U.S. patent application number 11/234707 was filed with the patent office on 2006-01-26 for method for preparing a fluid absorber.
This patent application is currently assigned to Grain Processing Corporation. Invention is credited to Frank W. Barresi, Helene G. Bazin.
Application Number | 20060018939 11/234707 |
Document ID | / |
Family ID | 22895781 |
Filed Date | 2006-01-26 |
United States Patent
Application |
20060018939 |
Kind Code |
A1 |
Bazin; Helene G. ; et
al. |
January 26, 2006 |
Method for preparing a fluid absorber
Abstract
Disclosed are a fluid absorber, a method for preparing a fluid
absorber, and a method for absorbing fluid from the skin. The
disclosed method for preparing a fluid absorber generally comprises
the steps of selecting a starch and an enzyme for hydrolysis of the
starch, determining a fluid absorption optimum hydrolysis level for
the starch, and ezymatically hydrolyzing the starch to
approximately the optimum level thus determined. The starch
alternatively may be hydrolyzed with acid hydrolysis without the
use of an enzyme catalyst. The disclosed method for absorbing fluid
from the skin includes the step of applying a fluid absorbing
effective amount of a fluid absorber thus prepared. Absorption
properties of the fluid absorber of the invention are comparable to
or exceed those of commercially available skin fluid absorbers,
such as talc and unmodified corn starch.
Inventors: |
Bazin; Helene G.;
(Cincinnati, OH) ; Barresi; Frank W.; (Coralville,
IA) |
Correspondence
Address: |
BANNER & WITCOFF, LTD.
TEN SOUTH WACKER DRIVE
SUITE 3000
CHICAGO
IL
60606
US
|
Assignee: |
Grain Processing
Corporation
Muscatine
IA
|
Family ID: |
22895781 |
Appl. No.: |
11/234707 |
Filed: |
September 23, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10459292 |
Jun 11, 2003 |
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11234707 |
Sep 23, 2005 |
|
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|
09971239 |
Oct 4, 2001 |
6946148 |
|
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10459292 |
Jun 11, 2003 |
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60237918 |
Oct 4, 2000 |
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Current U.S.
Class: |
424/401 ;
424/70.13 |
Current CPC
Class: |
A61Q 19/00 20130101;
C08B 30/12 20130101; A23L 27/70 20160801; A61Q 19/008 20130101;
C08B 30/18 20130101; A61Q 1/12 20130101; A61K 8/0279 20130101; A61Q
15/00 20130101; A61K 8/732 20130101 |
Class at
Publication: |
424/401 ;
424/070.13 |
International
Class: |
A61K 8/73 20060101
A61K008/73 |
Claims
1. A method for absorbing oil from the skin, the method comprising:
applying a fluid-absorbing effective amount of a fluid absorber,
said fluid absorber comprising a hydrolyzed starched product having
a degree of hydrolysis ranging from about 30% to about 40%.
2. A method according to claim 1, said hydrolysis level ranging
from about 35% to about 42%.
3. A method according to claim 1, said hydrolysis level ranging
from about 38% to about 42%.
4. A method according to claim 1, said hydrolysis level being about
40%.
5. A method according to claim 1, said porous starch granules
comprising ground granules.
6. A method according to claim 1, said starch comprising corn
starch.
7. A method according to claim 1, said fluid absorber including a
fragrance.
8. A method according to claim 1, said starch comprising a
crosslinked starch.
9. A method according to claim 1, said starch comprising an
acid-thinned starch.
Description
RELATED APPLICATION
[0001] This application claims priority to prior provisional
application 60/237,918, the entire contents of which are hereby
incorporated by reference.
TECHNICAL FIELD OF THE INVENTION
[0002] The invention relates to a method for absorbing fluid from
the skin, and towards a method for preparing a fluid absorber that
is suitable for absorbing fluid from the skin. The invention
further provides a fluid absorber which functions as a carrier for
other products, in particular oleogenous products such as certain
flavorings, and provides a method for absorbing such fluid, and a
product carried by such a fluid absorber. The fluid absorber used
in conjunction with the invention comprises granular starch that
has been partially hydrolyzed, preferably via enzymatic
hydrolysis.
BACKGROUND OF THE INVENTION
[0003] Enzymes capable of hydrolyzing granular starch at
temperatures below the starch gelatiniztion temperature are known
in the art. For instance, it has long been known that
alpha-amylases can hydrolyze granular starch, as disclosed in, for
instance, Richert et al., Publication of the Carnegie Institution
at Washington, No. 173, Part 1 (1913). More recently, other
enzymes, such as glucoamylase enzymes, have also been found to
hydrolyze granular starch below the starch gelatization
temperature. It is believed that the presence of a starch-binding
domain is essential for an enzyme to hydrolyze granular starch;
numerous enzymes having such domains are known, as disclosed, for
instance, in Walker, G. J. et al. Biochemical Journal, 86:452
(1963); Belshaw, N. J. et al., Biochim. Biophys. Acta, 1078:1117-20
(1991), and Svensson, B. et al., Eur. J. Biochem., 154:497-502
(1986). As is well known in the art, the term "enzyme hydrolysis"
refers to enzyme-catalyzed hydrolysis, and thus enzymes such as
alpha-amylase can be regarded as "hydrolyzing" starch via a
catalytic hydrolytic action.
[0004] As is also known in the art, when a granular starch is
treated with an alpha amylase or a glucoamylase, the granular
structure of the starch degrades, leaving behind a porous starch
granule upon partial hydrolysis of the starch, or, if the enzymatic
hydrolysis is allowed to continue, yielding a starch hydrolyzate or
ultimately glucose or another lower order sugar. It is also
recognized that the enzymatic attack on starch granules takes place
by exo-corrosion in which the enzyme either erodes the entire
surface of the granule or digests a channel from points on the
surface towards the center of the granule. In the latter mode of
attack, once the center is reached, the enzymatic attack proceeds
outwardly from the center over a broader front. The internal
structure of a porous starch granule that has been so modified is
open and cavernous and can exhibit either a tercaced or a
step-shaped appearance.
