U.S. patent application number 15/708129 was filed with the patent office on 2018-02-01 for ballast water treatment systems.
The applicant listed for this patent is Delone Bentz, William R. Peterson, II. Invention is credited to Delone Bentz, William R. Peterson, II.
Application Number | 20180028952 15/708129 |
Document ID | / |
Family ID | 54835346 |
Filed Date | 2018-02-01 |
United States Patent
Application |
20180028952 |
Kind Code |
A1 |
Peterson, II; William R. ;
et al. |
February 1, 2018 |
Ballast Water Treatment Systems
Abstract
A ballast water treatment system. Implementations may include an
intake screen, a ballast water intake pump coupled to the intake
screen, a screen filter coupled to an outlet of the ballast water
intake pump, and a multi-cartridge filter system coupled to the
screen filter and with one or more ballast tanks. A ballast water
dump pump may be coupled with the one or more ballast tanks. The
multi-cartridge filter system may include two or more cartridge
filters including a quaternary organosilane coating produced from a
quaternary ammonium organosilane reagent.
Inventors: |
Peterson, II; William R.;
(Chandler, AZ) ; Bentz; Delone; (Phoenix,
AZ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Peterson, II; William R.
Bentz; Delone |
Chandler
Phoenix |
AZ
AZ |
US
US |
|
|
Family ID: |
54835346 |
Appl. No.: |
15/708129 |
Filed: |
September 19, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14832937 |
Aug 21, 2015 |
9764264 |
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15708129 |
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14226720 |
Mar 26, 2014 |
9364572 |
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14832937 |
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10850121 |
May 19, 2004 |
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14226720 |
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62040348 |
Aug 21, 2014 |
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61805477 |
Mar 26, 2013 |
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60472429 |
May 22, 2003 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C02F 1/004 20130101;
C02F 1/50 20130101; B01D 37/025 20130101; A23L 3/3463 20130101;
C02F 2103/008 20130101; C02F 2303/24 20130101; A23L 3/358 20130101;
C02F 2303/04 20130101; B01D 29/56 20130101 |
International
Class: |
B01D 37/02 20060101
B01D037/02; A23L 3/358 20060101 A23L003/358; A23L 3/3463 20060101
A23L003/3463; C02F 1/00 20060101 C02F001/00; C02F 1/50 20060101
C02F001/50; B01D 29/56 20060101 B01D029/56 |
Claims
1. A ballast water treatment system comprising: a ballast water
intake pump coupled to the intake screen and adapted to draw
untreated water in through the intake screen; a particulate filter
system coupled to the screen filter and with one or more ballast
tanks configured to be coupled to the ship, the particulate filter
system comprising particles 0.6 mm to 6 mm in length; a ballast
water dump pump coupled with the one or more ballast tanks and
adapted to draw out treated water stored in the one or more ballast
tanks and discharge it back to the body of water surrounding the
ship; wherein the particulate filter system comprises particles
comprising a quaternary organosilane coating produced from a
quaternary ammonium organosilane reagent having the formula:
##STR00006## wherein A is a member independently selected from the
group consisting of --OR.sup.4, substituted or unsubstituted alkyl,
substituted or unsubstituted heteroalkyl, substituted or
unsubstituted cycloalkyl, substituted or unsubstituted
heterocycloalkyl, substituted or unsubstituted aryl, and
substituted or unsubstituted heteroaryl; and wherein R.sup.4 is a
member selected from the group consisting of hydrogen, substituted
or unsubstituted alkyl, substituted or unsubstituted heteroalkyl,
substituted or unsubstituted cycloalkyl, substituted or
unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,
and substituted or unsubstituted heteroaryl; and R is substituted
or unsubstituted alkylene; R.sup.1, R.sup.2, and R.sup.3 are
members each independently selected from the group consisting of
hydrogen, substituted or unsubstituted alkyl, substituted or
unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or
unsubstituted aryl; and substituted or unsubstituted heteroaryl; Z
is a member selected from the group consisting of fluoride,
chloride, bromide, iodide, tosylate, hydroxide, sulfate, and
phosphate; and n is 1, 2, or 3.
2. The system of claim 1, wherein the body of water comprising
microorganisms is one of salt water and fresh water.
