (e.g., spun laid
and/or melt blown).
[0514] In some embodiments, silk fibroin fragments may be applied
to fibers and/or yarn having a diameter of less than about 100 nm,
or less than about 200 nm, or less than about 300 nm, or less than
about 400 nm, or less than about 500 nm, or less than about 600 nm,
or less than about 700 nm, or less than about 800 nm, or less than
about 900 nm, or less than about 1000 nm, or less than about 2
.mu.m, or less than about 5 .mu.m, or less than about 10 .mu.m, or
less than about 20 .mu.m, or less than about 30 .mu.m, or less than
about 40 .mu.m, or less than about 50 .mu.m, or less than about 60
.mu.m, or less than about 70 .mu.m, or less than about 80 .mu.m, or
less than about 90 .mu.m, or less than about 100 .mu.m, or less
than about 200 .mu.m, or less than about 300 .mu.m, or less than
about 400 .mu.m, or less than about 500 .mu.m, or less than about
600 .mu.m, or less than about 700 .mu.m, or less than about 800
.mu.m, or less than about 900 .mu.m, or less than about 1000 .mu.m,
or less than about 2 mm, or less than about 3 mm, or less than
about 4 mm, or less than about 5 mm, 6 mm, or less than about 7 mm,
or less than about 8 mm, or less than about 9 mm, or less than
about 10 mm, or less than about 20 mm, or less than about 30 mm, or
less than about 40 mm, or less than about 50 mm, or less than about
60 mm, or less than about 70 mm, or less than about 80 mm, or less
than about 90 mm, or less than about 100 mm, or less than about 200
mm, or less than about 300 mm, or less than about 400 mm, or less
than about 500 mm, or less than about 600 mm, or less than about
700 mm, or less than about 800 mm, or less than about 900 mm, or
less than about 1000 mm.
[0515] In some embodiments, silk fibroin fragments may be applied
to fibers and/or yarn having a diameter of greater than about 100
nm, or greater than about 200 nm, or greater than about 300 nm, or
greater than about 400 nm, or greater than about 500 nm, or greater
than about 600 nm, or greater than about 700 nm, or greater than
about 800 nm, or greater than about 900 nm, or greater than about
1000 nm, or greater than about 2 .mu.m, or greater than about 5
.mu.m, or greater than about 10 .mu.m, or greater than about 20
.mu.m, or greater than about 30 .mu.m, or greater than about 40
.mu.m, or greater than about 50 .mu.m, or greater than about 60
.mu.m, or greater than about 70 .mu.m, or greater than about 80
.mu.m, or greater than about 90 .mu.m, or greater than about 100
.mu.m, or greater than about 200 .mu.m, or greater than about 300
.mu.m, or greater than about 400 .mu.m, or greater than about 500
.mu.m, or greater than about 600 .mu.m, or greater than about 700
.mu.m, or greater than about 800 .mu.m, or greater than about 900
.mu.m, or greater than about 1000 .mu.m, or greater than about 2
mm, or greater than about 3 mm, or greater than about 4 mm, or
greater than about 5 mm, 6 mm, or greater than about 7 mm, or
greater than about 8 mm, or greater than about 9 mm, or greater
than about 10 mm, or greater than about 20 mm, or greater than
about 30 mm, or greater than about 40 mm, or greater than about 50
mm, or greater than about 60 mm, or greater than about 70 mm, or
greater than about 80 mm, or greater than about 90 mm, or greater
than about 100 mm, or greater than about 200 mm, or greater than
about 300 mm, or greater than about 400 mm, or greater than about
500 mm, or greater than about 600 mm, or greater than about 700 mm,
or greater than about 800 mm, or greater than about 900 mm, or
greater than about 1000 mm.
[0516] In some embodiments, silk fibroin fragments may be applied
to fibers and/or yarn having a length of less than about 100 nm, or
less than about 200 nm, or less than about 300 nm, or less than
about 400 nm, or less than about 500 nm, or less than about 600 nm,
or less than about 700 nm, or less than about 800 nm, or less than
about 900 nm, or less than about 1000 nm, or less than about 2
.mu.m, or less than about 5 .mu.m, or less than about 10 .mu.m, or
less than about 20 .mu.m, or less than about 30 .mu.m, or less than
about 40 .mu.m, or less than about 50 .mu.m, or less than about 60
.mu.m, or less than about 70 .mu.m, or less than about 80 .mu.m, or
less than about 90 .mu.m, or less than about 100 .mu.m, or less
than about 200 .mu.m, or less than about 300 .mu.m, or less than
about 400 .mu.m, or less than about 500 .mu.m, or less than about
600 .mu.m, or less than about 700 .mu.m, or less than about 800
.mu.m, or less than about 900 .mu.m, or less than about 1000 .mu.m,
or less than about 2 mm, or less than about 3 mm, or less than
about 4 mm, or less than about 5 mm, 6 mm, or less than about 7 mm,
or less than about 8 mm, or less than about 9 mm, or less than
about 10 mm, or less than about 20 mm, or less than about 30 mm, or
less than about 40 mm, or less than about 50 mm, or less than about
60 mm, or less than about 70 mm, or less than about 80 mm, or less
than about 90 mm, or less than about 100 mm, or less than about 200
mm, or less than about 300 mm, or less than about 400 mm, or less
than about 500 mm, or less than about 600 mm, or less than about
700 mm, or less than about 800 mm, or less than about 900 mm, or
less than about 1000 mm.
[0517] In some embodiments, silk fibroin fragments may be applied
to fibers and/or yarn having a length of greater than about 100 nm,
or greater than about 200 nm, or greater than about 300 nm, or
greater than about 400 nm, or greater than about 500 nm, or greater
than about 600 nm, or greater than about 700 nm, or greater than
about 800 nm, or greater than about 900 nm, or greater than about
1000 nm, or greater than about 2 .mu.m, or greater than about 5
.mu.m, or greater than about 10 .mu.m, or greater than about 20
.mu.m, or greater than about 30 .mu.m, or greater than about 40
.mu.m, or greater than about 50 .mu.m, or greater than about 60
.mu.m, or greater than about 70 .mu.m, or greater than about 80
.mu.m, or greater than about 90 .mu.m, or greater than about 100
.mu.m, or greater than about 200 .mu.m, or greater than about 300
.mu.m, or greater than about 400 .mu.m, or greater than about 500
.mu.m, or greater than about 600 .mu.m, or greater than about 700
.mu.m, or greater than about 800 .mu.m, or greater than about 900
.mu.m, or greater than about 1000 .mu.m, or greater than about 2
mm, or greater than about 3 mm, or greater than about 4 mm, or
greater than about 5 mm, 6 mm, or greater than about 7 mm, or
greater than about 8 mm, or greater than about 9 mm, or greater
than about 10 mm, or greater than about 20 mm, or greater than
about 30 mm, or greater than about 40 mm, or greater than about 50
mm, or greater than about 60 mm, or greater than about 70 mm, or
greater than about 80 mm, or greater than about 90 mm, or greater
than about 100 mm, or greater than about 200 mm, or greater than
about 300 mm, or greater than about 400 mm, or greater than about
500 mm, or greater than about 600 mm, or greater than about 700 mm,
or greater than about 800 mm, or greater than about 900 mm, or
greater than about 1000 mm.
[0518] In some embodiments, silk fibroin fragments may be applied
to fibers and/or yarn having a weight (g/m.sup.2) of less than
about 1 g/m.sup.2, or less than about 2 g/m.sup.2, or less than
about 3 g/m.sup.2, or less than about 4 g/m.sup.2, or less than
about 5 g/m.sup.2, or less than about 6 g/m.sup.2, or less than
about 7 g/m.sup.2, or less than about 8 g/m.sup.2, or less than
about 9 g/m.sup.2, or less than about 10 g/m.sup.2, or less than
about 20 g/m.sup.2, or less than about 30 g/m.sup.2, or less than
about 40 g/m.sup.2, or less than about 50 g/m.sup.2, or less than
about 60 g/m.sup.2, or less than about 70 g/m.sup.2, or less than
about 80 g/m.sup.2, or less than about 90 g/m.sup.2, or less than
about 100 g/m.sup.2, or less than about 200 g/m.sup.2, or less than
about 300 g/m.sup.2, or less than about 400 g/m.sup.2, or less than
about 500 g/m.sup.2.
[0519] In some embodiments, silk fibroin fragments may be applied
to fibers and/or yarn having a weight (g/m.sup.2) of at greater
than about 1 g/m.sup.2, or greater than about 2 g/m.sup.2, or
greater than about 3 g/m.sup.2, or greater than about 4 g/m.sup.2,
or greater than about 5 g/m.sup.2, or greater than about 6
g/m.sup.2, or greater than about 7 g/m.sup.2, or greater than about
8 g/m.sup.2, or greater than about 9 g/m.sup.2, or greater than
about 10 g/m.sup.2, or greater than about 20 g/m.sup.2, or greater
than about 30 g/m.sup.2, or greater than about 40 g/m.sup.2, or
greater than about 50 g/m.sup.2, or greater than about 60
g/m.sup.2, or greater than about 70 g/m.sup.2, or greater than
about 80 g/m.sup.2, or greater than about 90 g/m.sup.2, or greater
than about 100 g/m.sup.2, or greater than about 200 g/m.sup.2, or
greater than about 300 g/m.sup.2, or greater than about 400
g/m.sup.2, or greater than about 500 g/m.sup.2.
[0520] In some embodiments, silk fibroin fragments may be applied
to fabric having a thickness of less than about 100 nm, or less
than about 200 nm, or less than about 300 nm, or less than about
400 nm, or less than about 500 nm, or less than about 600 nm, or
less than about 700 nm, or less than about 800 nm, or less than
about 900 nm, or less than about 1000 nm, or less than about 2
.mu.m, or less than about 5 .mu.m, or less than about 10 .mu.m, or
less than about 20 .mu.m, or less than about 30 .mu.m, or less than
about 40 .mu.m, or less than about 50 .mu.m, or less than about 60
.mu.m, or less than about 70 .mu.m, or less than about 80 .mu.m, or
less than about 90 .mu.m, or less than about 100 .mu.m, or less
than about 200 .mu.m, or less than about 300 .mu.m, or less than
about 400 .mu.m, or less than about 500 .mu.m, or less than about
600 .mu.m, or less than about 700 .mu.m, or less than about 800
.mu.m, or less than about 900 .mu.m, or less than about 1000 .mu.m,
or less than about 2 mm, or less than about 3 mm, or less than
about 4 mm, or less than about 5 mm, 6 mm, or less than about 7 mm,
or less than about 8 mm, or less than about 9 mm, or less than
about 10 mm.
[0521] In some embodiments, silk fibroin fragments may be applied
to fabric having a thickness of greater than about 100 nm, or
greater than about 200 nm, or greater than about 300 nm, or greater
than about 400 nm, or greater than about 500 nm, or greater than
about 600 nm, or greater than about 700 nm, or greater than about
800 nm, or greater than about 900 nm, or greater than about 1000
nm, or greater than about 2 .mu.m, or greater than about 5 .mu.m,
or greater than about 10 .mu.m, or greater than about 20 .mu.m, or
greater than about 30 .mu.m, or greater than about 40 .mu.m, or
greater than about 50 .mu.m, or greater than about 60 .mu.m, or
greater than about 70 .mu.m, or greater than about 80 .mu.m, or
greater than about 90 .mu.m, or greater than about 100 .mu.m, or
greater than about 200 .mu.m, or greater than about 300 .mu.m, or
greater than about 400 .mu.m, or greater than about 500 .mu.m, or
greater than about 600 .mu.m, or greater than about 700 .mu.m, or
greater than about 800 .mu.m, or greater than about 900 .mu.m, or
greater than about 1000 .mu.m, or greater than about 2 mm, or
greater than about 3 mm, or greater than about 4 mm, or greater
than about 5 mm, 6 mm, or greater than about 7 mm, or greater than
about 8 mm, or greater than about 9 mm, or greater than about 10
mm.
[0522] In some embodiments, silk fibroin fragments may be applied
to fabric having a width of less than about 100 nm, or less than
about 200 nm, or less than about 300 nm, or less than about 400 nm,
or less than about 500 nm, or less than about 600 nm, or less than
about 700 nm, or less than about 800 nm, or less than about 900 nm,
or less than about 1000 nm, or less than about 2 .mu.m, or less
than about 5 .mu.m, or less than about 10 .mu.m, or less than about
20 .mu.m, or less than about 30 .mu.m, or less than about 40 .mu.m,
or less than about 50 .mu.m, or less than about 60 .mu.m, or less
than about 70 .mu.m, or less than about 80 .mu.m, or less than
about 90 .mu.m, or less than about 100 .mu.m, or less than about
200 .mu.m, or less than about 300 .mu.m, or less than about 400
.mu.m, or less than about 500 .mu.m, or less than about 600 .mu.m,
or less than about 700 .mu.m, or less than about 800 .mu.m, or less
than about 900 .mu.m, or less than about 1000 .mu.m, or less than
about 2 mm, or less than about 3 mm, or less than about 4 mm, or
less than about 5 mm, 6 mm, or less than about 7 mm, or less than
about 8 mm, or less than about 9 mm, or less than about 10 mm, or
less than about 20 mm, or less than about 30 mm, or less than about
40 mm, or less than about 50 mm, or less than about 60 mm, or less
than about 70 mm, or less than about 80 mm, or less than about 90
mm, or less than about 100 mm, or less than about 200 mm, or less
than about 300 mm, or less than about 400 mm, or less than about
500 mm, or less than about 600 mm, or less than about 700 mm, or
less than about 800 mm, or less than about 900 mm, or less than
about 1000 mm, or less than about 2 m, or less than about 3 m, or
less than about 4 m, or less than about 5 m.
[0523] In some embodiments, silk fibroin fragments may be applied
to fabric having a width of greater than about 100 nm, or greater
than about 200 nm, or greater than about 300 nm, or greater than
about 400 nm, or greater than about 500 nm, or greater than about
600 nm, or greater than about 700 nm, or greater than about 800 nm,
or greater than about 900 nm, or greater than about 1000 nm, or
greater than about 2 .mu.m, or greater than about 5 .mu.m, or
greater than about 10 .mu.m, or greater than about 20 .mu.m, or
greater than about 30 .mu.m, or greater than about 40 .mu.m, or
greater than about 50 .mu.m, or greater than about 60 .mu.m, or
greater than about 70 .mu.m, or greater than about 80 .mu.m, or
greater than about 90 .mu.m, or greater than about 100 .mu.m, or
greater than about 200 .mu.m, or greater than about 300 .mu.m, or
greater than about 400 .mu.m, or greater than about 500 .mu.m, or
greater than about 600 .mu.m, or greater than about 700 .mu.m, or
greater than about 800 .mu.m, or greater than about 900 .mu.m, or
greater than about 1000 .mu.m, or greater than about 2 mm, or
greater than about 3 mm, or greater than about 4 mm, or greater
than about 5 mm, 6 mm, or greater than about 7 mm, or greater than
about 8 mm, or greater than about 9 mm, or greater than about 10
mm, or greater than about 20 mm, or greater than about 30 mm, or
greater than about 40 mm, or greater than about 50 mm, or greater
than about 60 mm, or greater than about 70 mm, or greater than
about 80 mm, or greater than about 90 mm, or greater than about 100
mm, or greater than about 200 mm, or greater than about 300 mm, or
greater than about 400 mm, or greater than about 500 mm, or greater
than about 600 mm, or greater than about 700 mm, or greater than
about 800 mm, or greater than about 900 mm, or greater than about
1000 mm, or greater than about 2 m, or greater than about 3 m, or
greater than about 4 m, or greater than about 5 m.