[0005] When a glucoamylase enzyme is allowed to completely
hydrolyze a starch granule, the resulting product typically is
glucose. U.S. Pat. Nos. 2,583,451; 3,922,198; 3,922,199; 4,612,284;
and 4,618,579 disclose processes for converting granular starch to
glucose by treating of the starch with glucoamylase or a mixture of
glucoamylase with alpha-amylase. Other reaction products are
possible; for instance, U.S. Pat. No. 3,922,201 discloses a process
for the preparation of levulose-containing compositions from
granular starch by treating the starch with alpha-amylase,
glucoamylase, and glucose isomerase.
[0006] The prior art also has described the enzymatic hydrolysis of
starch below the gelatinization temperature to produce starch
hydrolyzes other than glucose. For instance, U.S. Pat. No.
3,922,196 discloses a process for converting granular starch to a
starch hydrolyzate having a DE (dextrose equivalent) between 40 and
55 and including a high percentage of disaccharides and
trisaccharides. The process disclosed in this patent employs
alpha-amylase, glucoamylase, beta-amylase and isoamylase. Another
document, U.S. Pat. No. 4,113,509, discloses an enzymatically
produced high maltose-maltotriose starch hydrolyzate having a DE of
40 to 55. This patent discloses a process in which alpha-amylase,
alone or with a saccharifying enzyme such as glucoamylase or
beta-amylase, is used to hydrolyze the starch. Methods for the
production of other malto-oligosaccharides such as maltose and
maltotetraose by treatment of starch with specific alpha-amylases
have also been employed on an industrial scale.
[0007] The prior art also has provided applications for porous
starches that are obtained by partial enzymatic digestion of the
granular starch. For instance, U.S. Pat. No. 4,985,082 discloses a
starch matrix material comprising granular starch that is partially
hydrolyzed with an alpha-amylase and/or a glucoamylase and treated
chemically to modify the structural integrity and surface
characteristics of the starch. The disclosed starches are said to
be useful as adjuvants for antiperspirants and as bulking agents
for foods and drinks. U.S. Pat. No. 4,551,177 discloses a
compressible starch said to be useful as a binder for a tablet or
capsule and which is said to be prepared by treating granular
starch with an acid and/or with an alpha-amylase enzyme at a
temperature below the gelatinization temperature of the starch. Yet
another document, U.S. Pat. No. 5,445,950, discloses a method of
using alpha amylase to prepare slightly decomposed starch granules
having low viscosity. The starch granules are said to be useful as
a raw material in the starch and sugar industry. U.S. Pat. No.
5,904,941 discloses a viscosifier that comprises an enzymatically
hydrolyzed, ungelatinized granular starch with a dextrose
equivalent of from about 5 to 60. Still another document, U.S. Pat.
No. 5,935,826, discloses a modified starch prepared by the
glucoamylase hydrolysis of a starch derivative that contains a
hydrophobic group or both a hydrophobic and a hydrophilic group.
The starches are said to be characterized by having a DE from 20 to
80, and are said to be useful as emulsifiers or an encapsulating
agents. International Patent Publication WO 96/10586 discloses a
method for preparing a fat substitute based on hydrolyzed granular
starch. U.S. Pat. No. 5,919,486 discloses a powder preparation that
comprises a porous starch grain carrier and a material carried
within the pores of the carrier, the porous starch grain carrier
having been prepared by partially hydrolyzing starch with raw
starch digestive enzyme.
[0008] Other starches also have been used in dusting powder
applications for many years, primarily to absorb more fluids from
the skin. For example, U.S. Pat. No. 4,568,539 discloses
compositions said to exhibit excellent moisture absorbency and
comprising starch and a specific pregelatinized starch. Another
document, EP 182,296, discloses a body dusting powder that
comprises a porous starch granule which consists essentially of the
residue remaining after about from 45% to 95% by weight of the
granular starch has been solublized with an enzyme.
[0009] Skin fluids found on the skin surface typically comprise a
complex mixture of sebum, lipids, sweat, and environmental or
applied material. Because such fluids can provide nutrients and a
moisture-rich environment for microorganism to proliferate, such
fluids can cause body odors and even in some cases bacterial and
fungal infections. These effects can be mitigated by applying a
fluid-absorbing effective amount of a powdered starch composition
as described in the prior art, or other known absorbents such as
talc, cellulose derivatives, and so forth. The aforementioned
starch-based compositions are said to control excess moisture,
(i.e. the aqueous component of skin fluid), but are not said to
control the oily secretions produced by sebaceous glands.
[0010] It is a general object of the invention to provide a method
for preparing a fluid absorber that is effective in absorbing oil
from the skin, and, more generally, that is effective in absorbing
fluid from the skin. In other embodiments it is a general object to
provide a fluid absorber.
THE INVENTION
[0011] It has now been discovered that in many cases the oil
absorbency of a porous starch product will be maximized at a starch
hydrolysis level that is less in the hydrolysis level at which
water absorption is maximized. The invention makes use of this
discovery by providing a method in which the hydrolysis level of
the starch is controlled to optimize the fluid absorbency
properties of the porous starch granules for use in absorbing fluid
from the skin. It has further been found that oil absorption of a
porous starch granule will reach a plateau after hydrolysis has
proceeded to a certain extent, typically from about 30% to about
60%. The invention makes use of this discovery in certain
embodiments to provide an essential fluid absorber not only for use
in absorbing fluids from the skin, but also for use in numerous
other applications, such as a carrier. The term "fluid absorber"
thus may be deemed to include without limitation a product that in
intended use absorbs fluid (such as from the skin) or a product
that carries another product, i.e. a carrier.
[0012] In accordance with a preferred embodiment of the invention,
a method is provided for preparing a fluid absorber. Generally, a
granular starch and an enzyme for hydrolysis of the starch are
selected, and, based on the starch and enzyme chosen, a fluid
absorption optimum hydrolysis level is estimated. The starch then
is enzymatically hydrolyzed under reaction conditions suitable to
result in a porous granular starch, and the enzymatic hydrolysis is
terminated when the hydrolysis has proceeded through a point within
a predetermined range, typically within .+-.15%, or less, of the
estimated fluid absorption optimum hydrolysis level. In other
general embodiments, the starch is hydrolyzed without the use of an
enzyme catalyst. In some embodiments, two hydrolyses are performed;
one an acid hydrolysis that is not catalyzed enzymatically and one
that is catalyzed enzymatically. These hydrolyses may be performed
sequentially, in either order. In accordance with another
embodiment of the invention, a method for absorbing fluid from the
skin is provided. The method comprises applying a fluid-absorbing
effective amount of porous starch granules prepared as described
above. The fluid absorption optimum hydrolysis level may in some
embodiments be considered to be that in which the oil absorption is
maximized. In other embodiments of the invention, the fluid
absorption optimum hydrolysis level may be based on the cumulative
absorbence of the porous starch granule for various fluids, such as
fluids that approximate the fluids found on the skin. One such
fluid is a fluid that is composed of a mixture of water, I% saline
(NaCl), and oil. The invention further encompasses a fluid absorber
prepared in accordance with the present teachings. Other features
and-embodiments of the invention are set forth hereinbelow.