3. The system of claim 1, further comprising a recirculation pump
coupled with the one or more ballast water tanks, the recirculation
pump coupled with a recirculation filter comprising particles 0.6
mm to 6 mm in length coated with the quaternary organosilane
coating, the recirculation pump adapted to draw treated water from
the one or more ballast water tanks through the recirculation
filter and back into the one or more ballast water tanks.
4. The system of claim 1, wherein the one or more ballast water
tanks further comprise an open-celled foam coated with the
quaternary organosilane coating.
5. The system of claim 4, wherein the open-celled foam comprises a
material selected from the group consisting of polymeric materials,
stainless steel, copper, silicon, carbon, and silicon carbide.
6. The system of claim 4, wherein the open-celled foam comprises a
range of pores per inch (PPI) between 10 PPI and 110 PPI.
7. The system of claim 4, wherein the open-celled foam comprises a
surface area per gram less than a surface area per gram of one of
filter sand and zeolite.
8. The system of claim 1, wherein a surface of the one or more
ballast tanks is coated with the quaternary organosilane
coating.
9. The system of claim 1, wherein the quaternary ammonium
organosilane reagent comprises one of
Tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;
Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;
Didecylmethyl-N-(3-trimethoxysilylpropyl)ammonium chloride; and any
combination thereof.
10. A ballast water treatment system comprising: a ballast water
intake pump coupled to the intake screen and adapted to draw
untreated water in through the intake screen; a particulate filter
system coupled to the screen filter and with one or more ballast
tanks configured to be coupled to the ship, the particulate filter
system comprising particles 0.6 mm-6 mm in length; a ballast water
dump pump coupled with the one or more ballast tanks and adapted to
draw out treated water stored in the one or more ballast tanks and
discharge it back to the body of water surrounding the ship;
wherein the particulate filter system comprises particles
comprising a quaternary organosilane coating produced from a
quaternary ammonium organosilane reagent having the formula:
A.sub.4-nSi(R NHaR.sup.1.sub.b Z).sub.n wherein A is a member
selected from the group consisting of alkoxy radicals of 1 to 8
carbon atoms, alkylether alkoxy radicals of 2 to 10 carbon atoms,
and alkyl radicals with 1 to 4 carbon atoms; R is a divalent
hydrocarbon radical with 1 to 8 carbon atoms; R.sup.1 is a member
selected from the group consisting of alkyl radicals with 1 to 12
carbon atoms, alkyl ether hydrocarbon radicals of 2 to 12 carbon
atoms, hydroxy-containing alkyl radicals of 1 to 10 carbon atoms,
and nitrogen-containing hydrocarbon radicals of 1 to 10 carbon
atoms, wherein the nitrogen atom has three bonds; a is 0, 1, or 2;
b is 1, 2 or 3; and the sum of a and b is 3; Z is a member selected
from the group consisting of chloride, bromide, iodide, tosylate,
hydroxide, sulfate, and phosphate; and n is 1, 2 or 3.
11. The system of claim 10, wherein the body of water comprising
microorganisms is one of salt water and fresh water.
12. The system of claim 10, further comprising a recirculation pump
coupled with the one or more ballast water tanks, the recirculation
pump coupled with a recirculation filter comprising particles 0.6
mm to 6 mm in length coated with the quaternary organosilane
coating, the recirculation pump adapted to draw treated water from
the one or more ballast water tanks through the recirculation
filter and back into the one or more ballast water tanks.
13. The system of claim 10, wherein the one or more ballast water
tanks further comprise an open-celled foam coated with the
quaternary organosilane coating.
14. The system of claim 13, wherein the open-celled foam comprises
a material selected from the group consisting of polymeric
materials, stainless steel, copper, silicon, carbon, and silicon
carbide.
15. The system of claim 13, wherein the open-celled foam comprises
a range of pores per inch (PPI) between 10 PPI and 110 PPI.
16. The system of claim 13, wherein the open-celled foam comprises
a surface area per gram less than a surface area per gram of one of
filter sand and zeolite.
17. The system of claim 10, wherein a surface of the one or more
ballast tanks is coated with the quaternary organosilane
coating.