[0524] In some embodiments, silk fibroin fragments may be applied
to fabric having a length of less than about 100 nm, or less than
about 200 nm, or less than about 300 nm, or less than about 400 nm,
or less than about 500 nm, or less than about 600 nm, or less than
about 700 nm, or less than about 800 nm, or less than about 900 nm,
or less than about 1000 nm, or less than about 2 .mu.m, or less
than about 5 .mu.m, or less than about 10 .mu.m, or less than about
20 .mu.m, or less than about 30 .mu.m, or less than about 40 .mu.m,
or less than about 50 .mu.m, or less than about 60 .mu.m, or less
than about 70 .mu.m, or less than about 80 .mu.m, or less than
about 90 .mu.m, or less than about 100 .mu.m, or less than about
200 .mu.m, or less than about 300 .mu.m, or less than about 400
.mu.m, or less than about 500 .mu.m, or less than about 600 .mu.m,
or less than about 700 .mu.m, or less than about 800 .mu.m, or less
than about 900 .mu.m, or less than about 1000 .mu.m, or less than
about 2 mm, or less than about 3 mm, or less than about 4 mm, or
less than about 5 mm, 6 mm, or less than about 7 mm, or less than
about 8 mm, or less than about 9 mm, or less than about 10 mm, or
less than about 20 mm, or less than about 30 mm, or less than about
40 mm, or less than about 50 mm, or less than about 60 mm, or less
than about 70 mm, or less than about 80 mm, or less than about 90
mm, or less than about 100 mm, or less than about 200 mm, or less
than about 300 mm, or less than about 400 mm, or less than about
500 mm, or less than about 600 mm, or less than about 700 mm, or
less than about 800 mm, or less than about 900 mm, or less than
about 1000 mm.
[0525] In some embodiments, silk fibroin fragments may be applied
to fabric having a length of greater than about 100 nm, or greater
than about 200 nm, or greater than about 300 nm, or greater than
about 400 nm, or greater than about 500 nm, or greater than about
600 nm, or greater than about 700 nm, or greater than about 800 nm,
or greater than about 900 nm, or greater than about 1000 nm, or
greater than about 2 .mu.m, or greater than about 5 .mu.m, or
greater than about 10 .mu.m, or greater than about 20 .mu.m, or
greater than about 30 .mu.m, or greater than about 40 .mu.m, or
greater than about 50 .mu.m, or greater than about 60 .mu.m, or
greater than about 70 .mu.m, or greater than about 80 .mu.m, or
greater than about 90 .mu.m, or greater than about 100 .mu.m, or
greater than about 200 .mu.m, or greater than about 300 .mu.m, or
greater than about 400 .mu.m, or greater than about 500 .mu.m, or
greater than about 600 .mu.m, or greater than about 700 .mu.m, or
greater than about 800 .mu.m, or greater than about 900 .mu.m, or
greater than about 1000 .mu.m, or greater than about 2 mm, or
greater than about 3 mm, or greater than about 4 mm, or greater
than about 5 mm, 6 mm, or greater than about 7 mm, or greater than
about 8 mm, or greater than about 9 mm, or greater than about 10
mm, or greater than about 20 mm, or greater than about 30 mm, or
greater than about 40 mm, or greater than about 50 mm, or greater
than about 60 mm, or greater than about 70 mm, or greater than
about 80 mm, or greater than about 90 mm, or greater than about 100
mm, or greater than about 200 mm, or greater than about 300 mm, or
greater than about 400 mm, or greater than about 500 mm, or greater
than about 600 mm, or greater than about 700 mm, or greater than
about 800 mm, or greater than about 900 mm, or greater than about
1000 mm.
[0526] In some embodiments, silk fibroin fragments may be applied
to fabric having a stretch percentage of less than about 1%, or
less than about 2%, or less than about 3%, or less than about 4%,
or less than about 5%, or less than about 6%, or less than about
7%, or less than about 8%, or less than about 9%, or less than
about 10%, or less than about 20%, or less than about 30%, or less
than about 40%, or less than about 50%, or less than about 60%, or
less than about 70% , or less than about 80%, or less than about
90%, or less than about 100, or less than about 110%, or less than
about 120%, or less than about 130%, or less than about 140%, or
less than about 150%, or less than about 160%, or less than about
170%, or less than about 180%, or less than about 190%, or less
than about 200%. Stretch percentage may be determined for a fabric
having an unstretched width and stretching the fabric to a
stretched width, then subtracting the unstretched width from the
stretched width to yield the net stretched width, then dividing the
net stretched width and multiplying the quotient by 100 to find the
stretch percentage (%):
Stretch .times. .times. Percentage = ( Stretched .times. .times.
Width - Unstretched .times. .times. Width ) Unstretched .times.
.times. Width * 100 ##EQU00001##
[0527] In some embodiments, silk fibroin fragments may be applied
to fabric having a stretch percentage of greater than about 1%, or
greater than about 2%, or greater than about 3%, or greater than
about 4%, or greater than about 5%, or greater than about 6%, or
greater than about 7%, or greater than about 8%, or greater than
about 9%, or greater than about 10%, or greater than about 20%, or
greater than about 30%, or greater than about 40%, or greater than
about 50%, or greater than about 60%, or greater than about 70% ,
or greater than about 80%, or greater than about 90%, or greater
than about 100, or greater than about 110%, or greater than about
120%, or greater than about 130%, or greater than about 140%, or
greater than about 150%, or greater than about 160%, or greater
than about 170%, or greater than about 180%, or greater than about
190%, or greater than about 200%
[0528] In some embodiments, silk fibroin fragments may be applied
to fabric having a tensile energy (N/cm.sup.2) of less than about 1
cN/cm.sup.2, or less than about 2 cN/cm.sup.2, or less than about 3
cN/cm.sup.2, or less than about 4 cN/cm.sup.2, or less than about 5
cN/cm.sup.2, or less than about 5 cN/cm.sup.2, or less than about 6
cN/cm.sup.2, or less than about 7 cN/cm.sup.2, or less than about 8
cN/cm.sup.2, or less than about 9 cN/cm.sup.2, or less than about
10 cN/cm.sup.2, or less than about 20 cN/cm.sup.2, or less than
about 30 cN/cm.sup.2, or less than about 40 cN/cm.sup.2, or less
than about 50 cN/cm.sup.2, or less than about 60 cN/cm.sup.2, or
less than about 70 cN/cm.sup.2, or less than about 80 cN/cm.sup.2,
or less than about 90 cN/cm.sup.2, or less than about 100
cN/cm.sup.2, or less than about 2 N/cm.sup.2, or less than about 3
N/cm.sup.2, or less than about 4 N/cm.sup.2, or less than about 5
N/cm.sup.2, or less than about 6 N/cm.sup.2, or less than about 7
N/cm.sup.2, or less than about 8 N/cm.sup.2, or less than about 9
N/cm.sup.2, or less than about 10 N/cm.sup.2, or less than about 20
N/cm.sup.2, or less than about 30 N/cm.sup.2, or less than about 40
N/cm.sup.2, or less than about 50 N/cm.sup.2, or less than about 60
N/cm.sup.2, or less than about 70 N/cm.sup.2, or less than about 80
N/cm.sup.2, or less than about 90 N/cm.sup.2, or less than about
100 N/cm.sup.2, or less than about 150 N/cm.sup.2, or less than
about 200 N/cm.sup.2.
[0529] In some embodiments, silk fibroin fragments may be applied
to fabric having a tensile energy (N/cm.sup.2) of greater than
about 1 cN/cm.sup.2, or greater than about 2 cN/cm.sup.2, or
greater than about 3 cN/cm.sup.2, or greater than about 4
cN/cm.sup.2, or greater than about 5 cN/cm.sup.2, or greater than
about 5 cN/cm.sup.2, or greater than about 6 cN/cm.sup.2, or
greater than about 7 cN/cm.sup.2, or greater than about 8
cN/cm.sup.2, or greater than about 9 cN/cm.sup.2, or greater than
about 10 cN/cm.sup.2, or greater than about 20 cN/cm.sup.2, or
greater than about 30 cN/cm.sup.2, or greater than about 40
cN/cm.sup.2, or greater than about 50 cN/cm.sup.2, or greater than
about 60 cN/cm.sup.2, or greater than about 70 cN/cm.sup.2, or
greater than about 80 cN/cm.sup.2, or greater than about 90
cN/cm.sup.2, or greater than about 100 cN/cm.sup.2, or greater than
about 2 N/cm.sup.2, or greater than about 3 N/cm.sup.2, or greater
than about 4 N/cm.sup.2, or greater than about 5 N/cm.sup.2, or
greater than about 6 N/cm.sup.2, or greater than about 7
N/cm.sup.2, or greater than about 8 N/cm.sup.2, or greater than
about 9 N/cm.sup.2, or greater than about 10 N/cm.sup.2, or greater
than about 20 N/cm.sup.2, or greater than about 30 N/cm.sup.2, or
greater than about 40 N/cm.sup.2, or greater than about 50
N/cm.sup.2, or greater than about 60 N/cm.sup.2, or greater than
about 70 N/cm.sup.2, or greater than about 80 N/cm.sup.2, or
greater than about 90 N/cm.sup.2, or greater than about 100
N/cm.sup.2, or greater than about 150 N/cm.sup.2, or greater than
about 200 N/cm.sup.2.
[0530] In some embodiments, silk fibroin fragments may be applied
to fabric having a shear rigidity (N/cm-degree) of less than about
1 cN/cm-degree, or less than about 2 cN/cm-degree, or less than
about 3 cN/cm-degree, or less than about 4 cN/cm-degree, or less
than about 5 cN/cm-degree, or less than about 5 cN/cm-degree, or
less than about 6 cN/cm-degree, or less than about 7 cN/cm-degree,
or less than about 8 cN/cm-degree, or less than about 9
cN/cm-degree, or less than about 10 cN/cm-degree, or less than
about 20 cN/cm-degree, or less than about 30 cN/cm-degree, or less
than about 40 cN/cm-degree, or less than about 50 cN/cm-degree, or
less than about 60 cN/cm-degree, or less than about 70
cN/cm-degree, or less than about 80 cN/cm-degree, or less than
about 90 cN/cm-degree, or less than about 100 cN/cm-degree, or less
than about 2 N/cm-degree, or less than about 3 N/cm-degree, or less
than about 4 N/cm-degree, or less than about 5 N/cm-degree, or less
than about 6 N/cm-degree, or less than about 7 N/cm-degree, or less
than about 8 N/cm-degree, or less than about 9 N/cm-degree, or less
than about 10 N/cm-degree, or less than about 20 N/cm-degree, or
less than about 30 N/cm-degree, or less than about 40 N/cm-degree,
or less than about 50 N/cm-degree, or less than about 60
N/cm-degree, or less than about 70 N/cm-degree, or less than about
80 N/cm-degree, or less than about 90 N/cm-degree, or less than
about 100 N/cm-degree, or less than about 150 N/cm-degree, or less
than about 200 N/cm-degree.
[0531] In some embodiments, silk fibroin fragments may be applied
to fabric having a shear rigidity (N/cm-degree) of greater than
about 1 cN/cm-degree, or greater than about 2 cN/cm-degree, or
greater than about 3 cN/cm-degree, or greater than about 4
cN/cm-degree, or greater than about 5 cN/cm-degree, or greater than
about 5 cN/cm-degree, or greater than about 6 cN/cm-degree, or
greater than about 7 cN/cm-degree, or greater than about 8
cN/cm-degree, or greater than about 9 cN/cm-degree, or greater than
about 10 cN/cm-degree, or greater than about 20 cN/cm-degree, or
greater than about 30 cN/cm-degree, or greater than about 40
cN/cm-degree, or greater than about 50 cN/cm-degree, or greater
than about 60 cN/cm-degree, or greater than about 70 cN/cm-degree,
or greater than about 80 cN/cm-degree, or greater than about 90
cN/cm-degree, or greater than about 100 cN/cm-degree, or greater
than about 2 N/cm-degree, or greater than about 3 N/cm-degree, or
greater than about 4 N/cm-degree, or greater than about 5
N/cm-degree, or greater than about 6 N/cm-degree, or greater than
about 7 N/cm-degree, or greater than about 8 N/cm-degree, or
greater than about 9 N/cm-degree, or greater than about 10
N/cm-degree, or greater than about 20 N/cm-degree, or greater than
about 30 N/cm-degree, or greater than about 40 N/cm-degree, or
greater than about 50 N/cm-degree, or greater than about 60
N/cm-degree, or greater than about 70 N/cm-degree, or greater than
about 80 N/cm-degree, or greater than about 90 N/cm-degree, or
greater than about 100 N/cm-degree, or greater than about 150
N/cm-degree, or greater than about 200 N/cm-degree.
[0532] In some embodiments, silk fibroin fragments may be applied
to fabric having a bending rigidity (Ncm.sup.2/cm) of less than
about 1 cNcm.sup.2/cm, or less than about 2 cNcm.sup.2/cm, or less
than about 3 cNcm.sup.2/cm, or less than about 4 cNcm.sup.2/cm, or
less than about 5 cNcm.sup.2/cm, or less than about 5
cNcm.sup.2/cm, or less than about 6 cNcm.sup.2/cm, or less than
about 7 cNcm.sup.2/cm, or less than about 8 cNcm.sup.2/cm, or less
than about 9 cNcm.sup.2/cm, or less than about 10 cNcm.sup.2/cm, or
less than about 20 cNcm.sup.2/cm, or less than about 30
cNcm.sup.2/cm, or less than about 40 cNcm.sup.2/cm, or less than
about 50 cNcm.sup.2/cm, or less than about 60 cNcm.sup.2/cm, or
less than about 70 cNcm.sup.2/cm, or less than about 80
cNcm.sup.2/cm, or less than about 90 cNcm.sup.2/cm, or less than
about 100 cNcm.sup.2/cm, or less than about 2 Ncm.sup.2/cm, or less
than about 3 Ncm.sup.2/cm, or less than about 4 Ncm.sup.2/cm, or
less than about 5 Ncm.sup.2/cm, or less than about 6 Ncm.sup.2/cm,
or less than about 7 Ncm.sup.2/cm, or less than about 8
Ncm.sup.2/cm, or less than about 9 Ncm.sup.2/cm, or less than about
10 Ncm.sup.2/cm, or less than about 20 Ncm.sup.2/cm, or less than
about 30 Ncm.sup.2/cm, or less than about 40 Ncm.sup.2/cm, or less
than about 50 Ncm.sup.2/cm, or less than about 60 Ncm.sup.2/cm, or
less than about 70 Ncm.sup.2/cm, or less than about 80
Ncm.sup.2/cm, or less than about 90 Ncm.sup.2/cm, or less than
about 100 Ncm.sup.2/cm, or less than about 150 Ncm.sup.2/cm, or
less than about 200 Ncm.sup.2/cm.