BRIEF DESCRIPTION OF THE FIGURES
[0013] FIG. 1 is a graph illustrating the data set forth in Example
1.
[0014] FIG. 2 is a graph illustrating the data set forth in Example
4.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0015] Generally, the invention contemplates the partial hydrolysis
of a granular starch, preferably with an enzyme. The starches that
may be used as starting materials in preparing the porous starch
granules may be derived from any native source, and typical starch
sources include cereals, tubers, roots, legumes, and fruits.
Exemplary starches include those obtained from corn, potato, wheat,
rice, sago, tapioca, and sorghum. Corn starch is preferred in light
of its low cost and ready availability, and also in light of the
known skin affinity of corn starch and relative ease of
modification of the granular structure of corn starch compared to
starches such as potato. Suitable starches include pearl starches,
such as PURE-DENT.RTM. B700 and corn starch B200, both sold by
Grain Processing Corporation of Muscatine, Iowa The starches used
in conjunction with the invention not only may be native starches
but also may be starches that have been modified prior to enzymatic
hydrolysis. Exemplary of such modified starches are crossed-linked
starches, which may comprise a native starch that have been
crossed-linked via any suitable cross-linking technique known in
the art or otherwise found to be suitable in conjunction with the
invention. An example of a commercially available cross-linked
starch is PURE-DENT.RTM. B850, sold by Grain Processing Corporation
of Muscatine, Iowa Other starches are deemed suitable for use in
conjunction with the invention, and thus, it is contemplated that,
for instance, derivatized, or acid-thinned starches, or starches
that have otherwise modified may be employed. Exemplars starches
include PURE-SET.RTM. B950, PURE-SET.RTM. B990, PURE-COAT.RTM. B70,
SUPERBOND.RTM. B300, SUPERCORE.RTM. S22, COATMASTER.RTM. K56F and
starch C-165, all available from Grain Processing Corporation,
Muscatine, Iowa.
[0016] In accordance with the invention, the starch is partially
hydrolyzed, preferably with an enzyme. Suitable enzymes for using
in conjunction with the invention include any of the wide variety
of art-recognized enzymes suitable for hydrolyzing starch, and
include, for instance, amylases derived from fungal, bacterial,
higher plant, or animal origin. Preferred examples of suitable
enzymes include endo-alpha-amylases, which cleave the 1-4 glucoside
linkage of starch. In addition, the enzyme may include or comprise
a beta-amylase, which removes maltose-units in a stepwise fashion
from the non-reducing ends of the alpha 1-4 linkages; a
glucoamylase, which remove glucose units in a stepwise manner from
the non-reducing end of starch and which cleaves both 1-4 and the
1-6 linkages; and debranching enzymes such as isoamylase and
pullulanase which cleave the 1-6 glucosidic linkages of the starch.
Such enzymes can be used alone or in combination. More generally,
any starch that hydrolyses granular starch via the porous starch
granules may be employed in conjunction with the invention.
[0017] Preferred sources of alpha-amylases and pullulanases include
several species of the Bacillus micro-organism, such as Bacillus
subtilis, Bacillus licheniformis, Bacillus coagulans, Bacillus
amyloliquefaciens, Bacillus stearothermophilus, and Bacillus
acidopullulyticlus, preferably the thermal stable amylases produced
by Bacillus stearothermophilus, Bacillus licheniformis, and
Bacillus acidopullulyticus. Maltogenic alpha-amylase, an enzyme
that produces high quantities of maltose and low molecular weight
saccaharides, is produced in Bacillus species; this enzyme can be
obtained from Novo Nordisk under the trademark MALTOGENASE.TM..
Preferred glucoamylases include those obtained from strans from
Aspergillus niger. One alpha-amylase suitable in conjunction with
the invention is G995, an alpha-amylase enzyme that is commercially
available from Enzyme Biosystems LTD. One glucoamylase that is
suitable for use in conjunction with the invention is G990, sold by
Enzyme Biosystems Ltd.
[0018] The starch should be partially hydrolyzed with the selected
enzyme to yield a porous starch granule. Generally, the enzymatic
hydrolysis is accomplished in an aqueous or buffered slurry at any
suitable starch solids level, preferably a solids level ranging
from about 10% to about 55% by weight on dry starch basis, more
preferably about 25% to about 35% by weight. The pH and temperature
of the slurry should be adjusted to any conditions effective to
allow enzyme hydrolysis. These will vary depending on the enzyme
and starch selected, and are not critical so long as the starch
does not gelatinize; generally, this can be accomplished so long as
the temperature remains below the gelatinization temperature of the
starch. In general, the pH will range from about 3.5 to about 7.5,
more preferably from about 4.0 to about 6.0. To reach this pH, any
suitable acid or base may be added, or a buffer may be employed.
The temperature preferably is maintained at least 3.degree. C.
below the gelatinization temperature of the starch. For corn
starch, the gelatinization temperature falls within a range between
about 62.degree. and 72.degree. C. Accordingly, the temperature of
the slurry should be below about 62.degree. C., preferably ranging
from about 22.degree. C. to about 59.degree. C., and more
preferably from about 51.degree. C. to about 61.degree. C.
[0019] The enzyme may be employed in any amount suitable to
effectuate a partial hydrolysis of the starch granules in the
slurry. Preferably, the enzyme is employed in the slurry in a
concentration ranging from about 0.2% to about 3% by weight on dry
starch, and more preferably from about 0.4% to about 2%. For
glucoamylase, this range is based on a 300 unit per ml enzyme
(based on the Enzyme Biosystems unit definition); for
alpha-amylase, this range is based on a 2200-5000 unit/ml enzyme
For the maltogenic alpha-amylase, the units are based on a
commercial 4000 unit/ml enzyme (MALTOGENASE from Novo Nordisk).