18. A ballast water treatment system comprising: a ballast water
intake pump coupled to the intake screen; a particulate filter
system coupled to the screen filter and with one or more ballast
tanks, the particulate filter system comprising particles 0.6 mm-6
mm in length; a ballast water dump pump coupled with the one or
more ballast tanks; wherein the multi-cartridge filter system
comprises two or more cartridge filters comprising a quaternary
organosilane coating produced from a quaternary ammonium
organosilane reagent having the formula: ##STR00007## wherein A is
a member independently selected from the group consisting of
--OR.sup.4, substituted or unsubstituted alkyl, substituted or
unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or
unsubstituted aryl, and substituted or unsubstituted heteroaryl;
and wherein R.sup.4 is a member selected from the group consisting
of hydrogen, substituted or unsubstituted alkyl, substituted or
unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or
unsubstituted aryl, and substituted or unsubstituted heteroaryl;
and R is substituted or unsubstituted alkylene; R.sup.1, R.sup.2,
and R.sup.3 are members each independently selected from the group
consisting of hydrogen, substituted or unsubstituted alkyl,
substituted or unsubstituted heteroalkyl, substituted or
unsubstituted cycloalkyl, substituted or unsubstituted
heterocycloalkyl, substituted or unsubstituted aryl; and
substituted or unsubstituted heteroaryl; Z is a member selected
from the group consisting of fluoride, chloride, bromide, iodide,
tosylate, hydroxide, sulfate, and phosphate; and n is 1, 2, or 3;
and wherein the ballast water treatment system is adapted to
receive untreated water via the intake screen from a body of sea
water comprising microorganisms and achieve at least a 95%
reduction in a number of the microorganisms in the untreated water
after a single pass through the particulate filter system.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This document claims the benefit of the filing date of U.S.
Provisional Patent Application 62/040,348 to William R. Peterson
II, et al., entitled "Ballast Water Treatment Systems," which was
filed on Aug. 21, 2014, the disclosure of which is hereby
incorporated entirely herein by reference. This document also
claims the benefit of the filing date of U.S. Provisional Patent
Application 61/805,477, entitled "Static Microbial Fluid
Disinfection Utilizing Open Cell Substrates Treated With
Organosilane Quaternary Ammonium Chloride Compounds" to William R.
Peterson II, et al. which was filed on Mar. 26, 2013, the
disclosure of which is hereby incorporated entirely herein by
reference.
[0002] This application is also a continuation application of the
earlier U.S. Utility patent application to William R. Peterson II
et al., entitled "Ballast Water Treatment Systems," application
Ser. No. 14/832,937, filed Aug. 21, 2015, now pending, which is a
continuation-in-part application of the earlier U.S. Utility patent
application to William R. Peterson II et al., entitled "Static
Fluid Disinfecting Systems and Related Methods," application Ser.
No. 14/226,720, filed Mar. 26, 2014, which issued as U.S. Pat. No.
9,364,572 on Jun. 14, 2016, which was a continuation-in-part
application of the earlier U.S. Utility patent application to
William R. Peterson II et al., entitled "Antimicrobial Quaternary
Ammonium Organosilane Coatings," application Ser. No. 10/850,121,
filed May 19, 2004, now abandoned, which claimed the benefit of the
filing date of U.S. Provisional Patent Application 60/472,429
entitled "Water & Fluids Purification With Bonded Quaternary
Ammonium Organosilanes," to William R. Peterson II, which was filed
on May 22, 2003, the disclosures of each of which are hereby
incorporated entirely herein by reference.
BACKGROUND
1. Technical Field
[0003] Aspects of this document relate generally to methods and
compositions for reducing the number of microorganisms in a liquid
using a solid phase carrier coated with a quaternary ammonium
organosilane coating.
2. Background Art
[0004] Quaternary ammonium organosilanes have been used in a wide
variety of applications. U.S. Pat. No. 6,613,755 to Peterson II et
al. entitled "Antimicrobial Skin Preparations Containing
Organosilane Quaternaries," issued Sep. 2, 2003, the disclosure of
which is hereby incorporated entirely herein by reference,
discloses various examples of uses of quaternary ammonium
organosilane compounds that have antimicrobial properties.