[0533] In some embodiments, silk fibroin fragments may be applied
to fabric having a bending rigidity (Ncm.sup.2/cm) of greater than
about 1 cNcm.sup.2/cm, or greater than about 2 cNcm.sup.2/cm, or
greater than about 3 cNcm.sup.2/cm, or greater than about 4
cNcm.sup.2/cm, or greater than about 5 cNcm.sup.2/cm, or greater
than about 5 cNcm.sup.2/cm, or greater than about 6 cNcm.sup.2/cm,
or greater than about 7 cNcm.sup.2/cm, or greater than about 8
cNcm.sup.2/cm, or greater than about 9 cNcm.sup.2/cm, or greater
than about 10 cNcm.sup.2/cm, or greater than about 20
cNcm.sup.2/cm, or greater than about 30 cNcm.sup.2/cm, or greater
than about 40 cNcm.sup.2/cm, or greater than about 50
cNcm.sup.2/cm, or greater than about 60 cNcm.sup.2/cm, or greater
than about 70 cNcm.sup.2/cm, or greater than about 80
cNcm.sup.2/cm, or greater than about 90 cNcm.sup.2/cm, or greater
than about 100 cNcm.sup.2/cm, or greater than about 2 Ncm.sup.2/cm,
or greater than about 3 Ncm.sup.2/cm, or greater than about 4
Ncm.sup.2/cm, or greater than about 5 Ncm.sup.2/cm, or greater than
about 6 Ncm.sup.2/cm, or greater than about 7 Ncm.sup.2/cm, or
greater than about 8 Ncm.sup.2/cm, or greater than about 9
Ncm.sup.2/cm, or greater than about 10 Ncm.sup.2/cm, or greater
than about 20 Ncm.sup.2/cm, or greater than about 30 Ncm.sup.2/cm,
or greater than about 40 Ncm.sup.2/cm, or greater than about 50
Ncm.sup.2/cm, or greater than about 60 Ncm.sup.2/cm, or greater
than about 70 Ncm.sup.2/cm, or greater than about 80 Ncm.sup.2/cm,
or greater than about 90 Ncm.sup.2/cm, or greater than about 100
Ncm.sup.2/cm, or greater than about 150 Ncm.sup.2/cm, or greater
than about 200 Ncm.sup.2/cm.
[0534] In some embodiments, silk fibroin fragments may be applied
to fabric having a compression energy (Ncm/cm.sup.2) of less than
about 1 cNcm/cm.sup.2, or less than about 2 cNcm/cm.sup.2, or less
than about 3 cNcm/cm.sup.2, or less than about 4 cNcm/cm.sup.2, or
less than about 5 c Ncm/cm.sup.2, or less than about 5
cNcm/cm.sup.2, or less than about 6 cNcm/cm.sup.2, or less than
about 7 cNcm/cm.sup.2, or less than about 8 cNcm/cm.sup.2, or less
than about 9 cNcm/cm.sup.2, or less than about 10 cNcm/cm.sup.2, or
less than about 20 cNcm/cm.sup.2, or less than about 30
cNcm/cm.sup.2, or less than about 40 cNcm/cm.sup.2, or less than
about 50 cNcm/cm.sup.2, or less than about 60 cNcm/cm.sup.2, or
less than about 70 cNcm/cm.sup.2, or less than about 80
cNcm/cm.sup.2, or less than about 90 cNcm/cm.sup.2, or less than
about 100 cNcm/cm.sup.2, or less than about 2 Ncm/cm.sup.2, or less
than about 3 Ncm/cm.sup.2, or less than about 4 Ncm/cm.sup.2, or
less than about 5 Ncm/cm.sup.2, or less than about 6 Ncm/cm.sup.2,
or less than about 7 Ncm/cm.sup.2, or less than about 8
Ncm/cm.sup.2, or less than about 9 Ncm/cm.sup.2, or less than about
10 Ncm/cm.sup.2, or less than about 20 Ncm/cm.sup.2, or less than
about 30 Ncm/cm.sup.2, or less than about 40 Ncm/cm.sup.2, or less
than about 50 Ncm/cm.sup.2, or less than about 60 Ncm/cm.sup.2, or
less than about 70 Ncm/cm.sup.2, or less than about 80
Ncm/cm.sup.2, or less than about 90 Ncm/cm.sup.2, or less than
about 100 Ncm/cm.sup.2, or less than about 150 Ncm/cm.sup.2, or
less than about 200 Ncm/cm.sup.2.
[0535] In some embodiments, silk fibroin fragments may be applied
to fabric having a compression energy (Ncm/cm.sup.2) of greater
than about 1 cNcm/cm.sup.2, or greater than about 2 cNcm/cm.sup.2,
or greater than about 3 cNcm/cm.sup.2, or greater than about 4
cNcm/cm.sup.2, or greater than about 5 cNcm/cm.sup.2, or greater
than about 5 cNcm/cm.sup.2, or greater than about 6 cNcm/cm.sup.2,
or greater than about 7 cNcm/cm.sup.2, or greater than about 8
cNcm/cm.sup.2, or greater than about 9 cNcm/cm.sup.2, or greater
than about 10 cNcm/cm.sup.2, or greater than about 20
cNcm/cm.sup.2, or greater than about 30 cNcm/cm.sup.2, or greater
than about 40 cNcm/cm.sup.2, or greater than about 50
cNcm/cm.sup.2, or greater than about 60 cNcm/cm.sup.2, or greater
than about 70 cNcm/cm.sup.2, or greater than about 80
cNcm/cm.sup.2, or greater than about 90 cNcm/cm.sup.2, or greater
than about 100 cNcm/cm.sup.2, or greater than about 2 Ncm/cm.sup.2,
or greater than about 3 Ncm/cm.sup.2, or greater than about 4
Ncm/cm.sup.2, or greater than about 5 Ncm/cm.sup.2, or greater than
about 6 Ncm/cm.sup.2, or greater than about 7 Ncm/cm.sup.2, or
greater than about 8 Ncm/cm.sup.2, or greater than about 9
Ncm/cm.sup.2, or greater than about 10 Ncm/cm.sup.2, or greater
than about 20 Ncm/cm.sup.2, or greater than about 30 Ncm/cm.sup.2,
or greater than about 40 Ncm/cm.sup.2, or greater than about 50
Ncm/cm.sup.2, or greater than about 60 Ncm/cm.sup.2, or greater
than about 70 Ncm/cm.sup.2, or greater than about 80 Ncm/cm.sup.2,
or greater than about 90 Ncm/cm.sup.2, or greater than about 100
Ncm/cm.sup.2, or greater than about 150 Ncm/cm.sup.2, or greater
than about 200 Ncm/cm.sup.2.
[0536] In some embodiments, silk fibroin fragments may be applied
to fabric having a coefficient of friction of less than about 0.04,
or less than about 0.05, or less than about 0.06, or less than
about 0.07, or less than about 0.08, or less than about 0.09, or
less than about 0.10, or less than about 0.10, or less than about
0.15, or less than about 0.20, or less than about 0.25, or less
than about 0.30, or less than about 0.35, or less than about 0.40,
or less than about 0.45, or less than about 0.50, or less than
about 0.55, or less than about 0.60, or less than about 0.65, or
less than about 0.70, or less than about 0.75, or less than about
0.80, or less than about 0.85, or less than about 0.90, or less
than about 0.95, or less than about 1.00, or less than about
1.05.
[0537] In some embodiments, silk fibroin fragments may be applied
to fabric having a coefficient of friction of greater than about
0.04, or greater than about 0.05, or greater than about 0.06, or
greater than about 0.07, or greater than about 0.08, or greater
than about 0.09, or greater than about 0.10, or greater than about
0.10, or greater than about 0.15, or greater than about 0.20, or
greater than about 0.25, or greater than about 0.30, or greater
than about 0.35, or greater than about 0.40, or greater than about
0.45, or greater than about 0.50, or greater than about 0.55, or
greater than about 0.60, or greater than about 0.65, or greater
than about 0.70, or greater than about 0.75, or greater than about
0.80, or greater than about 0.85, or greater than about 0.90, or
greater than about 0.95, or greater than about 1.00, or greater
than about 1.05.
[0538] In some embodiments, chemical finishes may be applied to
textiles before or after such textiles are coated with SFS. In an
embodiment, chemical finishing may be intended as the application
of chemical agents and/or SFS to textiles, including fibers, yarn,
and fabric, or to garments that are prepared by such fibers, yarn,
and fabric to modify the original textile's or garment's properties
and achieve properties in the textile or garment that would be
otherwise absent. With chemical finishes, textiles treated with
such chemical finishes may act as surface treatments and/or the
treatments may modify the elemental analysis of treated textile
base polymers.
[0539] In an embodiment, a type of chemical finishing may include
the application of certain silk-fibroin based solutions to
textiles. For example, SFS may be applied to a fabric after it is
dyed, but there are also scenarios that may require the application
of SFS during processing, during dyeing, or after a garment is
assembled from a selected textile or fabric, thread, or yarn. In
some embodiments, after its application, SFS may be dried with the
use of heat. SFS may then be fixed to the surface of the textile in
a processing step called curing.
[0540] In some embodiments, silk fibroin fragments may be supplied
in a concentrated form suspended in water. In some embodiments,
silk fibroin fragments may have a concentration by weight (% w/w or
% w/v) or by volume (v/v) of less than about 50%, or less than
about 45%, or less than about 40%, or less than about 35%, or less
than about 30%, or less than about 25%, or less than about 20%, or
less than about 15%, or less than about 10%, or less than about 5%,
or less than about 4%, or less than about 3%, or less than about
2%, or less than about 1%, or less than about 0.1%, or less than
about 0.01%, or less than about 0.001%, or less than about 0.0001%,
or less than about 0.00001%. In some embodiments, SFS may have a
concentration by weight (% w/w or % w/v) or by volume (v/v) of
greater than about 50%, or greater than about 45%, or greater than
about 40%, or greater than about 35%, or greater than about 30%, or
greater than about 25%, or greater than about 20%, or greater than
about 15%, or greater than about 10%, or greater than about 5%, or
greater than about 4%, or greater than about 3%, or greater than
about 2%, or greater than about 1%, or greater than about 0.1%, or
greater than about 0.01%, or greater than about 0.001%, or greater
than about 0.0001%, or greater than about 0.00001%.
[0541] In some embodiments, the solution concentration and the wet
pick of the material determines the amount of silk fibroin
solution, which may include silk-based proteins or fragments
thereof, that may be fixed or otherwise adhered to the textile
being coated. The wet pick up may be expressed by the following
formula:
wet .times. .times. pick .times. .times. up .times. .times. ( % ) =
weight .times. .times. of .times. .times. SFS .times. .times.
applied .times. 100 weight .times. .times. of .times. .times. dry
.times. .times. textile .times. .times. material . ##EQU00002##
[0542] The total amount of silk fibroin fragments added to the
textile material may be expressed by the following formula:
SFS .times. .times. added .times. .times. ( % ) = weight .times.
.times. of .times. .times. dry .times. .times. SFS .times. .times.
coated .times. .times. textile .times. .times. material .times. 100
weight .times. .times. of .times. .times. dry .times. .times.
textile .times. .times. material .times. .times. before .times.
.times. coating . ##EQU00003##
[0543] Regarding methods for applying silk fibroin fragments to
textiles more broadly, silk fibroin fragments may be applied to
textiles by methods known in the art, for example methods described
in U.S. Patent Application Publications Nos. 20160222579,
20160281294, and 20190003113.
[0544] In an embodiment, "substantially modifying" silk fibroin
coating performance may be a decrease in a selected property of
silk fibroin coating, such as wetting time, absorption rate,
spreading speed, accumulative one-way transport, or overall
moisture management capability as compared to a control silk
fibroin coating that was not subjected to the selected temperature
for drying, curing, wash cycling, and/or heat setting purposes,
where such decrease is less than about a 1% decrease, or less than
about a 2% decrease, or less than about a 3% decrease, or less than
about a 4% decrease, or less than about a 5% decrease, or less than
about a 6% decrease, or less than about a 7% decrease, or less than
about an 8% decrease, or less than about a 9% decrease, or less
than about a 10% decrease, or less than about a 15% decrease, or
less than about a 20% decrease, or less than about a 25% decrease,
or less than about a 30% decrease, or less than about a 35%
decrease, or less than about a 40% decrease, or less than about a
45% decrease, or less than about a 50% decrease, or less than about
a 60% decrease, or less than about a 70% decrease, or less than
about a 80% decrease, or less than about a 90% decrease, or less
than about 100% decrease in wetting time, absorption rate,
spreading speed, accumulative one-way transport, or overall
moisture management capability as compared to a control silk
fibroin coating that was not subjected to the selected temperature
for drying, curing, wash cycling, and/or heat setting purposes. In
some embodiments, "wash cycling" may refer to at least one wash
cycle, or at least two wash cycles, or at least three wash cycles,
or at least four wash cycles, or at least five wash cycles.
[0545] In an embodiment, "substantially modifying" silk fibroin
coating performance may be an increase in a selected property of
silk fibroin coating, such as wetting time, absorption rate,
spreading speed, accumulative one-way transport, or overall
moisture management capability as compared to a control silk
fibroin coating that was not subjected to the selected temperature
for drying, curing, wash cycling, and/or heat setting purposes,
where such increase is less than about a 1% increase, or less than
about a 2% increase, or less than about a 3% increase, or less than
about a 4% increase, or less than about a 5% increase, or less than
about a 6% increase, or less than about a 7% increase, or less than
about an 8% increase, or less than about a 9% increase, or less
than about a 10% increase, or less than about a 15% increase, or
less than about a 20% increase, or less than about a 25% increase,
or less than about a 30% increase, or less than about a 35%
increase, or less than about a 40% increase, or less than about a
45% increase, or less than about a 50% increase, or less than about
a 60% increase, or less than about a 70% increase, or less than
about a 80% increase, or less than about a 90% increase, or less
than about 100% increase in wetting time, absorption rate,
spreading speed, accumulative one-way transport, or overall
moisture management capability as compared to a control silk
fibroin coating that was not subjected to the selected temperature
for drying, curing, wash cycling, and/or heat setting purposes. In
some embodiments, "wash cycling" may refer to at least one wash
cycle, or at least two wash cycles, or at least three wash cycles,
or at least four wash cycles, or at least five wash cycles.
[0546] In some embodiments, silk fibroin fragments may be used in
combination with chemical agents. In some embodiments, silk fibroin
fragments may be applied in conjunction with a chemical agent, for
example a chemical modifier and/or a physical modifier. In some
embodiments, the chemical modifier is chemically linked to one or
more of a silk fibroin side group and a silk fibroin terminal
group. In some embodiments, the silk fibroin side group and the
silk fibroin terminal group are independently selected from an
amine group, an amide group, a carboxyl group, a hydroxyl group, a
thiol group, and a sulfhydryl group. In some embodiments, the
chemical modifier is chemically linked to one or more functional
groups on the substrate. n some embodiments, the functional group
on the substrate is selected from an amine group, an amide group, a
carboxyl group, a hydroxyl group, a thiol group, and a sulfhydryl
group. In some embodiments, the chemical modifier includes one or
more of a chemically linked functional group, or functional group
residue, and a linker. In some embodiments, the chemical modifier
includes one or more of --CR.sup.a.sub.2--,
--CR.sup.a.dbd.CR.sup.a--, --C.ident.C--, -alkyl-, -alkenyl-,
-alkynyl-, -aryl-, -heteroaryl-, --O--, --S--, --OC(O)--,
--N(R.sup.a)--, --N.dbd.N--, .dbd.N--, --C(O)--, --C(O)O--,
--OC(O)N(R.sup.a)--, --C(O)N(R.sup.a)--, --N(R.sup.a)C(O)O--,
--N(R.sup.a)C(O)--, --N(R.sup.a)C(O)N(R.sup.a)--,
--N(R.sup.a)C(NR.sup.a)N(R.sup.a)--, --N(R.sup.a)S(O).sub.t--,
--S(O).sub.tO--, --S(O).sub.tN(R.sup.a)--,
--S(O).sub.tN(R.sup.a)C(O)--, --OP(O)(OR.sup.a)O--, wherein t is 1
or 2, and wherein at each independent occurrence R.sup.a is
selected from hydrogen, alkyl, alkenyl, fluoroalkyl, carbocyclyl,
carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl,
heterocycloalkylalkyl, heteroaryl, or heteroarylalkyl.