[0020] When it is desired to terminate the enzymatic hydrolysis,
the enzymatic hydrolysis may be terminated by any suitable
techniques known in the art, including acid or base deactivation,
ion exchange, solvent extraction, or other suitable techniques.
Preferably, heat deactivation is not employed, since a granular
starch product is desired and since the application of heat in an
amount sufficient to terminate the enzymatic reaction may cause
gelatinization of the starch. For typical enzymes, acid
deactivation may be accomplished by lowering the pH to a value
lower than 2.0 for at least 5 minutes, typically for 5 to 30
minutes. After deactivation, the pH of the slurry may be readjusted
to the desired pH according to the intended end use of the
granules. Typically, the pH will be adjusted to a pH within the
range from about 5.0 to 7.0, more preferably from about 5.0 to
about 6.0. The starch granules thus prepared then can be recovered
using techniques known in the art, including filtration and
centrifugation. Preferably, the reducing sugars and other
byproducts produced during the enzymatic treatment are removed
during the washing steps. Most preferably, the starch granules
subsequently are dried to a moisture content of or below about
12%.
[0021] In other embodiments of the invention, the starch granules
are hydrolyzed via acid hydrolysis without the use of an enzyme. In
such embodiments, the starch is placed in an aqueous acid medium at
a low pH (typically a pH below 2.0, and more preferably below 1.0)
at an elevated temperature for a time sufficient to hydrolyze the
starch. Those skilled in the art will appreciate that many reaction
conditions may be employed. For instance, the hydrolysis time may
range from a few hours to a period of days. Generally, the starch
solids level and temperature should be within the ranges described
above with respect to enzymatic hydrolysis. When it is desired to
terminate the hydrolysis, the pH should be adjusted to a level
sufficient to terminate substantially completely the hydrolysis
(typically to a pH ranging from about 5-7). The starch is
preferably dried, as discussed hereinabove. While this method is
suitable for the hydrolysis of starch, use of an enzyme is
preferred, inasmuch as it is believed such use will provide a
degree of regional specificity of hydrolysis of the starch granule
that will be lacking absent the use of an enzyme. It is further
believed that the use of an enzyme will affect the absorption
properties of the resulting porous starch granules. Also, enzyme
catalysts allow operation at more moderate pH levels.
[0022] In some embodiments of the invention, two hydrolyses are
performed; one an emzymatically catalyzed hydrolysis and one not
catalyzed enzymatically. The hydrolyses may be performed in either
order. Preferably, the first of the hydrolyses is terminated after
the starch granule has been hydrolyzed to an extent of about 50% of
the desired extent of hydrolysis and the second hydrolysis is next
commenced and allowed to proceed to finish the hydrolysis to the
desired extent. More generally, the first hydrolysis may be allowed
to proceed from about 10% to about 90% of the desired extent.
[0023] In accordance with a preferred embodiment of the invention,
the starch is hydrolyzed to an optimum fluid absorption hydrolysis
level. By "hydrolysis level" is contemplated the percentage of the
starch granule that is enzymatically hydrolyzed and thus no longer
remaining in granular form. The optimum fluid absorption hydrolysis
level most preferably is determined empirically, that is, by
testing the absorption properties for a specific starch hydrolyzed
with the specific enzyme being contemplated at various hydrolysis
levels and estimating from this information the hydrolysis level
that yields the optimum fluid absorption property. The hydrolysis
level alternatively may be determined via reference to a
predetermined correlation of fluid absorption levels and hydrolysis
levels. If the optimum hydrolysis level is known in advance, the
"determination" of the optimum hydrolysis level may be simply
predetermining the hydrolysis level with reference or regard to the
known optimum level. In any event, the extent of hydrolysis of
starch in a given hydrolysis reaction may be determined or
estimated from the reaction time.
[0024] The optimum fluid absorption property may be defined in any
manner consistent with the ultimate intended purpose of the starch,
for instance, in connection with the goal of absorbing fluids from
the skin. For instance, in one embodiment of the invention, the
optimum fluid absorption may be defined as the maximum oil
absorption, i.e., the fluid absorption optimum hydrolysis level may
be taken as the minimum hydrolysis level at which oil absorption is
maximized (reaches an apparent plateau). Any suitable oil, such as
a mineral oil, may be used to approximate oils found in the surface
of the skin. More generally, other fluids may be used to
approximate the composition of fluids on the skin. For instance,
the fluid on the surface of the skin may be estimated to comprise a
combination of water, 1% saline (NaCl), and oil. The fluid
absorption optimum hydrolysis level may be regarded as that
hydrolysis level at which the absorption of oil water, 1% saline,
and oil is deemed to be cumulatively optimized; this may be
regarded as the minimum hydrolysis level at when the oil absorption
reaches an apparent maximum. Alternatively, weighting factors may
be applied to the water, saline, and oil absorption parameters in
order to further approximate the composition of fluids from the
skin. Such weighting factors may be empirically determined. If
there is no one level which the fluid absorption is maximized (for
instance, if there is a range of hydrolysis levels at which fluid
hydrolysis is constant), any point in such range may be regarded as
the optimum level. Alternatively, the lowest hydrolysis level in
such range may be regarded as optimum. In other embodiments the
optimum fluid hydrolysis level may be empirically estimated.
[0025] The enzymatic or acid hydrolysis-should be allowed to
continue to within a selected range surrounding the estimated fluid
absorption optimum hydrolysis level. Any suitable range may be
selected. For instance, once the fluid absorption optimum
hydrolysis level has been estimated, the hydrolysis may be allowed
to proceed to within .+-.5%, more preferably .+-.10% and even more
preferably .+-.5%, of the estimated optimum level. For instance,
using corn starch, the optimum hydrolysis level in several
embodiments may range from about 30% to about 50%, in some
embodiments, about 30% to about 44%; in other embodiments; from
about 35% to about 44%; in other embodiments from about 38% to
about 42%; and in other embodiments the hydrolysis level may be
about 40%. This optimum represents the lowest hydrolysis level at
which oil absorption reaches an apparent plateau.