SUMMARY
[0005] Implementations of ballast water treatment systems (ballast
water management systems) may include: an intake screen adapted to
receive ballast water from a body of water surrounding a ship
including microorganisms and a ballast water intake pump coupled to
the intake screen and adapted to draw ballast water in through the
intake screen. A screen filter may be coupled to the ballast water
intake pump and may be adapted to perform a screening of the
ballast water output by the ballast water intake pump. A
multi-cartridge filter system may be coupled to the screen filter
and with one or more ballast tanks configured to be coupled to the
ship. A ballast water dump pump may be coupled with the one or more
ballast tanks and may be adapted to draw out ballast water stored
in the one or more ballast tanks and discharge it back to the body
of water surrounding the ship. The multi-cartridge filter system
may include two or more cartridge filters including a quaternary
ammonium organosilane coating produced from a quaternary ammonium
organosilane reagent having the formula:
##STR00001##
[0006] A may be a member independently selected from the group
consisting of --OR.sup.4, substituted or unsubstituted alkyl,
substituted or unsubstituted heteroalkyl, substituted or
unsubstituted cycloalkyl, substituted or unsubstituted
heterocycloalkyl, substituted or unsubstituted aryl, and
substituted or unsubstituted heteroaryl; wherein R.sup.4 may be a
member selected from the group consisting of hydrogen, substituted
or unsubstituted alkyl, substituted or unsubstituted heteroalkyl,
substituted or unsubstituted cycloalkyl, substituted or
unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,
and substituted or unsubstituted heteroaryl; R may be substituted
or unsubstituted alkylene; R.sup.1, R.sup.2, and R.sup.3 may be
members each independently selected from the group consisting of
hydrogen, substituted or unsubstituted alkyl, substituted or
unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or
unsubstituted aryl; and substituted or unsubstituted heteroaryl; Z
may be a member selected from the group consisting of fluoride,
chloride, bromide, iodide, tosylate, hydroxide, sulfate, and
phosphate; and n may be 1, 2, or 3.
[0007] Implementations of ballast water treatment systems may
include one, all, or any of the following:
[0008] The body of water including microorganisms may be one of
salt water and fresh water.
[0009] A recirculation pump may be coupled with the one or more
ballast water tanks where the recirculation pump may be coupled
with a recirculation filter including one or more filter cartridges
coated with the quaternary organosilane coating. The recirculation
pump may be adapted to draw water from the one or more ballast
water tanks through the recirculation filter and back into the one
or more ballast water tanks.
[0010] The one or more ballast water tanks may further include an
open-celled foam coated with the quaternary organosilane
coating.
[0011] The open-celled foam may include a material selected from
the group consisting of polymeric materials, stainless steel,
copper, silicon, carbon, and silicon carbide.
[0012] The open-celled foam may include a range of pores per inch
(PPI) of between 10 PPI and 110 PPI.
[0013] The open-celled foam may have a surface area per gram less
than a surface area per gram of one of filter sand and zeolite.
[0014] A surface of the one or more ballast tanks may be coated
with the quaternary organosilane coating.
[0015] The quaternary ammonium organosilane reagent includes
Tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;
Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;
Didecylmethyl-N-(3-trimethoxysilylpropyl)ammonium chloride; and any
combination thereof.
[0016] Implementations of a ballast water treatment system may
include an intake screen adapted to receive ballast water from a
body of water surrounding a ship including microorganisms. A
ballast water intake pump may be coupled to the intake screen and
may be adapted to draw ballast water in through the intake screen.
A screen filter may be coupled to an outlet of the ballast water
intake pump, where the screen filter is adapted to perform a
screening of the ballast water output by the ballast water intake
pump. A multi-cartridge filter system may be coupled with the
screen filter and with one or more ballast tanks configured to be
coupled with the ship. A ballast water dump pump may be coupled
with the one or more ballast tanks and may be adapted draw out
ballast water stored in the one or more ballast tanks and discharge
it back to the body of water surrounding the ship. The
multi-cartridge filter system comprises two or more cartridge
filters including a quaternary organosilane coating produced from a
quaternary ammonium organosilane reagent having the formula:
A.sub.4-nSi(R NHaR.sup.1.sub.b Z).sub.n
[0017] A may be a member selected from the group consisting of
alkoxy radicals of 1 to 8 carbon atoms, alkylether alkoxy radicals
of 2 to 10 carbon atoms, and alkyl radicals with 1 to 4 carbon
atoms. R may be a divalent hydrocarbon radical with 1 to 8 carbon
atoms. R.sup.1 may be a member selected from the group consisting
of alkyl radicals with 1 to 12 carbon atoms, alkyl ether
hydrocarbon radicals of 2 to 12 carbon atoms, hydroxy-containing
alkyl radicals of 1 to 10 carbon atoms, and nitrogen-containing
hydrocarbon radicals of 1 to 10 carbon atoms, wherein the nitrogen
atoms has three bonds. The a may be 0, 1, or 2; b may be 1, 2, or
3; and the sum of a and b may be 3. Z may be a member selected from
the group consisting of chloride, bromide, iodide, tosylate,
hydroxide, sulfate, and phosphate. The n may be 1, 2 or 3.