[0547] "Alkyl" refers to a straight or branched hydrocarbon chain
radical consisting solely of carbon and hydrogen atoms, containing
no unsaturation, having from one to ten carbon atoms (e.g.,
(C.sub.1-10)alkyl or C.sub.1-10 alkyl). Whenever it appears herein,
a numerical range such as "1 to 10" refers to each integer in the
given range--e.g., "1 to 10 carbon atoms" means that the alkyl
group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms,
etc., up to and including 10 carbon atoms, although the definition
is also intended to cover the occurrence of the term "alkyl" where
no numerical range is specifically designated. Typical alkyl groups
include, but are in no way limited to, methyl, ethyl, propyl,
isopropyl, n-butyl, isobutyl, sec-butyl isobutyl, tertiary butyl,
pentyl, isopentyl, neopentyl, hexyl, septyl, octyl, nonyl and
decyl. The alkyl moiety may be attached to the rest of the molecule
by a single bond, such as for example, methyl (Me), ethyl (Et),
n-propyl (Pr), 1-methylethyl (isopropyl), n-butyl, n-pentyl,
1,1-dimethylethyl (t-butyl) and 3-methylhexyl. Unless stated
otherwise specifically in the specification, an alkyl group is
optionally substituted by one or more of substituents which are
independently heteroalkyl, alkenyl, alkynyl, cycloalkyl,
heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl,
hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro,
trimethylsilanyl, --OR.sup.a, --SR.sup.a, --OC(O)--R.sup.a,
--N(R.sup.a).sub.2, --C(O)R.sup.a, --C(O)OR.sup.a,
--OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2 where each R.sup.a is independently
hydrogen, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0548] "Alkylaryl" refers to an -(alkyl)aryl radical where aryl and
alkyl are as disclosed herein and which are optionally substituted
by one or more of the substituents described as suitable
substituents for aryl and alkyl respectively.
[0549] "Alkylhetaryl" refers to an -(alkyl)hetaryl radical where
hetaryl and alkyl are as disclosed herein and which are optionally
substituted by one or more of the substituents described as
suitable substituents for aryl and alkyl respectively.
[0550] "Alkylheterocycloalkyl" refers to an -(alkyl) heterocyclyl
radical where alkyl and heterocycloalkyl are as disclosed herein
and which are optionally substituted by one or more of the
substituents described as suitable substituents for
heterocycloalkyl and alkyl respectively.
[0551] An "alkene" moiety refers to a group consisting of at least
two carbon atoms and at least one carbon-carbon double bond, and an
"alkyne" moiety refers to a group consisting of at least two carbon
atoms and at least one carbon-carbon triple bond. The alkyl moiety,
whether saturated or unsaturated, may be branched, straight chain,
or cyclic.
[0552] "Alkenyl" refers to a straight or branched hydrocarbon chain
radical group consisting solely of carbon and hydrogen atoms,
containing at least one double bond, and having from two to ten
carbon atoms (i.e., (C.sub.2-10)alkenyl or C.sub.2-10 alkenyl).
Whenever it appears herein, a numerical range such as "2 to 10"
refers to each integer in the given range--e.g., "2 to 10 carbon
atoms" means that the alkenyl group may consist of 2 carbon atoms,
3 carbon atoms, etc., up to and including 10 carbon atoms. The
alkenyl moiety may be attached to the rest of the molecule by a
single bond, such as for example, ethenyl (i.e., vinyl),
prop-1-enyl (i.e., allyl), but-1-enyl, pent-1-enyl and
penta-1,4-dienyl. Unless stated otherwise specifically in the
specification, an alkenyl group is optionally substituted by one or
more substituents which are independently alkyl, heteroalkyl,
alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl,
heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0553] "Alkenyl-cycloalkyl" refers to an -(alkenyl)cycloalkyl
radical where alkenyl and cycloalkyl are as disclosed herein and
which are optionally substituted by one or more of the substituents
described as suitable substituents for alkenyl and cycloalkyl
respectively.
[0554] "Alkynyl" refers to a straight or branched hydrocarbon chain
radical group consisting solely of carbon and hydrogen atoms,
containing at least one triple bond, having from two to ten carbon
atoms (i.e., (C.sub.2-10)alkynyl or C.sub.2-10 alkynyl). Whenever
it appears herein, a numerical range such as "2 to 10" refers to
each integer in the given range--e.g., "2 to 10 carbon atoms" means
that the alkynyl group may consist of 2 carbon atoms, 3 carbon
atoms, etc., up to and including 10 carbon atoms. The alkynyl may
be attached to the rest of the molecule by a single bond, for
example, ethynyl, propynyl, butynyl, pentynyl and hexynyl. Unless
stated otherwise specifically in the specification, an alkynyl
group is optionally substituted by one or more substituents which
independently are: alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0555] "Alkynyl-cycloalkyl" refers to an -(alkynyl)cycloalkyl
radical where alkynyl and cycloalkyl are as disclosed herein and
which are optionally substituted by one or more of the substituents
described as suitable substituents for alkynyl and cycloalkyl
respectively.
[0556] "Carboxaldehyde" refers to a --(C.dbd.O)H radical.
[0557] "Carboxyl" refers to a --(C.dbd.O)OH radical.
[0558] "Cyano" refers to a --CN radical.
[0559] "Cycloalkyl" refers to a monocyclic or polycyclic radical
that contains only carbon and hydrogen, and may be saturated, or
partially unsaturated. Cycloalkyl groups include groups having from
3 to 10 ring atoms (i.e. (C.sub.3-10)cycloalkyl or C.sub.3-10
cycloalkyl). Whenever it appears herein, a numerical range such as
"3 to 10" refers to each integer in the given range--e.g., "3 to 10
carbon atoms" means that the cycloalkyl group may consist of 3
carbon atoms, etc., up to and including 10 carbon atoms.
Illustrative examples of cycloalkyl groups include, but are not
limited to the following moieties: cyclopropyl, cyclobutyl,
cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, norbornyl, and the like. Unless
stated otherwise specifically in the specification, a cycloalkyl
group is optionally substituted by one or more substituents which
independently are: alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0560] "Cycloalkyl-alkenyl" refers to a -(cycloalkyl)alkenyl
radical where cycloalkyl and alkenyl are as disclosed herein and
which are optionally substituted by one or more of the substituents
described as suitable substituents for cycloalkyl and alkenyl,
respectively.
[0561] "Cycloalkyl-heterocycloalkyl" refers to a
-(cycloalkyl)heterocycloalkyl radical where cycloalkyl and
heterocycloalkyl are as disclosed herein and which are optionally
substituted by one or more of the substituents described as
suitable substituents for cycloalkyl and heterocycloalkyl,
respectively.
[0562] "Cycloalkyl-heteroaryl" refers to a -(cycloalkyl)heteroaryl
radical where cycloalkyl and heteroaryl are as disclosed herein and
which are optionally substituted by one or more of the substituents
described as suitable substituents for cycloalkyl and heteroaryl,
respectively.
[0563] The term "alkoxy" refers to the group --O-alkyl, including
from 1 to 8 carbon atoms of a straight, branched, cyclic
configuration and combinations thereof attached to the parent
structure through an oxygen. Examples include, but are not limited
to, methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy and
cyclohexyloxy. "Lower alkoxy" refers to alkoxy groups containing
one to six carbons.
[0564] The term "substituted alkoxy" refers to alkoxy wherein the
alkyl constituent is substituted (i.e., --O-(substituted alkyl)).
Unless stated otherwise specifically in the specification, the
alkyl moiety of an alkoxy group is optionally substituted by one or
more substituents which independently are: alkyl, heteroalkyl,
alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl,
heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0565] The term "alkoxycarbonyl" refers to a group of the formula
(alkoxy)(C.dbd.O)-attached through the carbonyl carbon wherein the
alkoxy group has the indicated number of carbon atoms. Thus a
(C.sub.1-6)alkoxycarbonyl group is an alkoxy group having from 1 to
6 carbon atoms attached through its oxygen to a carbonyl linker.
"Lower alkoxycarbonyl" refers to an alkoxycarbonyl group wherein
the alkoxy group is a lower alkoxy group.
[0566] The term "substituted alkoxycarbonyl" refers to the group
(substituted alkyl)-O--C(O)-- wherein the group is attached to the
parent structure through the carbonyl functionality. Unless stated
otherwise specifically in the specification, the alkyl moiety of an
alkoxycarbonyl group is optionally substituted by one or more
substituents which independently are: alkyl, heteroalkyl, alkenyl,
alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0567] "Acyl" refers to the groups (alkyl)-C(O)--, (aryl)-C(O)--,
(heteroaryl)-C(O)--, (heteroalkyl)-C(O)-- and
(heterocycloalkyl)-C(O)--, wherein the group is attached to the
parent structure through the carbonyl functionality. If the R
radical is heteroaryl or heterocycloalkyl, the hetero ring or chain
atoms contribute to the total number of chain or ring atoms. Unless
stated otherwise specifically in the specification, the alkyl, aryl
or heteroaryl moiety of the acyl group is optionally substituted by
one or more substituents which are independently alkyl,
heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl,
arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano,
trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl,
--OR.sup.a, --SR.sup.a, --OC(O)--R.sup.a, --N(R.sup.a).sub.2,
--C(O)R.sup.a, --C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2,
--C(O)N(R.sup.a).sub.2, --N(R.sup.a)C(O)OR.sup.a,
--N(R.sup.a)C(O)R.sup.a, --N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0568] "Acyloxy" refers to a R(C.dbd.O)O-- radical wherein R is
alkyl, aryl, heteroaryl, heteroalkyl or heterocycloalkyl, which are
as described herein. If the R radical is heteroaryl or
heterocycloalkyl, the hetero ring or chain atoms contribute to the
total number of chain or ring atoms. Unless stated otherwise
specifically in the specification, the R of an acyloxy group is
optionally substituted by one or more substituents which
independently are: alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0569] "Acylsulfonamide" refers a
--S(O).sub.2--N(R.sup.a)--C(.dbd.O)-- radical, where R.sup.a is
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl. Unless stated otherwise specifically in the
specification, an acylsulfonamide group is optionally substituted
by one or more substituents which independently are: alkyl,
heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl,
arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano,
trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl,
--OR.sup.a, --SR.sup.a, --OC(O)--R.sup.a, --N(R.sup.a).sub.2,
--C(O)R.sup.a, --C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2,
--C(O)N(R.sup.a).sub.2, --N(R.sup.a)C(O)OR.sup.a,
--N(R.sup.a)C(O)R.sup.a, --N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0570] "Amino" or "amine" refers to a --N(R.sup.a).sub.2 radical
group, where each R.sup.a is independently hydrogen, alkyl,
fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl,
heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl, unless stated otherwise specifically in the
specification. When a --N(R.sup.a).sub.2 group has two R.sup.a
substituents other than hydrogen, they can be combined with the
nitrogen atom to form a 4-, 5-, 6- or 7-membered ring. For example,
--N(R.sup.a).sub.2 is intended to include, but is not limited to,
1-pyrrolidinyl and 4-morpholinyl. Unless stated otherwise
specifically in the specification, an amino group is optionally
substituted by one or more substituents which independently are:
alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl,
aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano,
trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl,
--OR.sup.a, --SR.sup.a, --OC(O)--R.sup.a, --N(R.sup.a).sub.2,
--C(O)R.sup.a, --C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2,
--C(O)N(R.sup.a).sub.2, --N(R.sup.a)C(O)OR.sup.a,
--N(R.sup.a)C(O)R.sup.a, --N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0571] The term "substituted amino" also refers to N-oxides of the
groups --NHR.sup.a, and NR.sup.aR.sup.a each as described above.
N-oxides can be prepared by treatment of the corresponding amino
group with, for example, hydrogen peroxide or m-chloroperoxybenzoic
acid.
[0572] "Amide" or "amido" refers to a chemical moiety with formula
--C(O)N(R).sub.2 or --NHC(O)R, where R is selected from the group
consisting of hydrogen, alkyl, cycloalkyl, aryl, heteroaryl (bonded
through a ring carbon) and heteroalicyclic (bonded through a ring
carbon), each of which moiety may itself be optionally substituted.
The R.sub.2 of --N(R).sub.2 of the amide may optionally be taken
together with the nitrogen to which it is attached to form a 4-,
5-, 6- or 7-membered ring. Unless stated otherwise specifically in
the specification, an amido group is optionally substituted
independently by one or more of the substituents as described
herein for alkyl, cycloalkyl, aryl, heteroaryl, or
heterocycloalkyl. An amide may be an amino acid or a peptide
molecule attached to a compound disclosed herein, thereby forming a
prodrug. The procedures and specific groups to make such amides are
known to those of skill in the art and can readily be found in
seminal sources such as Greene and Wuts, Protective Groups in
Organic Synthesis, 3.sup.rd Ed., John Wiley & Sons, New York,
N.Y., 1999, which is incorporated herein by reference in its
entirety.
[0573] "Aromatic" or "aryl" or "Ar" refers to an aromatic radical
with six to ten ring atoms (e.g., C.sub.6-C.sub.10 aromatic or
C.sub.6-C.sub.10 aryl) which has at least one ring having a
conjugated pi electron system which is carbocyclic (e.g., phenyl,
fluorenyl, and naphthyl). Bivalent radicals formed from substituted
benzene derivatives and having the free valences at ring atoms are
named as substituted phenylene radicals. Bivalent radicals derived
from univalent polycyclic hydrocarbon radicals whose names end in
"-yl" by removal of one hydrogen atom from the carbon atom with the
free valence are named by adding "-idene" to the name of the
corresponding univalent radical, e.g., a naphthyl group with two
points of attachment is termed naphthylidene. Whenever it appears
herein, a numerical range such as "6 to 10" refers to each integer
in the given range; e.g., "6 to 10 ring atoms" means that the aryl
group may consist of 6 ring atoms, 7 ring atoms, etc., up to and
including 10 ring atoms. The term includes monocyclic or fused-ring
polycyclic (i.e., rings which share adjacent pairs of ring atoms)
groups. Unless stated otherwise specifically in the specification,
an aryl moiety is optionally substituted by one or more
substituents which are independently alkyl, heteroalkyl, alkenyl,
alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0574] The term "aryloxy" refers to the group --O-aryl.
[0575] The term "substituted aryloxy" refers to aryloxy wherein the
aryl substituent is substituted (i.e --O-(substituted aryl)).
Unless stated otherwise specifically in the specification, the aryl
moiety of an aryloxy group is optionally substituted by one or more
substituents which independently are: alkyl, heteroalkyl, alkenyl,
alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0576] "Aralkyl" or "arylalkyl" refers to an (aryl)alkyl-radical
where aryl and alkyl are as disclosed herein and which are
optionally substituted by one or more of the substituents described
as suitable substituents for aryl and alkyl respectively.
[0577] "Ester" refers to a chemical radical of formula --COOR,
where R is selected from the group consisting of alkyl, cycloalkyl,
aryl, heteroaryl (bonded through a ring carbon) and heteroalicyclic
(bonded through a ring carbon). The procedures and specific groups
to make esters are known to those of skill in the art and can
readily be found in seminal sources such as Greene and Wuts,
Protective Groups in Organic Synthesis, 3.sup.rd Ed., John Wiley
& Sons, New York, N.Y., 1999, which is incorporated herein by
reference in its entirety. Unless stated otherwise specifically in
the specification, an ester group is optionally substituted by one
or more substituents which independently are: alkyl, heteroalkyl,
alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl,
heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl,
trifluoromethoxy, nitro, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0578] "Fluoroalkyl" refers to an alkyl radical, as defined above,
that is substituted by one or more fluoro radicals, as defined
above, for example, trifluoromethyl, difluoromethyl,
2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, and the like.