[0026] Once the fluid absorption optimum hydrolysis level has been
determined, the starch is hydrolyzed with the enzyme to within the
selected range surrounding the optimum level. The granules can be
recovered using any suitable technique known in the art or
otherwise found to be suitable, including filtration and
centrifugation.
[0027] In preparing a fluid absorber for the skin, the starch
granules thus prepared most preferably are ground to provide ground
granules after washing and drying. In absorbing fluid from the
skin, the ground granules may be applied in any amount effective to
absorb fluid therefrom. The ground granules may be used alone, or
in combination with other ingredients. In accordance with one
embodiment of the invention, for instance, a fluid absorber
includes the ground granules prepared in accordance with the
present technical and a fragrance. In other embodiments, the
granules are used as a carrier for materials such as colorants,
flavorants and other materials (in particular oleogenous
materials).
[0028] Exemplary applications for the non-ground starches prepared
in accordance with the invention include plating agents for flavors
and fragrances; plating agents for sticky or oily food products
such as peanut butter, honey, and molasses; plating of lecithin;
plating of colors; flow aids on shredded cheeses; stabilizing
agents for products (e.g. cream cheese, to keep oil from separating
out); coating agents (e.g., for pepperoni slices to prevent
sticking together); plating for fats, such as chicken fat; plating
to prevent oil separation in sauces; flow aids in dry sauce mixes;
absorbers for moisture in dry mixes; plating agents for
pharmaceutically active materials (e.g. prior to encapsulation);
plating of oleoresins; carriers for oils such as fish oil, and
thickeners for materials such as oils (e.g. olive oil). Exemplary
applications for the ground starches prepared in accordance with
the invention include fluid absorbing agents in body and "shower"
powders; fluid absorbing agents in other personal care products
such as dry hair care products, lip balms, antiperspirants and
deodorants, foot powers, dispensing body powders, natural soaps,
sun tan lotions, and body lotions; plating agents for colors and
flavors (for instance, as a carrier for colorants for facial
powder); plating agents for pharmaceutically active materials;
absorbents in medicated patches and plating agents for simethicone.
This list is by no means exhaustive, but to the contrary it is
contemplated that the starches prepared in accordance with the
invention will find use in numerous other applications. More
generally, any starch that has been hydrolyzed via enzymatic
hydrolysis or otherwise to form a fluid absorber should be deemed
useful in connection with such applications. The invention should
be deemed to include the use of such porous starches in such
applications. Preferably, but necessarily, the starch used in such
applications is hydrolyzed to an estimated fluid absorption optimum
hydrolysis level.
[0029] The following examples are provided to further illustrate
the invention, but should not be construed as limiting the
invention in scope.
EXAMPLES
[0030] The following procedure was used to estimate water, saline,
and oil absorption.
[0031] Prior to testing, each sample was screened through a 120
mesh (US) screen (0.0125 cm-0.0049 in.). In accordance with ASTM
D281-95, to 10.0 g (dry solid basis) starch (weighed in a 100 ml
beaker) was added dropwise water, 1% salt water, or a mineral oil
(CHEVRON SUPERLA #7) until a stiff, putty-like paste was formed.
The precision of this test is +/-0.5 ml and gives an indication of
the saturation value of the starch.
Example 1
[0032] This example shows how the degree of hydrolysis can affect
the water, salt water, and oil absorption properties of starch
granules.
[0033] In 1250 ml tap water was slurried 500 grams (dry solids
basis) of dent corn starch. The slurry was heated to a temperature
of either 51.degree. C. or 60.degree. C., as indicated in Table 1,
and the pH was adjusted to the indicated value using dilute
hydrochloric acid. The amount of alpha-amylase (G995, commercially
available from Enzyme Bio-Systems Ltd., and BAN and TERMAMYL 120 L,
commercially available from Novo Nordisk) indicated in Table 1 was
added and the reaction was allowed to proceed at the indicated
temperature with constant mixing for the indicated amount of time.
The enzyme was then deactivated by reducing the pH to 1.9 with
dilute hydrochloric acid. After 5 minutes at pH 1.9, the pH of the
slurry was adjusted to 5.0-5.5 with dilute sodium hydroxide. The
reaction mixture was filtered, washed with tap water, and dried.
The hydrolysis conditions and absorption test results are shown in
Table 1. "Yield" in these tables refers to yield of insoluble
starch granules. TABLE-US-00001 TABLE 1 Absorption (ml/10 g basis)
Conditions 1% Temp. pH Enzyme Time Yield Water Salt Oil -- -- None
-- -- 8.0 9.0 7.0 51.degree. C. 6.30 0.26 ml BAN 8 h 87.1% 9.5 10.0
9.5 51.degree. C. 6.50 0.26 ml 8 h 84.9% 10.0 10.5 10.0 TERMAMYL
51.degree. C. 5.80 0.13 ml G995 24 h 75.5% 11.0 12.0 11.0
60.degree. C. 5.20 1.3 ml G995 8 h 58.8% 14.5 15.5 12.5 51.degree.
C. 5.80 1.30 ml G995 48 h 55.0% 15.5 16.5 13.0 60.degree. C. 5.80
13.0 ml G995 8 h 40.4% 16.5 17.0 12.0
[0034] In this example, water and 1% salt water absorption of
alpha-amylase treated corn starches are similar and increase with
increasing hydrolysis yield, while a limit surprisingly is observed
with oil absorption, this limit occurring at around 60% yield (40%
hydrolysis). All alpha-amylase treated starches display higher
water and oil absorption than untreated corn starch. FIG. 1 shows
that, for water and 1% saline, the relationship between absorption
and percent hydrolysis is essentially linear over a broad range,
while the oil absorbance reaches a plateau.
Example 2
[0035] This example shows how the degree of hydrolysis can affect
the water and oil absorption of starch granules that have been
hydrolyzed with a maltogenic alpha-amylase, and how similar
treatment with alpha-amylase or a maltogenic alpha-amylase can lead
to different absorption properties.
[0036] 500 grams (dry solids basis) of dent corn starch were
slurried in 1250 ml tap water. The slurry was heated to 60.degree.