[0018] Implementations of ballast water treatment systems may
include one, any, or all of the following:
[0019] The body of water including microorganisms may be one of
salt water and fresh water.
[0020] A recirculation pump may be included coupled with the one or
more ballast water tanks. The recirculation pump may be coupled
with a recirculation filter including one or more filter cartridges
coated with the quaternary organosilane coating. The recirculation
pump may be adapted to draw water from the one or more ballast
water tanks through the recirculation filter and back into the one
or more ballast water tanks.
[0021] The one or more ballast water tanks may further include an
open-celled foam coated with the quaternary organosilane
coating.
[0022] The open-celled foam may include a material selected from
the group consisting of polymeric materials, stainless steel,
copper, silicon, carbon, and silicon carbide.
[0023] The open-celled foam includes a range of pores per inch
(PPI) between 10 PPI and 110 PPI.
[0024] The open-celled foam may include a surface area per gram
less than a surface area per gram of one of filter sand and
zeolite.
[0025] A surface of the one or more ballast tanks may be coated
with the quaternary organosilane coating.
[0026] A ballast water treatment system may include an intake
screen, a ballast water intake pump coupled to the intake screen, a
screen filter coupled to an outlet of the ballast water intake
pump, and a multi-cartridge filter system coupled to the screen
filter and with one or more ballast tanks. A ballast water dump
pump may be coupled with the one or more ballast tanks. The
multi-cartridge filter system may include two or more cartridge
filters including a quaternary organosilane coating produced from a
quaternary ammonium organosilane reagent having the formula:
##STR00002##
[0027] A may be a member independently selected from the group
consisting of --OR.sup.4, substituted or unsubstituted alkyl,
substituted or unsubstituted heteroalkyl, substituted or
unsubstituted cycloalkyl, substituted or unsubstituted
heterocycloalkyl, substituted or unsubstituted aryl, and
substituted or unsubstituted heteroaryl; wherein R.sup.4 may be a
member selected from the group consisting of hydrogen, substituted
or unsubstituted alkyl, substituted or unsubstituted heteroalkyl,
substituted or unsubstituted cycloalkyl, substituted or
unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,
and substituted or unsubstituted heteroaryl; R may be substituted
or unsubstituted alkylene; R.sup.1, R.sup.2, and R.sup.3 may be
members each independently selected from the group consisting of
hydrogen, substituted or unsubstituted alkyl, substituted or
unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or
unsubstituted aryl; and substituted or unsubstituted heteroaryl; Z
may be a member selected from the group consisting of fluoride,
chloride, bromide, iodide, tosylate, hydroxide, sulfate, and
phosphate; and n may be 1, 2, or 3. The ballast water treatment
system may be adapted to receive ballast water via the intake
screen from a body of sea water including microorganisms and
achieve at least a 95% reduction in a number of the microorganisms
in the ballast water after a single pass through the
multi-cartridge filter system.
[0028] The foregoing and other aspects, features, and advantages
will be apparent to those artisans of ordinary skill in the art
from the DESCRIPTION and DRAWINGS, and from the CLAIMS.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Implementations will hereinafter be described in conjunction
with the appended drawings, where like designations denote like
elements, and:
[0030] FIG. 1 illustrates the reduction in the viable number of
bacteriophages by quaternary ammonium organosilane coated
zeolite;
[0031] FIG. 2 illustrates the reduction in the viable number of (A)
K. terriena bacteria and (B) E. Coli bacteria by quaternary
ammonium organosilane coated zeolite;
[0032] FIG. 3 illustrates the average reduction in the viable
number of bacteria and bacteriophages by quaternary ammonium
organosilane coated zeolite;
[0033] FIG. 4 illustrates the reduction in the viable number of
algae by quaternary ammonium organosilane coated zeolite;
[0034] FIG. 5 illustrates the reduction in the viable number of
protozoa parasites by quaternary ammonium organosilane coated
zeolite;
[0035] FIG. 6 illustrates an experimental apparatus containing a
column packed with quaternary ammonium organosilane coated zeolite
for use in decreasing the viable number of microorganisms in a
liquid;
[0036] FIG. 7 illustrates a block diagram of a first implementation
of a ballast water management system (BWMS);
[0037] FIG. 8 illustrates a block diagram of a second
implementation of a BWMS;
[0038] FIG. 9 illustrates an exemplary cartridge filter for use in
a multi-cartridge filter system.