The alkyl part of the fluoroalkyl radical may be optionally
substituted as defined above for an alkyl group.
[0579] "Halo," "halide," or, alternatively, "halogen" is intended
to mean fluoro, chloro, bromo or iodo. The terms "haloalkyl,"
"haloalkenyl," "haloalkynyl," and "haloalkoxy" include alkyl,
alkenyl, alkynyl and alkoxy structures that are substituted with
one or more halo groups or with combinations thereof. For example,
the terms "fluoroalkyl" and "fluoroalkoxy" include haloalkyl and
haloalkoxy groups, respectively, in which the halo is fluorine.
[0580] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" refer to
optionally substituted alkyl, alkenyl and alkynyl radicals and
which have one or more skeletal chain atoms selected from an atom
other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus or
combinations thereof. A numerical range may be given--e.g.,
C.sub.1-C.sub.4 heteroalkyl which refers to the chain length in
total, which in this example is 4 atoms long. A heteroalkyl group
may be substituted with one or more substituents which
independently are: alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo,
trimethylsilanyl, --OR.sup.a, --SR.sup.a, --OC(O)--R.sup.a,
--N(R.sup.a).sub.2, --C(O)R.sup.a, --C(O)OR.sup.a,
--OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0581] "Heteroalkylaryl" refers to an -(heteroalkyl)aryl radical
where heteroalkyl and aryl are as disclosed herein and which are
optionally substituted by one or more of the substituents described
as suitable substituents for heteroalkyl and aryl,
respectively.
[0582] "Heteroalkylheteroaryl" refers to an
-(heteroalkyl)heteroaryl radical where heteroalkyl and heteroaryl
are as disclosed herein and which are optionally substituted by one
or more of the substituents described as suitable substituents for
heteroalkyl and heteroaryl, respectively.
[0583] "Heteroalkylheterocycloalkyl" refers to an
-(heteroalkyl)heterocycloalkyl radical where heteroalkyl and
heterocycloalkyl are as disclosed herein and which are optionally
substituted by one or more of the substituents described as
suitable substituents for heteroalkyl and heterocycloalkyl,
respectively.
[0584] "Heteroalkylcycloalkyl" refers to an
-(heteroalkyl)cycloalkyl radical where heteroalkyl and cycloalkyl
are as disclosed herein and which are optionally substituted by one
or more of the substituents described as suitable substituents for
heteroalkyl and cycloalkyl, respectively.
[0585] "Heteroaryl" or "heteroaromatic" or "HetAr" refers to a 5-
to 18-membered aromatic radical (e.g., C.sub.5-C.sub.13 heteroaryl)
that includes one or more ring heteroatoms selected from nitrogen,
oxygen and sulfur, and which may be a monocyclic, bicyclic,
tricyclic or tetracyclic ring system. Whenever it appears herein, a
numerical range such as "5 to 18" refers to each integer in the
given range--e.g., "5 to 18 ring atoms" means that the heteroaryl
group may consist of 5 ring atoms, 6 ring atoms, etc., up to and
including 18 ring atoms. Bivalent radicals derived from univalent
heteroaryl radicals whose names end in "-yl" by removal of one
hydrogen atom from the atom with the free valence are named by
adding "-idene" to the name of the corresponding univalent
radical--e.g., a pyridyl group with two points of attachment is a
pyridylidene. A N-containing "heteroaromatic" or "heteroaryl"
moiety refers to an aromatic group in which at least one of the
skeletal atoms of the ring is a nitrogen atom. The polycyclic
heteroaryl group may be fused or non-fused. The heteroatom(s) in
the heteroaryl radical are optionally oxidized. One or more
nitrogen atoms, if present, are optionally quaternized. The
heteroaryl may be attached to the rest of the molecule through any
atom of the ring(s). Examples of heteroaryls include, but are not
limited to, azepinyl, acridinyl, benzimidazolyl, benzindolyl,
1,3-benzodioxolyl, benzofuranyl, benzooxazolyl, benzo[d]thiazolyl,
benzothiadiazolyl, benzo[b][1,4]dioxepinyl, benzo[b][1,4]oxazinyl,
1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl,
benzodioxolyl, benzodioxinyl, benzoxazolyl, benzopyranyl,
benzopyranonyl, benzofuranyl, benzofuranonyl, benzofurazanyl,
benzothiazolyl, benzothienyl(benzothiophenyl),
benzothieno[3,2-d]pyrimidinyl, benzotriazolyl,
benzo[4,6]imidazo[1,2-a]pyridinyl, carbazolyl, cinnolinyl,
cyclopenta[d]pyrimidinyl,
6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidinyl,
5,6-dihydrobenzo[h]quinazolinyl, 5,6-dihydrobenzo[h]cinnolinyl,
6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-c]pyridazinyl,
dibenzofuranyl, dibenzothiophenyl, furanyl, furazanyl, furanonyl,
furo[3,2-c]pyridinyl,
5,6,7,8,9,10-hexahydrocycloocta[d]pyrimidinyl,
5,6,7,8,9,10-hexahydrocycloocta[d]pyridazinyl,
5,6,7,8,9,10-hexahydrocycloocta[d]pyridinyl, isothiazolyl,
imidazolyl, indazolyl, indolyl, indazolyl, isoindolyl, indolinyl,
isoindolinyl, isoquinolyl, indolizinyl, isoxazolyl,
5,8-methano-5,6,7,8-tetrahydroquinazolinyl, naphthyridinyl,
1,6-naphthyridinonyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl,
oxiranyl, 5,6,6a,7,8,9,10,10a-octahydrobenzo[h]quinazolinyl,
1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl,
phthalazinyl, pteridinyl, purinyl, pyranyl, pyrrolyl, pyrazolyl,
pyrazolo[3,4-d]pyrimidinyl, pyridinyl, pyrido[3,2-d]pyrimidinyl,
pyrido[3,4-d]pyrimidinyl, pyrazinyl, pyrimidinyl, pyridazinyl,
pyrrolyl, quinazolinyl, quinoxalinyl, quinolinyl, isoquinolinyl,
tetrahydroquinolinyl, 5,6,7,8-tetrahydroquinazolinyl,
5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidinyl,
6,7,8,9-tetrahydro-5H-cyclohepta[4,5]thieno[2,3-d]pyrimidinyl,
5,6,7,8-tetrahydropyrido[4,5-c]pyridazinyl, thiazolyl,
thiadiazolyl, thiapyranyl, triazolyl, tetrazolyl, triazinyl,
thieno[2,3-d]pyrimidinyl, thieno[3,2-d]pyrimidinyl,
thieno[2,3-c]pyridinyl, and thiophenyl (i.e., thienyl). Unless
stated otherwise specifically in the specification, a heteroaryl
moiety is optionally substituted by one or more substituents which
are independently: alkyl, heteroalkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl,
heteroarylalkyl, hydroxy, halo, cyano, nitro, oxo, thioxo,
trimethylsilanyl, --OR.sup.a, --SR.sup.a, --OC(O)--R.sup.a,
--N(R.sup.a).sub.2, --C(O)R.sup.a, --C(O)OR.sup.a,
--OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0586] Substituted heteroaryl also includes ring systems
substituted with one or more oxide (--O--) substituents, such as,
for example, pyridinyl N-oxides.
[0587] "Heteroarylalkyl" refers to a moiety having an aryl moiety,
as described herein, connected to an alkylene moiety, as described
herein, wherein the connection to the remainder of the molecule is
through the alkylene group.
[0588] "Heterocycloalkyl" refers to a stable 3- to 18-membered
non-aromatic ring radical that comprises two to twelve carbon atoms
and from one to six heteroatoms selected from nitrogen, oxygen and
sulfur. Whenever it appears herein, a numerical range such as "3 to
18" refers to each integer in the given range--e.g., "3 to 18 ring
atoms" means that the heterocycloalkyl group may consist of 3 ring
atoms, 4 ring atoms, etc., up to and including 18 ring atoms.
Unless stated otherwise specifically in the specification, the
heterocycloalkyl radical is a monocyclic, bicyclic, tricyclic or
tetracyclic ring system, which may include fused or bridged ring
systems. The heteroatoms in the heterocycloalkyl radical may be
optionally oxidized. One or more nitrogen atoms, if present, are
optionally quaternized. The heterocycloalkyl radical is partially
or fully saturated. The heterocycloalkyl may be attached to the
rest of the molecule through any atom of the ring(s). Examples of
such heterocycloalkyl radicals include, but are not limited to,
dioxolanyl, thienyl[1,3]dithianyl, decahydroisoquinolyl,
imidazolinyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl,
morpholinyl, octahydroindolyl, octahydroisoindolyl,
2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl,
oxazolidinyl, piperidinyl, piperazinyl, 4-piperidonyl,
pyrrolidinyl, pyrazolidinyl, quinuclidinyl, thiazolidinyl,
tetrahydrofuryl, trithianyl, tetrahydropyranyl, thiomorpholinyl,
thiamorpholinyl, 1-oxo-thiomorpholinyl, and
1,1-dioxo-thiomorpholinyl. Unless stated otherwise specifically in
the specification, a heterocycloalkyl moiety is optionally
substituted by one or more substituents which independently are:
alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl,
aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano,
nitro, oxo, thioxo, trimethylsilanyl, --OR.sup.a, --SR.sup.a,
--OC(O)--R.sup.a, --N(R.sup.a).sub.2, --C(O)R.sup.a,
--C(O)OR.sup.a, --OC(O)N(R.sup.a).sub.2, --C(O)N(R.sup.a).sub.2,
--N(R.sup.a)C(O)OR.sup.a, --N(R.sup.a)C(O)R.sup.a,
--N(R.sup.a)C(O)N(R.sup.a).sub.2,
N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2,
--N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2),
--S(O).sub.tOR.sup.a (where t is 1 or 2),
--S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or
PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently
hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl,
aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or
heteroarylalkyl.
[0589] "Heterocycloalkyl" also includes bicyclic ring systems
wherein one non-aromatic ring, usually with 3 to 7 ring atoms,
contains at least 2 carbon atoms in addition to 1-3 heteroatoms
independently selected from oxygen, sulfur, and nitrogen, as well
as combinations comprising at least one of the foregoing
heteroatoms; and the other ring, usually with 3 to 7 ring atoms,
optionally contains 1-3 heteroatoms independently selected from
oxygen, sulfur, and nitrogen and is not aromatic.
[0590] "Nitro" refers to the --NO.sub.2 radical.
[0591] "Oxa" refers to the --O-- radical.
[0592] "Oxo" refers to the .dbd.O radical.
[0593] "Isomers" are different compounds that have the same
molecular formula. "Stereoisomers" are isomers that differ only in
the way the atoms are arranged in space--i.e., having a different
stereochemical configuration. "Enantiomers" are a pair of
stereoisomers that are non-superimposable mirror images of each
other. A 1:1 mixture of a pair of enantiomers is a "racemic"
mixture. The term "(.+-.)" is used to designate a racemic mixture
where appropriate. "Diastereoisomers" are stereoisomers that have
at least two asymmetric atoms, but which are not mirror-images of
each other. The absolute stereochemistry is specified according to
the Cahn-Ingold-Prelog R-S system. When a compound is a pure
enantiomer the stereochemistry at each chiral carbon can be
specified by either (R) or (S). Resolved compounds whose absolute
configuration is unknown can be designated (+) or (-) depending on
the direction (dextro- or levorotatory) which they rotate plane
polarized light at the wavelength of the sodium D line. Certain of
the compounds described herein contain one or more asymmetric
centers and can thus give rise to enantiomers, diastereomers, and
other stereoisomeric forms that can be defined, in terms of
absolute stereochemistry, as (R) or (S). The present chemical
entities, pharmaceutical compositions and methods are meant to
include all such possible isomers, including racemic mixtures,
optically pure forms and intermediate mixtures. Optically active
(R)- and (S)-isomers can be prepared using chiral synthons or
chiral reagents, or resolved using conventional techniques. When
the compounds described herein contain olefinic double bonds or
other centers of geometric asymmetry, and unless specified
otherwise, it is intended that the compounds include both E and Z
geometric isomers. "Substituted" means that the referenced group
may have attached one or more additional groups, radicals or
moieties individually and independently selected from, for example,
acyl, alkyl, alkylaryl, cycloalkyl, aralkyl, aryl, carbohydrate,
carbonate, heteroaryl, heterocycloalkyl, hydroxy, alkoxy, aryloxy,
mercapto, alkylthio, arylthio, cyano, halo, carbonyl, ester,
thiocarbonyl, isocyanato, thiocyanato, isothiocyanato, nitro, oxo,
perhaloalkyl, perfluoroalkyl, phosphate, silyl, sulfinyl, sulfonyl,
sulfonamidyl, sulfoxyl, sulfonate, urea, and amino, including mono-
and di-substituted amino groups, and protected derivatives thereof.
The substituents themselves may be substituted, for example, a
cycloalkyl substituent may itself have a halide substituent at one
or more of its ring carbons. The term "optionally substituted"
means optional substitution with the specified groups, radicals or
moieties.
[0594] "Sulfanyl" refers to groups that include --S-(optionally
substituted alkyl), --S-(optionally substituted aryl),
--S-(optionally substituted heteroaryl) and --S-(optionally
substituted heterocycloalkyl).
[0595] "Sulfinyl" refers to groups that include --S(O)--H,
--S(O)-(optionally substituted alkyl), --S(O)-(optionally
substituted amino), --S(O)-(optionally substituted aryl),
--S(O)-(optionally substituted heteroaryl) and --S(O)-(optionally
substituted heterocycloalkyl).
[0596] "Sulfonyl" refers to groups that include --S(O.sub.2)--H,
--S(O.sub.2)-(optionally substituted alkyl),
--S(O.sub.2)-(optionally substituted amino),
--S(O.sub.2)-(optionally substituted aryl),
--S(O.sub.2)-(optionally substituted heteroaryl), and
--S(O.sub.2)-(optionally substituted heterocycloalkyl).
[0597] "Sulfonamidyl" or "sulfonamido" refers to a
--S(.dbd.O).sub.2--NRR radical, where each R is selected
independently from the group consisting of hydrogen, alkyl,
cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and
heteroalicyclic (bonded through a ring carbon). The R groups in
--NRR of the --S(.dbd.O).sub.2--NRR radical may be taken together
with the nitrogen to which it is attached to form a 4-, 5-, 6- or
7-membered ring. A sulfonamido group is optionally substituted by
one or more of the substituents described for alkyl, cycloalkyl,
aryl, heteroaryl, respectively.
[0598] "Sulfoxyl" refers to a --S(.dbd.O).sub.2OH radical.
"Sulfonate" refers to a --S(.dbd.O).sub.2--OR radical, where R is
selected from the group consisting of alkyl, cycloalkyl, aryl,
heteroaryl (bonded through a ring carbon) and heteroalicyclic
(bonded through a ring carbon). A sulfonate group is optionally
substituted on R by one or more of the substituents described for
alkyl, cycloalkyl, aryl, heteroaryl, respectively.