C. and the pH adjusted to 5.15 using dilute hydrochloric acid. The
amount of maltogenic alpha-amylase (MALTOGENASE 4000L, commercially
available from Novo Nordisk) indicated in Table 2 was added and the
reaction was allowed to proceed at 60.degree. C. with constant
mixing for the indicated amount of time. The enzyme was then
deactivated by reducing the pH to 1.9 with dilute hydrochloric
acid. After 5 minutes at pH 1.9, the pH was adjusted to 5.0-5.5
with dilute sodium hydroxide. The reaction mixture was filtered,
washed with tap water and dried. The hydrolysis conditions and
absorption test results are shown in Table 2. TABLE-US-00002 TABLE
2 Absorption Conditions (ml/10 g basis) Temp. pH Enzyme Time Yield
Water 1% Salt Oil -- -- None -- -- 8.0 9.0 7.0 60.degree. C. 5.15
2.0 ml MALTOGENASE 8 h 85.7% 11.0 11.0 8.5 60.degree. C. 5.15 5.0
ml MALTOGENASE 8 h 77.0% 11.0 11.5 11.0 60.degree. C. 5.15 10.0 ml
MALTOGENASE 24 h 69.8% 13.5 12.5 11.0 60.degree. C. 5.15 10.0 ml
MALTOGENASE 8 h 54.7% 14.5 15.0 11.0 +5.0 ml MALTOGENASE +5 h
[0037] In the last experiment, the starch was treated with 10 ml
MALTOGENASE for 10 hours, and 5 ml MALTOGENASE were subsequently
added and the reaction allowed to proceed for 5 hours. In this
example, water and 1% salt water absorption of maltogenic
alpha-amylase treated corn starches are similar and increase with
increasing hydrolysis yield, while a unit is observed with oil
absorption, occurring at around 70% yield. Oil absorption was lower
for the of maltogenic alpha-amylase treated starches of the example
than for the alpha-amylase treated starches of example 1. For a
similar hydrolysis level, oil absorption of alpha-amylase and of
maltogenic alpha-amylase treated starches were different.
Example 3
[0038] This example shows how the level of hydrolysis can affect
the water and oil absorption of starch granules, and how similar
treatment with different enzymes can lead to different absorption
properties.
[0039] 500 grams (dry solids basis) of dent corn starch were
slurried in 1250 ml tap water. The slurry was heated to 60.degree.
C. and the pH adjusted to 5.20 using dilute hydrochloric acid. The
amounts of alpha-amylase and pullulanase (G995 and ULTRADEX, a
pullulanase enzyme commercially available from Enzyme Bio-Systems
Ltd., PROMOZYME, a pullulanase enzyme commercially available from
Novo Nordisk) indicated in Table 3 were added and the reaction was
allowed to proceed at 60.degree. C. with constant mixing for the
indicated amount of time. The enzymes were then deactivated by
reducing the pH to 1.9 with dilute hydrochloric acid. After 5
minutes at pH 1.9, the pH was adjusted to 5.0-5.5 with dilute
sodium hydroxide. The reaction mixture was filtered, washed with
tap water and dried. The hydrolysis conditions and absorption test
results are shown in Table 3. TABLE-US-00003 TABLE 3 Absorption
Conditions (ml/10 g basis) Enzyme Time Yield Water 1% Salt Oil None
-- -- 8.0 9.0 7.0 0.65 ml G995 + 2 h 71.2% 12.5 12.5 10.5 2.6 ml
PROMOZYME 1.3 ml G995 + 6 h 61.3% 14.0 15.0 12.5 1.3 ml ULTRADEX
2.6 ml G995 + 6 h 56.1% 15.0 14.5 12.0 2.6 ml ULTRADEX 4.0 ml G995
+ 8 h 52.5% 16.0 16.0 11.5 4.0 ml ULTRADEX
[0040] The water, and 1% salt water absorption of
alpha-amylase-pullulanase treated corn starches of this example
were similar to alpha-amylase treated starches of example 1, while
a lower oil absorption limit was observed, occurring at around 60%
hydrolysis yield.
Example 4
[0041] This example demonstrates that the degree of hydrolysis can
affect the water and oil absorption of starch granules, and how
similar treatment with different enzymes can lead to different
absorption properties.
[0042] 500 grams (dry solids basis) of dent corn starch were
slurried in 1250 ml tap water. The slurry was heated to 60.degree.
C. and the pH adjusted to 5.20 using dilute hydrochloric acid. The
amounts of glucoamylase and alpha-amylase (G990 and G995,
commercially available from Enzyme Bio-Systems Ltd.) indicated in
Table 4 were added and the reaction was allowed to proceed at
60.degree. C. with constant mixing for the indicated amount of
time. The enzymes were then deactivated by reducing the pH to 1.9
with dilute hydrochloric acid. After 5 minutes at pH 1.9, the pH
was adjusted to 5.0-5.5 with dilute sodium hydroxide. The reaction
mixture was filtered, washed with tap water and dried. The
conditions and absorption test results are shown in Table 4.
TABLE-US-00004 TABLE 4 Absorption Conditions (ml/10 g basis) Enzyme
Time Yield Water 1% Salt Oil None -- -- 8.0 9.0 7.0 5.0 ml G990 2 h
91.8% 11.5 11.0 8.5 5.0 ml G990 4 h 90.5% 12.0 11.5 8.5 10.0 ml
G990 2 h 89.7% 12.5 12.5 8.5 5.0 ml G990 6 h 87.5% 12.5 12.5 9.0
10.0 ml G990 6 h 70.4% 14.0 14.0 9.0 0.05 ml G995 + 5.0 ml G990 8 h
68.5% 15.0 15.5 11.0 0.65 ml G995 + 5.0 ml G990 2 h 50.9% 16.5 16.5
11.5 1.3 ml G995 + 10.0 ml G990 2 h 39.2% 16.0 17.0 10.0 1.3 ml
G995 + 10.0 ml G990 4 h 28.3% 17.5 17.5 10.5 1.3 ml G995 + 10.0 ml
G990 6 h 25.0% 17.5 17.5 11.0 1.3 ml G995 + 10.0 ml G990 8 h 21.0%
18.5 18.0 10.5
[0043] FIG. 4 illustrates that the oil absorbance reaches a plateau
at about 60% yield (40% hydrolysis), while absorbance of water and
saline increases in an approximately linear manner.
Example 5
[0044] This example shows how the starch type can affect the water
and oil absorption of starch granules, as indicated by hydrolysis
level.