DESCRIPTION
[0039] This disclosure, its aspects and implementations, are not
limited to the specific components, assembly procedures or method
elements disclosed herein. Many additional components, assembly
procedures and/or method elements known in the art consistent with
the intended static fluid disinfecting systems and related method
implementations will become apparent for use with particular
implementations from this disclosure. Accordingly, for example,
although particular implementations are disclosed, such
implementations and implementing components may comprise any shape,
size, style, type, model, version, measurement, concentration,
material, quantity, method element, step, and/or the like as is
known in the art for such static fluid disinfecting systems, and
implementing components and methods, consistent with the intended
operation and methods.
Definitions
[0040] As used herein, the term "reducing the viable number of
microorganisms," means reducing the number of microorganisms
capable of growing, working, functioning, and/or developing
adequately. The term includes, for example, reducing the overall
number of microorganisms, reducing the number of active
microorganisms (i.e. inactivating microorganisms), reducing the
number of microorganisms able to reproduce, reducing the number of
intact microorganisms, reducing the number of infectious agents,
removal of microorganisms, inactivation of microorganisms; and/or
and the like. "Eliminating the viable number of microorganisms"
means reducing the viable number of microorganisms to zero.
[0041] The term "microorganism," as used herein, means an organism
that, individually, can only be seen through a microscope. The term
microorganism includes, for example, bacteria, fungi,
actinomycetes, algae, protozoa, yeast, germs, ground pearls,
nematodes, viruses, prions, and algae.
[0042] The abbreviations used herein have their conventional
meaning within the chemical and biological arts.
[0043] Where chemical groups are specified by their conventional
chemical formulae, written from left to right, they equally
encompass the chemically identical substituents that would result
from writing the structure from right to left, e.g., --CH.sub.2O--
is equivalent to --OCH.sub.2--.
[0044] The term "alkyl," by itself or as part of another
substituent, means, unless otherwise stated, a straight (i.e.
unbranched) or branched carbon chain containing at least one
carbon, which may be fully saturated, mono- or polyunsaturated. An
unsaturated alkyl group is one having one or more double bonds or
triple bonds. An "unsubstituted alkyl" refers to branched or
unbranched alkyl groups wherein the backbone carbons are attached
to hydrogen and/or other backbone carbon. The term "alkylene"
refers to a divalent radical derivative of an alkyl.
[0045] A "backbone carbon" or "backbone heteroatom," as used
herein, refers to a carbon or heteroatom, respectively, that is not
at the point of attachment of an alkyl or heteroalkyl group, and
which forms part of a branched or unbranched chain containing at
least one carbon.
[0046] The term "alkoxy," refers to those alkyl groups attached to
the remainder of the molecule via an oxygen atom.
[0047] The term "alkylether" refers to an alkyl having at least one
carbon-oxygen-carbon linkage.
[0048] The term "hydroxy-substituted alkyl" refers to an alkyl
having at least one attached hydroxyl group.
[0049] The term "amine-substituted alkyl" refers to an alkyl having
at least one attached primary, secondary, or tertiary amine
group.
[0050] The term "hetero alkyl," by itself or in combination with
another term, means an alkyl having at least one heteroatom within
the carbon chain. The heteroatom is selected from the group
consisting of O, N, and S, wherein the nitrogen and sulfur atoms
may optionally be oxidized and the nitrogen heteroatom may
optionally be quaternized. The heteroatom(s) O, N, and S may be
placed at any interior position of the heteroalkyl group or at the
position at which the alkyl group is attached to the remainder of
the molecule. Up to two heteroatoms may be consecutive, such as,
for example, --CH.sub.2--NH--OCH.sub.3. Similarly, the term
"heteroalkylene" by itself or as part of another substituent means
a divalent radical derived from heteroalkyl. For heteroalkylene
groups, heteroatoms can also occupy either or both of the chain
termini.