[0599] In some embodiments, a chemical agent may be applied to a
textile to be coated prior to providing a silk fibroin fragments
coating. In some embodiments, a chemical agent may be applied to a
textile after such textile has been coated with a silk fibroin
fragments coating. One or more chemical agents may be applied, as
set forth above, and may include a first chemical agent, second
chemical agent, third chemical agent, and the like, where the
chemical agents may be the same or a combination of two or more of
the chemical agents described herein. In some embodiments, chemical
agents may provide selected properties to coated textile (e.g.,
fabric) including, but not limited to, an antimicrobial property, a
water repellant property, an oil repellant property, a coloring
property, a flame retardant property, a fabric softening property,
a pH adjusting property, an anticrocking property, an antipilling
property, and/or an antifelting property. Such chemical agents may
include, but are not limited to, softeners (e.g., silicone), acidic
agents, antimicrobials, finishing agents including monomers such as
melted polyester, or combinations thereof. Chemical agents have
been described in U.S. Patent Application Publications Nos.
20160222579, 20160281294, and 20190003113, all of which are
incorporated herein in their entireties. Any chemical agent
described herein may act as a precursor linker. In some
embodiments, a precursor linker reacts with a substrate, and then
fibroin can react with the linker. In some embodiments, a precursor
linker reacts with silk fibroin, and then the substrate can react
with the linker.
[0600] In some embodiments, the chemical agent may include one or
more of a silicone, an acidic agent, a dyeing agent, a pigment dye,
a traditional finishing agent, and a technical finishing agent. The
dyeing agent may include one or more of a dispersing agent, a
levelling agent, a fixing agent, a special resin, an antireducing
agent, and an anticreasing agent. The pigment dye may include one
or more of an antimigrating agent, a binding agent, an all in one
agent, and a delave agent. The traditional finishing agent may
include one or more of a wrinkle free treatment, a softener, a
handle modifier, a waterborne polyurethanes dispersion, and other
resins. The technical finishing agent may include one or more of a
waterborne polyurethanes dispersion, an oil repellant, a water
repellant, a crosslinker, and a thickener.
[0601] In some embodiments, the chemical agent may include an
acidic agent. In some embodiments, an acidic agent may be a
Bronsted acid. In an embodiment, the acidic agent includes one or
more of citric acid and acetic acid. In an embodiment, the acidic
agent aids the deposition and coating of silk fibroin fragments
mixtures on the textile to be coated as compared to the absence of
such acidic agent. In an embodiment, the acidic agent improves
crystallization of the SPF mixtures at the textile to be
coated.
[0602] In an embodiment, the acidic agent is added at a
concentration by weight (% w/w or % w/v) or by volume (v/v) of
greater than about 0.001% , or greater than about 0.002%, or
greater than about 0.003%, or greater than about 0.004%, or greater
than about 0.005%, or greater than about 0.006%, or greater than
about 0.007%, or greater than about 0.008%, or greater than about
0.009%, or greater than about 0.01%, or greater than about 0.02%,
or greater than about 0.03%, or greater than about 0.04%, or
greater than about 0.05%, or greater than about 0.06%, or greater
than about 0.07%, or greater than about 0.08%, or greater than
about 0.09%, or greater than about 0.1%, or greater than about
0.2%, or greater than about 0.3%, or greater than about 0.4%, or
greater than about 0.5%, or greater than about 0.6%, or greater
than about 0.7%, or greater than about 0.8%, or greater than about
0.9%, or greater than about 1.0% or greater than about 2.0%, or
greater than about 3.0%, or greater than about 4.0%, or greater
than about 5.0% .
[0603] In an embodiment, the acidic agent is added at a
concentration by weight (% w/w or % w/v) or by volume (v/v) of less
than about 0.001%, or less than about 0.002%, or less than about
0.003%, or less than about 0.004% , or less than about 0.005%, or
less than about 0.006%, or less than about 0.007%, or less than
about 0.008%, or less than about 0.009%, or less than about 0.01%,
or less than about 0.02%, or less than about 0.03%, or less than
about 0.04%, or less than about 0.05%, or less than about 0.06%, or
less than about 0.07%, or less than about 0.08%, or less than about
0.09%, or less than about 0.1%, or less than about 0.2%, or less
than about 0.3%, or less than about 0.4%, or less than about 0.5%,
or less than about 0.6%, or less than about 0.7%, or less than
about 0.8%, or less than about 0.9%, or less than about 1.0% or
less than about 2.0%, or less than about 3.0%, or less than about
4.0%, or less than about 5.0%.
[0604] In some embodiments, a composition including silk fibroin
fragments may have a pH of less than about 9, or less than about
8.5, or less than about 8, or less than about 7.5, or less than
about 7, or less than about 6.5, or less than about 6, or less than
about 5.5, or less than about 5, or less than about 4.5, or less
than about 4, or greater than about 3.5, or greater than about 4,
or greater than about 4.5, or greater than about 5, or greater than
about 5.5, or greater than about 6, or greater than about 6.5, or
greater than about 7, or greater than about 7.5, or greater than
about 8, or greater than about 8.5.
[0605] In some embodiments, a composition including silk fibroin
fragments may include an acidic agent, and may have a pH of less
than about 9, or less than about 8.5, or less than about 8, or less
than about 7.5, or less than about 7, or less than about 6.5, or
less than about 6, or less than about 5.5, or less than about 5, or
less than about 4.5, or less than about 4, or greater than about
3.5, or greater than about 4, or greater than about 4.5, or greater
than about 5, or greater than about 5.5, or greater than about 6,
or greater than about 6.5, or greater than about 7, or greater than
about 7.5, or greater than about 8, or greater than about 8.5.
[0606] In an embodiment, the chemical agent may include silicone.
In some embodiments, a SFS may include silicone. In some
embodiments, silicone may include a silicone emulsion. The term
"silicone," may generally refer to a broad family of synthetic
polymers, mixtures of polymers, and/or emulsions thereof, that have
a repeating silicon-oxygen backbone including, but not limited to,
polysiloxanes. For example, a silicone may include ULTRATEX.RTM.
CSP, which is a commercially available (Huntsman International LLC)
silicone emulsion that may be used as a softening agent and which
may also increase fabric resilience, elasticity of knitted fabrics,
and fiber lubrication and also improve sewability. A silicone may
also include ULTRATEX.RTM. CI, which is a commercially available
silicone composition (Huntsman International LLC) that may be used
as a fabric softening agent.
[0607] In some embodiments, a composition including silk fibroin
fragments may include silicone in a concentration by weight (% w/w
or % w/v) or by volume (v/v) of less than about 25%, or less than
about 20%, or less than about 15%, or less than about 10%, or less
than about 9%, or less than about 8% , or less than about 7%, or
less than about 6%, or less than about 5%, or less than about 4%,
or less than about 3%, or less than about 2%, or less than about
1%, or less than about 0.9%, or less than about 0.8%, or less than
about 0.7%, or less than about 0.6%, or less than about 0.5%, or
less than about 0.4%, or less than about 0.3%, or less than about
0.2%, or less than about 0.1%, or less than about 0.01%, or less
than about 0.001%.
[0608] In some embodiments, a composition including silk fibroin
fragments may include silicone in a concentration by weight (% w/w
or % w/v) or by volume (v/v) of greater than about 25%, or greater
than about 20%, or greater than about 15%, or greater than about
10%, or greater than about 9%, or greater than about 8% , or
greater than about 7%, or greater than about 6%, or greater than
about 5%, or greater than about 4%, or greater than about 3%, or
greater than about 2%, or greater than about 1%, or greater than
about 0.9%, or greater than about 0.8%, or greater than about 0.7%,
or greater than about 0.6%, or greater than about 0.5%, or greater
than about 0.4%, or greater than about 0.3%, or greater than about
0.2%, or greater than about 0.1%, or greater than about 0.01%, or
greater than about 0.001%.
[0609] In some embodiments, a composition including silk fibroin
fragments may be supplied in a concentrated form suspended in
water. In some embodiments, a composition including silk fibroin
fragments may have a concentration by weight (% w/w or % w/v) or by
volume (v/v) of less than about 50%, or less than about 45%, or
less than about 40%, or less than about 35%, or less than about
30%, or less than about 25%, or less than about 20%, or less than
about 15%, or less than about 10%, or less than about 5%, or less
than about 4%, or less than about 3%, or less than about 2%, or
less than about 1%, or less than about 0.1%, or less than about
0.01%, or less than about 0.001%, or less than about 0.0001%, or
less than about 0.00001%. In some embodiments, a composition
including silk fibroin fragments may have a concentration by weight
(% w/w or % w/v) or by volume (v/v) of greater than about 50%, or
greater than about 45%, or greater than about 40%, or greater than
about 35%, or greater than about 30%, or greater than about 25%, or
greater than about 20%, or greater than about 15%, or greater than
about 10%, or greater than about 5%, or greater than about 4%, or
greater than about 3%, or greater than about 2%, or greater than
about 1%, or greater than about 0.1%, or greater than about 0.01%,
or greater than about 0.001%, or greater than about 0.0001%, or
greater than about 0.00001%.
[0610] In some embodiments, the coating processes of the disclosure
may include a finishing step for the resulting coated textiles. In
some embodiments, the finishing or final finishing of the textiles
(e.g., fabrics) that are coated with a composition including silk
fibroin fragments under the processes disclosed herein may include
sueding, steaming, brushing, polishing, compacting, raising,
tigering, shearing, heatsetting, waxing, air jet, calendaring,
pressing, shrinking, treatment with polymerizer, coating,
lamination, and/or laser etching. In some embodiments, finishing of
the silk fibroin fragments coated textiles may include treatment of
the textiles with an AIRO.RTM. 24 dryer that may be used for
continuous and open-width tumbling treatments of woven, non-woven,
and knitted fabrics.
[0611] In some embodiments, the coated textiles (e.g., fabrics)
described herein may meet or exceed requirements established by the
following Test Methods:
TABLE-US-00026 Test Description Test Method Requirements
Dimensional AATCC 135 Maximum, Length: -3%, Stability Width: -3% to
Laundering Maximum, Length: -3%, Width: -5%, for twoway Stretch
Fabrics Maximum, Length: -5%, Width: -5%, for fourway Stretch
Fabrics No Growth Dimensional AATCC 158 Maximum, Length: -3%,
Stability Width: -3% to Dry Cleaning Maximum, Length: -3%, Width:
-5%, for twoway Stretch Fabrics Maximum, Length: -5%, Width: -5%,
for fourway Stretch Fabrics No Growth Pilling Resistance ASTM D
3512 Minimum 3.0 Abrasion ASTM D 4966 No rupture to 10,000 cycles
Resistance (plain fabrics up to 7.5 oz/yd.sup.2; or no rupture to
15,000 cycles (plain fabrics over 7.5 oz/yd.sup.2) Tearing Strength
ASTM D 1424 Shorts, Pants, Jeans, Jackets, All Plus Size Styles:
2.5 Lbs Minimum; or Blouse, Skirt Dress, Lining, excluding plus
size styles: 1.5 Lbs Minimum; or Intimate: <3 oz/yd.sup.2:
Minimum 1.5 lbs; 3-6oz/yd.sup.2: Minimum 2.0 lbs >6 oz/yd.sup.2:
Minimum 2.5 lbs Colorfastness to AATCC 61, 2A Color Change: Minimum
Laundering/ 4.0 Colorfastness to Staining: Minimum 3.0 Washing
Colorfastness to AATCC 132 Color Change: Minimum Dry Cleaning 4.0
Staining: Minimum 3.0 Colorfastness to AATCC 8 All except below -
Dry: Crocking/ Minimum 4.0; Wet: Colorfastness to Minimum 3.0; or
Rubbing Dark Shades (black, red, navy) - Dry: Minimum 4.0; Wet:
Minimum 2.5; or Indigos - Dry: Minimum 3.0; Wet: Minimum 2.0; or
Pigments - Dry: Minimum 3.5; Wet: Minimum 2.5. Colorfastness to
AATCC 107 Color Change: Minimum Water 4.0; Staining: Minimum 3.0
Colorfastness to AATCC 15 Color Change: Minimum Perspiration 4.0;
Staining: Minimum 3 Colorfastness to AATCC 16/20 Color Change:
Minimum Light AFU 4.0 AATCC 16/5 AFU pH Value AATCC 81 4.0~8.5 or
4.0~7.5 (children < 36 months) Antimicrobial AATCC 147 Original:
0% Bacterial Growth 20 Washes: 0% Bacterial Growth AATCC 100
Minimum 99.9% Reduction ASTM E 2149 Original: Minimum 99.9%
Reduction 20 Washes: Minimum 80% Reduction Wicking AATCC 79 1.0
second or less Water Repellency - AATCC 22 Original: 100 Rating
Spray Test After 3x Washes: Minimum 70 Rating Water Resistance -
AATCC 35 Maximum 1 gram on Rain Test original and after 3 x washes
Dimensional AATCC 150 Maximum, Length = -3%, Stability to Width =
-3% Laundering Maximum, Length = -3%, (Yoga Garment) Width = -5%
for two-way Stretch Fabrics Maximum, Length = -5%, Width = -5% for
four-way Stretch fabrics No Distortion Between Components No Growth
Dimensional AATCC 158 Maximum, Length = -3%, Stability to Width =
-3% Dry Cleaning Maximum, Length = -3%, (Yoga Garment) Width = -5%,
for two-way Stretch Fabrics Maximum, Length = -5%, Width = -5%, for
four-way Stretch Fabrics No Distortion Between Components No Growth
Pilling Resistance ASM D 3512 Minimum 3.0 (Yoga Garment)
Colorfastness to AATCC 61, 2A Color Change: Minimum Laundering/ 4.0
Colorfastness to Staining: Minimum 3.0 Washing (Yoga Garment)
Colorfastness AATCC 8 General: Dry: Minimum Crocking/ 4.0; Wet:
Minimum 3.0; Colorfastness to For Dark Colors (Black, Rubbing Red,
Navy): Wet: (Yoga Garment) Minimum 2.5 Pigment: Dry: Minimum 3.5;
Wet: Minimum 2.5 Indigos: Dry: Minimum 3.0; Wet: Minimum 2.0
Colorfastness AATCC 107 Color Change: Minimum to Water 4.0 (Yoga
Garment) Staining: Minimum 3.0 Colorfastness to AATCC 15 Color
Change: 4.0 or better Perspiration (Yoga Staining: 3.0 or better
Garment) Colorfastness AATCC 16, 20 Minimum 4.0, All, Except to
Light AFU/5 Silk/Minimum 4.0, Silk (Yoga Garment) AFU pH Value
AATCC 81 Children (>36 months) & (Yoga Garment) Adults:
4.0~8.5 Children (<36 months): 4.0~7.5
[0612] In some embodiments, the coated textiles (e.g., fabrics)
described herein may meet requirements established by the foregoing
Test Methods. In some embodiments, the coated textiles (e.g.,
fabrics) described herein may exceed the requirements established
by the foregoing Test Methods.
[0613] In some embodiments, the coated textiles (e.g., fabrics) may
have antimicrobial (e.g., antifungal and/or antibacterial activity)
due to the silk fibroin fragments coating. In an embodiment,
antibacterial activity may be determined by the ability of bacteria
on the coated textile's surface to be washed away from the coated
textile surface following one or more wash cycles, or two or more
wash cycles, or three or more wash cycles, or four or more wash
cycles, or five or more wash cycles, where the bacteria do not
adhere to the surface of the coated textile. In an embodiment,
antibacterial activity may be determined by the ability of the
coating to reduce the quantity of the bacteria deposited on a
surface of the coated textile, wherein the coating may reduce the
quantity of the bacteria by greater than about 1%, or greater than
about 2%, or greater than about 3%, or greater than about 4%, or
greater than about 5%, or greater than about 10%, or greater than
about 20%, or greater than about 30%, or greater than about 40%, or
greater than about 50%, or greater than about 60%, or greater than
about 70%, or greater than about 80%, or greater than about 90%, or
greater than about 95%, or greater than about 96%, or greater than
about 97%, or greater than about 98%, or greater than about 99%, or
by about 100%. In an embodiment, antibacterial activity of the
coating on the coated textile may be determined by fluorescent
activity (see, e.g., U.S. Pat. Nos. 5,089,395 and 5,968,762, the
entirety of which are incorporated herein by reference). In an
embodiment, antibacterial activity for a coating may be determined
by the ability of the coating on a coated textile to break up
colonies of bacteria that may be deposited on a surface of the
coated textile. In an embodiment, antibacterial activity for a
coating may be determined by the ability of the coating on a coated
textile to: (a) prevent the formation of a bacterial biofilm on the
coated textile; and/or (b) reduce the size of a bacterial biofilm
on the coated textile.