[0045] In separate experiments, 500 grams (dry solid basis) of
B850, a highly cross-linked corn starch sold by Grain Processing
Corporation of Muscatine, Iowa, and VINAMYL II, a high amylose
starch sold by National Starch, & Chemical Company, were
slurried in 1250 ml tap water. Each slurry was heated to 60.degree.
C. and the pH adjusted to 5.7 using dilute hydrochloric acid. The
amounts of alpha-amylase (G995, commercially available from Enzyme
Bio-Systems, Ltd.) indicated in Table 5 were added and the reaction
was allowed to proceed at 60.degree. C. with constant mixing for 8
h. The enzymes were then deactivated by reducing the pH to 1.9 with
dilute hydrochloric acid. After 5 minutes at pH 1.9, the pH was
adjusted to 5.0-5.5 with dilute sodium hydroxide. The reaction
mixture was filtered, washed with tap water and dried. The
hydrolysis conditions and absorption test results are shown in
Table 5. TABLE-US-00005 TABLE 5 Absorption G995 (ml/10 g basis)
Starch Type Dosage % Hydrolysis Water 1% Salt Water Oil Corn -- --
8.0 9.0 7.0 Corn 1.3 ml 41.2 14.5 15.5 12.5 B850 -- -- 8.5 9.0 7.0
B850 1.3 35.9 13.5 14.5 11.0 B850 2.6 43.6 16.0 15.5 11.5 High --
-- 11.0 11.0 10.5 Amylose High 1.3 34.9 17.5 15.5 9.0 Amylose
[0046] These results show that highly cross-linked corn starch and
high amylose starch are not as susceptible to G995 hydrolysis than
active corn starch, and that water and oil absorption can differ,
for the same hydrolysis level, with the starch type. Water
absorption in this example was the highest for high amylose starch
while oil absorption was lower for this starch.
Example 6
[0047] This example shows how the alpha-amylase treated corn starch
outperforms commercial baby powders for water, 1% salt water, and
oil absorption. TABLE-US-00006 TABLE 6 Absorption (ml/10 g basis)
Fluid Absorber Water 1% Salt Water Oil Commercial Talc 7.0 8.0 8.5
Commercial Talc 8.0 9.0 10.5 Commercial corn starch baby power 10.0
9.5 7.5 Alpha-amylase treated corn starch 14.5 15.5 12.5
[0048] As seen, the starch of the present invention outperformed
the commercial baby powders for water, 1% salt water, and oil
absorption.
Example 7
[0049] This example demonstrates how the characteristics of
granular starch can be affected by enzymatic treatment.
TABLE-US-00007 TABLE 7 Loose Bulk Surface/ Density Area Starch
Enzyme Treatment % Hydrolysis (g/cm.sup.3) (m.sup.2/g) Corn -- --
0.62 0.32 Corn .alpha.-Amylase G995 28.7 0.52 1.09 Corn
.alpha.-Amylase G995 41.2 0.46 1.14 Corn G995/G990 75.0 0.49
1.34
As seen, the enzymatic treatment increases the surface area while
lowering the density of the granules.
Example 8
[0050] This example illustrates the preparation of a fluid absorber
via acid hydrolysis of starch.
[0051] Starch, (B200, 643.5 g dry solids basis) was added to 1250
mL of water to make a 34% solids slurry. The mixture was heated to
59.degree. C. The pH was adjusted to below 1 by the addition of a
total of 50 mL of 1:1 concentrated hydrochloric acid:water. After
24 hours at 59.degree. C., the reaction was cooled and pH adjusted
to 5.3 with soda ash. The resulting mixture was filtered, washed
2.times.400 mL with water and dried overnight at 50.degree. C.
Example 9
[0052] This example illustrates the preparation of another fluid
absorber.
[0053] A fluid absorber was produced according to the procedure
described in Sample 8, except that 55 mL of 1:1 concentrated
hydrochloric acid:water was used instead of 50 mL.
Example 10
[0054] This example illustrates the preparation of a fluid absorber
via acid hydrolysis of starch followed by enzymatic hydrolysis.
[0055] Starch, (B200, 562 g dry solids basis) was added to 1250 mL
of water to make a 40% solids slurry. The mixture was heated to
60.degree. C. The pH was adjusted to below 1 by the addition of a
total of 30 mL of 1:1 concentrated hydrochloric acid:water. After
17 hours at 60.degree. C., the reaction was cooled and pH adjusted
to 5.8 with soda ash. Enzyme (G995 .alpha.-amylase, 1.3 mL) was
added to the mixture and it was stirred an additional 4 hours. The
slurry was then cooled to room temperature. The pH of the reaction
was then adjusted to 1.9 with 1:1 concentrated hydrochloric
acid:water and held at this pH for five minutes to terminate all
enzyme activity. The pH was then re-adjusted to 5.4 with 3% NaOH,
and filtered, washed and dried as in Example 8.
Example 11
[0056] This example illustrates the preparation of another fluid
absorber via acid hydrolysis of starch, followed by enzymatic
hydrolysis.
[0057] Acid thinned starch (B950, 500 g dry solids) was added to
1250 mL of water to make a 28% solids starch slurry. The mixture
was heated to 60.degree. C. The pH was adjusted to 5.8 with 3%
NaOH. Enzyme (G995 .alpha.-amylase, 1.3 mL) was added to the
mixture and it was stirred for 4 hours. The slurry was then cooled
to room temperature. The pH of the reaction was then adjusted to
1.9 with 1:1 concentrated hydrochloric acid:water and held at this
pH for five minutes to terminate all enzyme activity. The pH was
then re-adjusted to 5.4 with 3% NaOH, and filtered, washed and
dried as in Example 8.
Example 12
[0058] This example illustrates the preparation of a fluid absorber
by enzymatic hydrolysis of starch, followed by acid hydrolysis.
[0059] Starch, (B200, 500 g dry solids basis) was added to 1250 mL
of water to make a 28% solids slurry. The mixture was heated to
60.degree. C. The pH was adjusted to 5.8 with 3% NaOH. Enzyme (G995
.alpha.-amylase, 1.3 mL) was added to the mixture and it was
stirred for 4 hours. The pH of the reaction was then dropped to
below 1 by the addition of 50 mL of 1: 1 concentrated hydrochloric
acid:water. After 4 hours at 60.degree. C., the reaction was cooled
and pH adjusted to 5.8 with soda ash. The slurry was then filtered,
washed and dried as in Example 8.