[0051] An "unsubstituted heteroalkyl" refers to branched or
unbranched heteroalkyl groups wherein the backbone carbons are
attached to hydrogen, other backbone carbons, and/or backbone
heteroatoms. The backbone heteroatoms are attached to hydrogen,
backbone carbons, other backbone heteroatoms, and/or oxygen (in the
case of oxidized sulfur).
[0052] The terms "cycloalkyl" and "heterocycloalkyl," by themselves
or in combination with other terms, represent, unless otherwise
stated, cyclic versions of "alkyl" and "heteroalkyl," respectively.
Additionally, for heterocycloalkyl, a heteroatom can occupy the
position at which the heterocycle is attached to the remainder of
the molecule. The terms "cycloalkylene" and "heterocycloalkylene"
refer to the divalent derivatives of cycloalkyl and
heterocycloalkyl groups, respectively.
[0053] The terms "halo" or "halogen," by themselves or as part of
another substituent, mean, unless otherwise stated, a fluorine,
chlorine, bromine, or iodine atom. Additionally, terms such as
"haloalkyl," are meant to include monohaloalkyl and
polyhaloalkyl.
[0054] The term "aryl" means, unless otherwise stated, a
polyunsaturated, aromatic, hydrocarbon which can be a single ring
or multiple rings (preferably from 1 to 3 rings) which are fused
together or linked covalently. The term "heteroaryl" refers to aryl
groups (or rings) that contain from one to four heteroatoms
selected from N, O, and S, wherein the heteroatom occupies a ring
vertex (also referred to herein as a "ring heteroatom"). The
nitrogen and sulfur atoms are optionally oxidized, and the nitrogen
atom(s) are optionally quaternized. A heteroaryl group can be
attached to the remainder of the molecule through a carbon or
heteroatom. The terms "arylene" and "heteroarylene" refer to the
divalent derivatives of aryl and heteroaryl groups,
respectively.
[0055] An "unsubstituted aryl" or "unsubstituted heteroaryl" refers
to aryl and heteroaryl rings, respectively, in which the carbon
atoms occupying ring vertices that are not at a point of attachment
to the remainder of the molecule are attached only to hydrogen or
other atoms occupying ring vertices. Heteroatoms occupying ring
vertices that are not at a point of attachment to the remainder of
the molecule are attached only to hydrogen, other atoms occupying
ring vertices, or oxygen (in the case of oxidized ring
heteroatoms).
[0056] The term "oxo" as used herein means an oxygen that is double
bonded to a carbon atom.
[0057] A "liquid," as used herein, is a substance that flows
freely, lacks crystal structure, and, unlike a gas, retains the
same volume independent of the shape of its container at ambient
temperature and pressure. An "aqueous liquid" refers to a liquid
having a portion of water. Aqueous liquids suitable for the
practice of the present invention include, for example, waste water
and sewage water, fruit juices, milk, and medical fluids. Other
suitable fluids will be readily determined by those skilled in the
art and may be utilized in various implementations.
[0058] A "solid," as used herein, is a substance that does not
dissolve in water at ambient temperature. Thus, a "solid phase
carrier" is a carrier that is insoluble in water at ambient
temperature.
Methods
[0059] In one aspect, the present invention provides a method of
reducing or eliminating the viable number of microorganisms in a
liquid. The method includes contacting the liquid with a solid
phase carrier coated with a quaternary ammonium organosilane
coating. The quaternary ammonium organosilane coating may reduce
the viable number of microorganisms in a liquid by directly
contacting the microorganisms.
[0060] A wide variety of solid phase carriers are useful in
conjunction with the methods and compositions of the present
invention. The solid phase carrier may be any appropriate dimension
or shape, including, for example, a planar surface, the lining of
tubing or pipe, or a roughly spherical particle. The solid phase
carrier may also be any appropriate size, including, for example, a
microscopic carrier, a carrier detectable with the naked eye, a
roughly planar carrier with dimensions that are centimeters to
meters in length, and roughly spherical carrier with a radius that
is centimeters to meters in length.