EXAMPLES
[0614] The following examples are put forth so as to provide those
of ordinary skill in the art with a complete disclosure and
description of how to make and use the described embodiments, and
are not intended to limit the scope of what the inventors regard as
their disclosure nor are they intended to represent that the
experiments below are all or the only experiments performed.
Efforts have been made to ensure accuracy with respect to numbers
used (e.g., amounts, temperature, etc.) but some experimental
errors and deviations should be accounted for. Unless indicated
otherwise, parts are parts by weight, molecular weight is weight
average molecular weight, temperature is in degrees Centigrade, and
pressure is at or near atmospheric.
[0615] The compositions of this disclosure may be made by various
methods known in the art. Such methods include those of the
following examples, as well as the methods specifically exemplified
below. As used herein in the working examples, "low molecular
weight," "low MW," or "low-MW" silk fibroin fragments include
fragments with a molecular weight between about 14 and about 30
kDa. As used herein in the working examples, "medium molecular
weight," "medium MW," or "mid-MW" silk fibroin fragments include
fragments with a molecular weight between about 39 and about 54
kDa.
Example 1: Tangential Flow Filtration (TFF) to Remove Solvent from
Dissolved Silk Solutions
[0616] A variety of % silk concentrations have been produced
through the use of Tangential Flow Filtration (TFF). In all cases a
1% silk solution was used as the input feed. A range of 750-18,000
mL of 1% silk solution was used as the starting volume. Solution is
diafiltered in the TFF to remove lithium bromide. Once below a
specified level of residual LiBr, solution undergoes
ultrafiltration to increase the concentration through removal of
water. See examples below.
[0617] 7.30% Silk Solution: A 7.30% silk solution was produced
beginning with 30 minute extraction batches of 100 g silk cocoons
per batch. Extracted silk fibers were then dissolved using
100.degree. C. 9.3 M LiBr in a 100.degree. C. oven for 1 hour. 100
g of silk fibers were dissolved per batch to create 20% silk in
LiBr. Dissolved silk in LiBr was then diluted to 1% silk and
filtered through a 5 um filter to remove large debris. 15,500 mL of
1%, filtered silk solution was used as the starting
volume/diafiltration volume for TFF. Once LiBr was removed, the
solution was ultrafiltered to a volume around 1300 mL. 1262 mL of
7.30% silk was then collected. Water was added to the feed to help
remove the remaining solution and 547 mL of 3.91% silk was then
collected.
[0618] 6.44% Silk Solution: A 6.44% silk solution was produced
beginning with 60 minute extraction batches of a mix of 25, 33, 50,
75 and 100 g silk cocoons per batch. Extracted silk fibers were
then dissolved using 100.degree. C. 9.3 M LiBr in a 100.degree. C.
oven for 1 hour. 35, 42, 50 and 71 g per batch of silk fibers were
dissolved to create 20% silk in LiBr and combined. Dissolved silk
in LiBr was then diluted to 1% silk and filtered through a 5 um
filter to remove large debris. 17,000 mL of 1%, filtered silk
solution was used as the starting volume/diafiltration volume for
TFF. Once LiBr was removed, the solution was ultrafiltered to a
volume around 3000 mL. 1490 mL of 6.44% silk was then collected.
Water was added to the feed to help remove the remaining solution
and 1454 mL of 4.88% silk was then collected
[0619] 2.70% Silk Solution: A 2.70% silk solution was produced
beginning with 60 minute extraction batches of 25 g silk cocoons
per batch. Extracted silk fibers were then dissolved using
100.degree. C. 9.3 M LiBr in a 100.degree. C. oven for 1 hour.
35.48 g of silk fibers were dissolved per batch to create 20% silk
in LiBr. Dissolved silk in LiBr was then diluted to 1% silk and
filtered through a 5 um filter to remove large debris. 1000 mL of
1%, filtered silk solution was used as the starting
volume/diafiltration volume for TFF. Once LiBr was removed, the
solution was ultrafiltered to a volume around 300 mL. 312 mL of
2.7% silk was then collected.
Example 2: Silk Fibroin Chemically Linked to Nylon
[0620] Synthesis of chemically modified silk fibroin: 6% Low silk:
100 mL, was reacted with 2,3-Dibromopropionyl chloride (7.2 g=0.028
mol), as shown in FIG. 1, to afford a silk-conjugate construct.
Further application of this construct to a substrate including
reactive groups, results in substrate coated with silk, wherein the
silk is chemically linked to the substrate. As shown in FIG. 2,
this disclosure is not limited to any particular linker, but rather
discloses any suitable linker capable to chemically link silk to a
substrate.
Example 3: Coating Substrates with a Silk-Conjugate
[0621] Exhaustion: Nylon fabric: 300 g, LR: 1=13, temperature:
100.degree. C., time: 45 min, rinse, air dry. Nylon fabric (300g)
is placed in a container with coating solution in a liquor ratio
(LR) of 1:13. The container is closed, and the container is heated
to 100.degree. C. for 45 min. The container is cooled once the
exhaustion process is completed. The fabric is rinsed with water,
spinned to removed excess liquid, and allowed to air dry.
[0622] Samples used in various performance experiments:
TABLE-US-00027 Sample ID Solution STI-17100706 Control
STI-17100706-D001 Silk-Conjugate STI-17100706-D002 Silk only
STI-17100706-D003 Precursor linker only
[0623] Comparative vertical wicking test results for nylon samples
are shown in FIGS. 4A and 4B (STI-17100706-D001: samples coated
with silk-conjugate; STI-17100706-D002: samples coated with silk
only; STI-17100706-D003: samples coated with precursor linker only;
STI-17100706: control samples), at T=0 (FIG. 4A), and at T=3 (FIG.
4B). The higher the value the more water is absorbed by capillary
action through the fabric, which results in better performing
fabric. Samples coated with a silk-conjugate, and samples coated
with silk only improve wicking compared to an unfinished control
sample; samples coated with a silk-conjugate shows better wicking
than samples coated with silk only; unfinished control samples, and
samples coated with a precursor linker only show almost no
wicking.
[0624] Comparative absorbency test results for nylon samples coated
with chemically modified silk fibroin are shown in FIGS. 5A and 5B
(STI-17100706-D001: samples coated with silk-conjugate;
STI-17100706-D002: samples coated with silk only;
STI-17100706-D003: samples coated with precursor linker only;
STI-17100706: control samples), at T=0 (FIG. 5A), and at T=3 (FIG.
5B). Absorbency is measured in seconds. DNA: does not absorb the
water drop, the test is stopped at 60 seconds. The lower the
number, the faster the fabric absorbs, and therefore performance is
better for moisture management. Samples coated with a
silk-conjugate, and samples coated with silk only have a
significantly improved absorbency, and samples coated with a
silk-conjugate absorb better than samples coated with silk only;
unfinished control samples and samples coated with the precursor
linker only do not absorb at T=0.
[0625] Comparative dry rate test results for nylon samples coated
with chemically modified silk fibroin are shown in FIGS. 6A and 6B
(STI-17100706-D001: coated with silk-conjugate; STI-17100706-D002:
coated with silk only; STI-17100706-D003: coated with precursor
linker only; STI-17100706: control), at T=0 (FIG. 6A), and at T=3
(FIG. 6B). Dry rate (mL/h) is how long the fabric takes to dry, a
higher number means better performance. Samples coated with a
silk-conjugate have an improved dry rate compared to the unfinished
sample; samples coated with silk only have lower dry rate than
unfinished control samples (FIG. 6A); at T=3 samples coated with a
silk-conjugate show significant improvements (FIG. 6B).
[0626] Additional comparative vertical wicking test results for
nylon samples are shown in FIGS. 7A-7D (control: FIG. 7A; coated
with silk only: FIG. 7B; coated with in-situ modified silk: FIG.
7C; coated with purified silk-conjugate: FIG. 7D), tested after a
number (T) of laundering cycles (0, 3, and 20).
[0627] Additional comparative absorbency test results for nylon
samples coated with chemically modified silk fibroin are shown in
FIGS. 8A-8D (control: FIG. 8A; coated with silk only: FIG. 8B;
coated with in-situ modified silk: FIG. 8C; coated with purified
silk-conjugate: FIG. 8D), tested after a number (T) of laundering
cycles (0, 3, and 20).
[0628] Additional comparative dry rate test results for nylon
samples coated with chemically modified silk fibroin are shown in
FIGS. 9A-9D (control: FIG. 9A; coated with silk only: FIG. 9B;
coated with in-situ modified silk: FIG. 9C; coated with purified
silk-conjugate: FIG. 9D), tested after a number (T) of laundering
cycles (0, 3, and 20).
[0629] Comparative absorbency test results for nylon samples coated
with silk fibroin chemically modified with natural crosslinkers are
shown in FIG. 10 (control sample, sample coated with silk only,
sample coated with silk modified with caffeic acid, sample coated
with silk modified with genipin).
Example 4; Functionalized Silk
TABLE-US-00028 [0630] Functionalized Silk Chemical Structure
(Low-MW- 098-02-01) ##STR00040## (Mid-MW- 098-02-02) ##STR00041##
Hexamine (098-10-2) ##STR00042## ##STR00043## ##STR00044## (Mid-MW-
098-08-02) ##STR00045##
[0631] As used herein the symbols and conventions used in these
processes, schemes and examples are consistent with those used in
the contemporary scientific literature, for example, the Journal of
the American Chemical Society or the Journal of Biological
Chemistry.
[0632] Unless otherwise indicated, all temperatures are expressed
in .degree. C. (degrees Centigrade). All reactions conducted under
an inert atmosphere at room temperature unless otherwise noted.
Reagents employed without synthetic details are commercially
available or made according to literature procedures.
[0633] HPLC/Mass spectra were obtained on Dyonex series 3000 HPLC
coupled with Q Exactive.TM. Hybrid Quadrupole-Orbitrap.TM. Mass
Spectrometer. Detection is by MS, UV at 214 nM using either
Atmospheric Chemical Ionization (APCI) or Electrospray Ionization
(ESI) and an evaporative light-scattering detectior (ELSD). The
data was acquired using Thermo Scientific.TM. Xcalibur.TM.
Software. Data analysis was performed using PEAKS software.
[0634] Silk fibroin is secreted in the form of a 2.3 MDa protein
complex which consists of six sets of heavy chain-light chain
heterodimer and one molecule of fibrohexamerin (P25). Covalent
modification of silk fibroin was confirmed for different subunits
(heavy chain, light chain, and/or fibrohexamerin) based on m/z and
ms2 fragmentation patterns.
[0635] Prior to HPLC/MS, the functionalized silk synthesized was
subjected to protease digestion according to the procedures below.
In general, the functionalized silk in each sample were denatured
with 6M guanidine HCl and reduced with DTT at 60.degree. C. for 30
minutes followed by alkylation with iodoacetamide at room
temperature in the dark. The alkylation reaction was quenched by
the addition of excess DTT and the reaction was allowed to proceed
for another 30 minutes at room temperature. Chymotrypsin digestion
was carried out at 37.degree. C. overnight at a protein to protease
ratio of 1:50.
[0636] Attenuated Total Reflection was conducted on lyophilized
functionalized silk samples using Nicolet iS50 FTIR
Spectrometer.
[0637] The functionalized silk prepared according to the
experimental procedures described below are summarized below:
TABLE-US-00029 Sample ID Structure Characterization 077-027-1
##STR00046## MS, IEF.sup.a 077-024-2 ##STR00047## MS, IEF 077-028-2
##STR00048## MS, IEF 077-030-1 ##STR00049## MS, IEF 098-08-02
##STR00050## FTIR 098-29-02 ##STR00051## SEC-RI, FTIR 098-30-02
##STR00052## SEC-RI, FTIR .sup.aIEF stands for isoelectric
focus.
[0638] Functionalized SPF:
TABLE-US-00030 Structure ##STR00053## ##STR00054## ##STR00055##
##STR00056## ##STR00057## ##STR00058## ##STR00059##
[0639] Functionalized SPF:
TABLE-US-00031 Chemical Structure ##STR00060## ##STR00061##
##STR00062## ##STR00063## ##STR00064## ##STR00065##
##STR00066##
[0640] Low MW silk was placed on an ice bath and stirred at 300
rpm. The pH of the solution was adjusted to 9.5 and then glycidyl
methacrylate was added in 3 portions, over 3 hours. After the
addition, the ice bath was removed, and the mixture was allowed to
warm up to room temperature (RT). The mixture was allowed to react
at RT for 30 minutes. The reaction mixture was purified by dialysis
against water using a 10 kDa MWCO dialysis tubing.
[0641] Covalent modification of Low-MW silk fibroin was confirmed
for all three subunits (heavy chain, light chain, and
fibrohexamerin) based on m/z and ms2 fragmentation patterns from
the mass spectrum obtained in HPLC/MS analysis (See FIG. 9A and
FIGS. 12A-B).
##STR00067##
[0642] Low MW silk was placed on an ice bath and stirred at 300
rpm. Acetic anhydride was added in 3 portions, over 1 hour. After
each portion the pH was adjusted to 8.5-9.5 with sodium hydroxide.
After the last succinic acid addition, the ice bath was removed,
and the reaction was allowed to warm up to room temperature. The
mixture was allowed to react at RT for 30 minutes. The reaction
mixture was purified by dialysis against water using a 10 kDa MWCO
dialysis tubing.
[0643] Covalent modification of Low-MW silk fibroin was confirmed
for all three subunits (heavy chain, light chain, and
fibrohexamerin) based on m/z and ms2 fragmentation patterns from
the mass spectrum obtained in HPLC/MS analysis (See FIG. 9B and
FIGS. 13A-C).
##STR00068##
[0644] Low MW silk was placed on an ice bath and stirred at 300
rpm. Succinic anhydride was added in 3 portions, over 1 hour. After
each portion the pH was adjusted to 8.5-9.5 with sodium hydroxide.
After the last succinic acid addition, the ice bath was removed,
and the reaction was allowed to warm up to room temperature. The
mixture was allowed to react at RT for 30 minutes. The reaction
mixture was purified by dialysis against water using a 10 kDa MWCO
dialysis tubing.
[0645] Covalent modification of Low-MW silk fibroin was confirmed
for all three subunits (heavy chain, light chain, and
fibrohexamerin) based on m/z and ms2 fragmentation patterns from
the mass spectrum obtained in HPLC/MS analysis (See FIG. 9C and
FIG. 14).
##STR00069##
[0646] Covalent modification of Low-MW silk fibroin was confirmed
for all three subunits (heavy chain, light chain, and
fibrohexamerin) based on m/z and ms2 fragmentation patterns from
the mass spectrum obtained in HPLC/MS analysis (See FIG. 9D and
FIG. 15)
##STR00070##
[0647] Mid MW silk was adjusted to pH 7.2 with phosphate buffer and
heated to 37.degree. C. Hexanal was then added, followed by
hydrogen peroxide and the solution was allowed to react with
stirring 24 hr. The solution was then cooled to room temperature
and purified by dialysis against water using a 10 kDa MWCO dialysis
tubing.