Example 13
[0060] This example illustrates the preparation of a second fluid
absorber by enzymatic hydrolysis of starch followed by acid
hydrolysis.
[0061] A fluid absorber was produced according to the procedure
described in Example 12, except that 30 mL of 1:1 concentrated
hydrochloric acid:water was used instead of 50 mL.
Example 14
[0062] Starch (B200, 500 g dry solids basis) was added to 1250 mL
of water to make a 28% solids slurry. The mixture was heated to
60.degree. C. The pH was adjusted to 5.8 with 1:1 concentrated
hydrochloric acid:water. Enzyme (G995 .alpha.-amylase, 1.3 mL) was
added to the mixture and it was stirred for 8 hours. The pH of the
reaction was then adjusted to 1.8 with 1:1 concentrated
hydrochloric acid:water and held at this pH for five minutes to
kill enzyme activity. The pH was then re-adjusted to 5.3 with 3%
NaOH. The mixture then was filtered, washed (2.times.400 mL) and
dried. The resulting product had a oil absorbency of 12.0 mL per 10
g of starch and a water absorbency of 15.5 mL per 10 g of
starch.
[0063] The following table summarizes absorption data for
hydrolyzed granular starches made via enzyme, acid or combined
enzyme/acid procedures outlined in examples 5 and 8 through 14.
TABLE-US-00008 Absorption (mL/10 g) Sample Treatment % Yield Water
Oil B200 None -- 8.5 7.5 Example 5 Enzyme 59 14.5 12.5 (entry 2 in
Table 5) Example 8 Acid 70 15 7.5 Example 9 Acid 70 12.8 9.0
Example 10 Acid, then enzyme 52 19.8 8.0 Example 11 Acid, then
enzyme 66 12.8 9.0 Example 12 Enzyme, then acid 60 12.4 9.5 Example
13 Enzyme, then acid 60 12.4 10.5 Example 14 Enzyme 54 15.5
12.0
The data shows that acid hydrolysis and/or acid/enzyme hydrolysis
do improve water and oil absorption when compared to untreated
starch. Acid and enzyme sequential hydrolyses do not show any
improvements over enzyme catalyzed acid hydrolysis, especially in
the ability to absorb water and oil in relatively equal amounts.
Acid hydrolysis, followed by enzyme hydrolysis may be a way to
allow the enzyme more access to the granule, which could lead to
some unique properties, as demonstrated by the high water
absorption in Example 10. However, oil absorption of this sample
was relatively low.
Example 15
[0064] This example illustrates the hydrolysis of starch to prepare
a fluid absorber.
[0065] Based on the preceding examples, it was determined that, for
dent corn starch, the optimum hydrolysis level is about 40%
("optimum" being defined as the minimum hydrolysis level at which
the oil absorption reaches an apparent plateau).
[0066] Dent corn starch slurry was diluted to 28% solids (Baume
15.8 @ 60.degree. F.). The total volume of the mixture was 380
gallons (1000 lbs). The pH of the mixture was adjusted to 5.6 by
the addition of 250 mL of concentrated hydrochloric acid. The
reaction temperature was adjusted to 136-140.degree. F. and 1000 mL
of G995 alpha amylase enzyme (Enzyme Biosystems) was added to the
mixture. The reaction was stirred at temperature for 4 hours and
then another 100 mL of G995 was added. The reaction was stirred for
eight more hours. The pH of the reaction throughout the twelve-hour
reaction time was held at 5.4-5.8. The reaction was then quenched
by the addition of 2.0 L of concentrated HCL. The pH after quench
was 1.9. The starch slurry was held at pH 1.9 for 15 minutes and
then neutralized with 25.8 L of 3% NaOH to a pH of 5.3. The mixture
was then filtered, washed and dried. The oil absorbance of 10 g of
material was 13.0 mL.
Example 16
[0067] This example illustrates the preparation of a bleached
product.
[0068] Dent corn starch was diluted to 28% solids (Baume 15.8 @
60.degree. F.). The total volume was the mixture was 38 gallons
(100 lbs). The pH of the mixture was adjusted to 5.6 by the
addition of 18 mL of concentrated hydrochloric acid. The reaction
temperature was adjusted to 136-140.degree. F. and 100 mL of G995
alpha amylase enzyme (Enzyme Biosystems) was added to the mixture.
The reaction was stirred at temperature for 4 hours and then
another 100 mL of G995 was added. The reaction was stirred for
eight more hours. The pH of the reaction throughout the twelve-hour
reaction time was held at 5.4-5.8. The reaction was then quenched
by the addition of 0.34 gallons of sodium hypochlorite (0.5%,
17.65% active chlorine). The hypochlorite addition was over a 20
minute period, and the final pH of the reaction was 8.2. One hour
after the hypochlorite addition, sodium bisulfite, 100 grams, was
added and the mixture was stirred for an additional fifteen minutes
to ensure no residual oxidant remained. The pH of the mixture was
then adjusted to 5.4, filtered and washed. The resulting product
was dried and ground. The screen size of the ground product was
99.9% through a 100 mesh and 78% through a 325 mesh screen. The
Minolta color of the sample was L=97.00, b=2.37. The water and oil
absorbance of 10 g of material was 14.0 mL and 12.0 mL,
respectively.
Example 17
[0069] The fluid absorber prepared in accordance with Example 15 is
blended with a fragrance. The product thus prepared is used to
absorb oil from the skin.
Example 18
[0070] The fluid absorber used in accordance with Example 15 is
used to absorb an oleogenous flavoring agent. The product thus
prepared is added to a food product to provide flavor.
[0071] It is thus seen that the invention provides a method for
absorbing fluid from the skin, and also a method for preparing a
fluid absorber.
[0072] While particular embodiments of the invention have been
shown, it will be understood that the invention is not limited
thereto since modifications may be made by those skilled in the
art, particularly in light of the foregoing teachings. For
instance, the invention is operable to absorb fluids not only from
human skin but also from animal skin. It is, therefore,
contemplated by the appended claims to cover any such modifications
as incorporate those features which constitute the essential
features of these improvements within the true spirit and scope of
the invention. All references cited herein are hereby incorporated
by reference in their entireties.
* * * * *