##STR00071##
[0648] Mid MW silk was adjusted to pH 6.5 in phosphate buffer and
heated to 35.degree. C. Mushroom Tyrosinase was added and the
solution was allowed to stir for 2 hr. The solution was then heated
to 85.degree. C. for 10 min to deactivate the tyrosinase enzyme,
then the temperature was reduced to 60.degree. C. and
N,N-dimethylethylenediamine was added. The reaction mixture was
allowed to react for 2 hr. The solution was then cooled to room
temperature and purified by dialysis against water using a membrane
with MWCO of 10 kDa.
##STR00072##
[0649] Mid MW silk was adjusted to pH 6.5 in phosphate buffer and
heated to 35.degree. C. Mushroom Tyrosinase was added and the
solution was allowed to stir for 2 hr. The solution was then heated
to 85.degree. C. for 10 min to deactivate the tyrosinase enzyme,
then the temperature was reduced to 60.degree. C. and
1-aminopentane was added. The reaction mixture was allowed to react
for 2 hr. The solution was then cooled to room temperature and
purified by dialysis against water using a membrane with MWCO of 10
kDa.
[0650] The molecular weight bands of the functionalized silk
samples was obtained by gel electrophoresis using Novex precast
3-10 IEF gels. The gel electrophoresis experiments were run
according to ThermoFisher Novex "Pre-Cast Gel Electrophoresis
Guide" Version B, Jan. 27, 2003 IM-1002. In general, functionalized
silk samples were diluted to 14.7 mg/ml protein concentration in
3-10 IEF sample buffer before loading and BioRad 4.45-9.6 IEF
electrophoresis standards were used. The gels were focused at 100
constant volts for 1 hour, 200 constant volts for 1 hour, and 500
constant volts for 30 minutes. The gels were fixed in 12% TCA for
1/2 hour; stained in Coomassie Brilliant Blue R-250, stained in 10%
acetic acid, and dried between cellophane sheets.
[0651] FIGS. 12A-B show the results for the electrophoresis gel
experiments performed on the functionalized silk synthesized in
Examples 10 above and the controls. FIG. 12A shows the
electrophoresis gel from a few typical Activated Silks.TM., and
FIG. 10B shows the electrophoresis gel for chemically modified
Activated Silks.TM..
[0652] The mid-molecular weight Activated Silks.TM. have two
isoelectric point ranges, one between pH 4-5 and a second one
between pH 7-8. In contrast, low molecular weight Activated
Silks.TM. have only one isoelectric point, in the range of pH 4-5.
Upon chemical modification the isoelectric points of acetylated
(sample 077-024-2) and methacrylated (sample 077-027-1) silks are
unchanged. However, succinylation (sample 077-028-2) moves the
isoelectric point to lower values (pH <4.65), while amination
(sample 077-030-1) move the isoelectric point to a higher value (pH
5.1-6) and give rise to an additional isoelectric point (pH
7-8).
[0653] Sample description for the gel electrophoresis samples shown
in FIG. 10B
TABLE-US-00032 Lane Sample .mu.g load .mu.l Load 1 BioRad IEF Stds
-- 6 2 IEF Sample Buffer -- 7.35 3 077-024-2 100 7.35 4 077-027-1
100 7.35 5 077-027-2 100 7.35 6 077-028-2 100 7.35 7 077-030-1 100
7.35 8 MC-1 100 7.35 9 5700-SP 100 7.35 10 DBr-7 100 7.35 11 Ser-1
100 7.35 12 -- -- --
[0654] Molecular weight distribution for the functionalized silk
samples was obtained by the size exclusion chromatography analysis.
In general, sample solutions of the functionalized silk were
analyzed on an Agilent 1100 HPLC equipped with a PolySep GFC P-4000
(7.8.times.300 mm) size exclusion column and a refractive index
detector. The instrument was operated at a flow rate of 1 mL/min
using a mobile phase containing 100 mM sodium chloride+12.5 mM
sodium phosphate buffer (pH 7), for a sample run time of 20
minutes. The molecular weight distribution was calculated relative
to Dextran standards using the Cirrus software package.
[0655] FIG. 13 shows the chromatograms of two modified mid
molecular weight silks compared to a typical mid molecular silk.
The two modified silks have higher molecular weight compared to the
standard (evidenced by the shift towards early elution times).
[0656] All patents, patent applications, and published references
cited herein are hereby incorporated by reference in their
entirety. While the methods of the present disclosure have been
described in connection with the specific embodiments thereof, it
will be understood that it is capable of further modification.
Further, this application is intended to cover any variations,
uses, or adaptations of the methods of the present disclosure,
including such departures from the present disclosure as come
within known or customary practice in the art to which the methods
of the present disclosure pertain.
Sequence CWU 1
1
5316PRTArtificial SequenceSynthetic protein-like multiblock polymer
hexapeptideMISC_FEATURE(6)..(6)X can be is alanine, tyrosine,
valine, or serine 1Gly Ala Gly Ala Gly Xaa1 526PRTArtificial
SequenceSynthetic protein-like multiblock polymer hexapeptide 2Gly
Ala Gly Ala Gly Ser1 535PRTArtificial SequenceSynthetic mammalian
elastin 3Val Pro Gly Val Gly1 545PRTArtificial SequenceSynthetic
mammalian elastin 4Gly Val Gly Val Pro1 556PRTArtificial
SequenceSynthetic linker repetitve fragment 5Gly Ala Gly Ala Gly
Ser1 5644PRTArtificial SequenceSynthetic protein 6Ser Gly Phe Gly
Pro Val Ala Asn Gly Gly Ser Gly Glu Ala Ser Ser1 5 10 15Glu Ser Asp
Phe Gly Ser Ser Gly Phe Gly Pro Val Ala Asn Ala Ser 20 25 30Ser Gly
Glu Ala Ser Ser Glu Ser Asp Phe Ala Gly 35 4075PRTArtificial
SequenceSynthetic consensus peptidemisc_feature(4)..(4)Xaa can be
any naturally occurring amino acidMISC_FEATURE(5)..(6)X can be
alanine, serine, glycine, tyrocine, or proline 7Gly Pro Gly Xaa
Xaa1 589PRTArtificial SequenceSynthetic pro-resilin elastomeric
protein 8Gly Gly Arg Pro Ser Asp Thr Tyr Gly1 599PRTArtificial
SequenceSynthetic pro-resilin elastomeric protein 9Gly Gly Arg Pro
Ser Ser Ser Tyr Gly1 51035PRTAraneus diadematus 10Gly Ser Ser Ala
Ala Ala Ala Ala Ala Ala Ala Ser Gly Pro Gly Gly1 5 10 15Tyr Gly Pro
Glu Asn Gln Gly Pro Ser Gly Pro Gly Gly Tyr Gly Pro 20 25 30Gly Gly
Pro 35115PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 11Gly Pro Gly Ala Ser1 5125PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 12Gly Pro
Gly Ser Gly1 5135PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 13Gly Pro Gly Gly Tyr1 5145PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 14Gly Pro
Gly Gly Pro1 5155PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 15Gly Pro Gly Gly Ala1 5165PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 16Gly Pro
Gly Gln Gln1 5175PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 17Gly Pro Gly Gly Gly1 5185PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 18Gly Pro
Gly Gln Gly1 5195PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 19Gly Pro Gly Gly Ser1 5205PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 20Ala Ala
Ala Ala Ala1 5216PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 21Ala Ala Ala Ala Ala Ala1 5227PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 22Ala Ala
Ala Ala Ala Ala Ala1 5238PRTArtificial SequenceSynthetic
recombinant silk protein repetitve unit 23Ala Ala Ala Ala Ala Ala
Ala Ala1 5249PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 24Ala Ala Ala Ala Ala Ala Ala Ala Ala1
52510PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 25Ala Ala Ala Ala Ala Ala Ala Ala Ala Ala1 5
10269PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 26Gly Gly Arg Pro Ser Asp Thr Tyr Gly1
5279PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 27Gly Gly Arg Pro Ser Ser Ser Tyr Gly1
52824PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 28Gly Pro Tyr Gly Pro Gly Ala Ser Ala Ala Ala Ala
Ala Ala Gly Gly1 5 10 15Tyr Gly Pro Gly Ser Gly Gln Gln
202935PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 29Gly Ser Ser Ala Ala Ala Ala Ala Ala Ala Ala Ser
Gly Pro Gly Gly1 5 10 15Tyr Gly Pro Glu Asn Gln Gly Pro Ser Gly Pro
Gly Gly Tyr Gly Pro 20 25 30Gly Gly Pro 353020PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 30Gly Pro
Gly Gln Gln Gly Pro Gly Gln Gln Gly Pro Gly Gln Gln Gly1 5 10 15Pro
Gly Gln Gln 203127PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 31Gly Pro Gly Gly Ala Gly Gly Pro Tyr Gly
Pro Gly Gly Ala Gly Gly1 5 10 15Pro Tyr Gly Pro Gly Gly Ala Gly Gly
Pro Tyr 20 253228PRTArtificial SequenceSynthetic recombinant silk
protein repetitve unit 32Gly Gly Thr Thr Ile Ile Glu Asp Leu Asp
Ile Thr Ile Asp Gly Ala1 5 10 15Asp Gly Pro Ile Thr Ile Ser Glu Glu
Leu Thr Ile 20 253334PRTArtificial SequenceSynthetic recombinant
silk protein repetitve unit 33Pro Gly Ser Ser Ala Ala Ala Ala Ala
Ala Ala Ala Ser Gly Pro Gly1 5 10 15Gln Gly Gln Gly Gln Gly Gln Gly
Gln Gly Gly Arg Pro Ser Asp Thr 20 25 30Tyr Gly3439PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 34Ser Ala
Ala Ala Ala Ala Ala Ala Ala Gly Pro Gly Gly Gly Asn Gly1 5 10 15Gly
Arg Pro Ser Asp Thr Tyr Gly Ala Pro Gly Gly Gly Asn Gly Gly 20 25
30Arg Pro Ser Ser Ser Tyr Gly 353518PRTArtificial SequenceSynthetic
recombinant silk protein repetitve unit 35Gly Gly Ala Gly Gly Ala
Gly Gly Ala Gly Gly Ser Gly Gly Ala Gly1 5 10 15Gly
Ser3630PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 36Gly Pro Gly Gly Ala Gly Pro Gly Gly Tyr Gly Pro
Gly Gly Ser Gly1 5 10 15Pro Gly Gly Tyr Gly Pro Gly Gly Ser Gly Pro
Gly Gly Tyr 20 25 303724PRTArtificial SequenceSynthetic recombinant
silk protein repetitve unit 37Gly Pro Tyr Gly Pro Gly Ala Ser Ala
Ala Ala Ala Ala Ala Gly Gly1 5 10 15Tyr Gly Pro Gly Cys Gly Gln Gln
203824PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 38Gly Pro Tyr Gly Pro Gly Ala Ser Ala Ala Ala Ala
Ala Ala Gly Gly1 5 10 15Tyr Gly Pro Gly Lys Gly Gln Gln
203935PRTArtificial SequenceSynthetic recombinant silk protein
repetitve unit 39Gly Ser Ser Ala Ala Ala Ala Ala Ala Ala Ala Ser
Gly Pro Gly Gly1 5 10 15Tyr Gly Pro Glu Asn Gln Gly Pro Cys Gly Pro
Gly Gly Tyr Gly Pro 20 25 30Gly Gly Pro 354035PRTArtificial
SequenceSynthetic recombinant silk protein repetitve unit 40Gly Ser
Ser Ala Ala Ala Ala Ala Ala Ala Ala Ser Gly Pro Gly Gly1 5 10 15Tyr
Gly Pro Lys Asn Gln Gly Pro Ser Gly Pro Gly Gly Tyr Gly Pro 20 25
30Gly Gly Pro 354135PRTArtificial SequenceSynthetic recombinant
silk protein repetitve unit 41Gly Ser Ser Ala Ala Ala Ala Ala Ala
Ala Ala Ser Gly Pro Gly Gly1 5 10 15Tyr Gly Pro Lys Asn Gln Gly Pro
Ser Gly Pro Gly Gly Tyr Gly Pro 20 25 30Gly Gly Pro
354215PRTArtificial SequenceSynthetic silk protein-like multiblock
peptideMISC_FEATURE(1)..(1)X can be tyrosine or
glutamineMISC_FEATURE(4)..(4)X can be tyrosine or
glutamineMISC_FEATURE(8)..(8)X can be tyrosine or glutamine 42Xaa
Gly Gly Xaa Gly Ala Gly Xaa Gly Ala Gly Ala Gly Ala Gly1 5 10
154314PRTArtificial SequenceSynthetic silk protein-like multiblock
peptideMISC_FEATURE(11)..(12)X can be amino acid sequence GPS or
GPG 43Gly Pro Gly Gly Tyr Gly Pro Gly Gln Gln Xaa Xaa Ser Ala1 5
104411PRTArtificial SequenceSynthetic silk protein-like multiblock
peptideMISC_FEATURE(8)..(8)X can be tyrosine, glutamine, or alanine
44Gly Arg Gly Ala Ala Gly Gly Xaa Gly Ala Ala1 5
104515PRTArtificial SequenceSynthetic silk protein-like multiblock
peptideMISC_FEATURE(1)..(1)X can be tyrosine or
glutamineMISC_FEATURE(4)..(4)X can be tyrosine or
glutamineMISC_FEATURE(8)..(8)X can be tyrosine or glutamine 45Xaa
Gly Gly Xaa Gly Ala Gly Xaa Gly Ala Gly Ala Gly Ala Gly1 5 10
15468PRTArtificial SequenceSynthetic modified amino acid sequence
46Gly Cys Gly Gly Gly Gly Gly Gly1 5478PRTArtificial
SequenceSynthetic modified amino acid sequence 47Gly Lys Gly Gly
Gly Gly Gly Gly1 54814PRTArtificial SequenceSynthetic modified
amino acid sequence 48Gly Cys Gly Gly Ser Gly Gly Gly Gly Ser Gly
Gly Gly Gly1 5 104913PRTArtificial SequenceSynthetic modified amino
acid sequence 49Gly Lys Gly Gly Gly Gly Gly Gly Ser Gly Gly Gly
Gly1 5 105013PRTArtificial SequenceSynthetic modified amino acid
sequence 50Gly Cys Gly Gly Gly Gly Gly Gly Ser Gly Gly Gly Gly1 5
105133PRTAraneus diadematus 51Gly Ser Ser Ala Ala Ala Ala Ala Ala
Ala Ala Ser Gly Pro Gly Gln1 5 10 15Gly Gln Gly Gln Gly Gln Gly Gln
Gly Gly Arg Pro Ser Asp Thr Tyr 20 25 30Gly5239PRTAraneus
diadematus 52Ser Ala Ala Ala Ala Ala Ala Ala Ala Gly Pro Gly Gly
Gly Asn Gly1 5 10 15Gly Arg Pro Ser Asp Thr Tyr Gly Ala Pro Gly Gly
Gly Asn Gly Gly 20 25 30Arg Pro Ser Ser Ser Tyr Gly
355330PRTArtificial SequenceSynthetic recombinant silk protein
repetitve fragment 53Gly Pro Gly Gly Ala Gly Pro Gly Gly Tyr Gly
Pro Gly Gly Ser Gly1 5 10 15Pro Gly Gly Tyr Gly Pro Gly Gly Ser Gly
Pro Gly Gly Tyr 20 25 30
* * * * *