[0061] The solid phase carrier is typically composed of one or more
substance or material that is insoluble in liquid media (e.g.
organic media, aqueous media, water, etc.). Exemplary materials
include glass, silica, sand (e.g. manganese greensand and filter
sand), quartz, flint, zeolite, anthracite, activated carbon,
garnet, ilmenite, benn, aluminum (including non-hydrous aluminum
silicate (e.g. filter AG), oxides of iron and titanium (e.g.
ilmenite), diatomaceous earth, pozzolan (silicon/alumina material
that occurs naturally and is produced as a byproduct of coal
combustion), metal (e.g. tin), ceramic, and/or organic polymers and
plastics (e.g. high density polyethylene (HDPE), polypropylene (PP)
or polyvinyl chloride (PVC)).
[0062] In various implementations, the liquid is contacted with an
additional solid phase carrier. The additional solid phase carrier
may be coated with a different quaternary ammonium organosilane
coating than the solid phase carrier. The additional solid phase
carrier may also be composed of a different material than the solid
phase carrier.
Quaternary Ammonium Organosilane Reagents
[0063] The solid phase carriers of the current invention are coated
with a quaternary ammonium organosilane coating. The quaternary
ammonium organosilane coating is produced from a quaternary
ammonium organosilane reagent. The quaternary ammonium organosilane
reagent has the formula:
##STR00003##
[0064] In Formula (I), A is selected from --OR.sup.4, substituted
or unsubstituted alkyl, substituted or unsubstituted heteroalkyl,
substituted or unsubstituted cycloalkyl, substituted or
unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,
and substituted or unsubstituted heteroaryl. Where more than one A
is present, each A is independently selected from the groups
recited above or below.
[0065] R.sup.4 is selected from hydrogen, substituted or
unsubstituted alkyl, substituted or unsubstituted heteroalkyl,
substituted or unsubstituted cycloalkyl, substituted or
unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,
and substituted or unsubstituted heteroaryl.
[0066] R is selected from substituted or unsubstituted alkylene,
substituted or unsubstituted heteroalkylene, substituted or
unsubstituted cycloalkylene, substituted or unsubstituted
heterocycloalkylene, substituted or unsubstituted arylene, and
substituted or unsubstituted heteroarylene.
[0067] R.sup.1, R.sup.2, and R.sup.3 are independently selected
from hydrogen, substituted or unsubstituted alkyl, substituted or
unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,
substituted or unsubstituted heterocycloalkyl, substituted or
unsubstituted aryl, and substituted or unsubstituted
heteroaryl.
[0068] Z is selected from fluoride, chloride, bromide, iodide,
tosylate, hydroxide, sulfate and phosphate.
[0069] The symbol n is 1, 2 or 3.
[0070] In an exemplary implementation, each substituted alkyl,
substituted heteroalkyl, substituted cycloalkyl, substituted
heterocycloalkyl, substituted aryl, and substituted heteroaryl
described herein as possible A, R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 moieties are substituted only with at least one substituent
independently selected from --OH, unsubstituted
(C.sub.1-C.sub.5)alkyl, unsubstituted 2 to 5 membered heteroalkyl,
unsubstituted (C.sub.5-C.sub.7) membered cycloalkyl, unsubstituted
5 to 7 membered heterocycloalkyl, unsubstituted aryl, and
unsubstituted heteroaryl. For example, where A is a substituted
(C.sub.1-C.sub.10)alkyl, the substituted (C.sub.1-C.sub.10)alkyl is
substituted only with at least one substituent independently
selected from --OH, unsubstituted (C.sub.1-C.sub.5)alkyl,
unsubstituted 2 to 5 membered heteroalkyl, unsubstituted
(C.sub.5-C.sub.7) membered cycloalkyl, unsubstituted 5 to 7
membered heterocycloalkyl, unsubstituted aryl, and unsubstituted
heteroaryl.
[0071] In other implementations, each substituted alkyl,
substituted heteroalkyl, substituted cycloalkyl, substituted
heterocycloalkyl, substituted aryl, and substituted heteroaryl
described herein as possible A, R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 moieties are substituted only with at least one substituent
independently selected from --OH, unsubstituted
(C.sub.1-C.sub.5)alkyl, unsubstituted 2 to 5 membered heteroalkyl,
unsubstituted (C.sub.5-C.sub.7) membered cycloalkyl, unsubstituted
5 to 7 membered heterocycloalkyl, unsubstituted aryl, and
unsubstituted heteroaryl. In other implementations, each
substituted alkyl, substituted heteroalkyl, substituted cycloalkyl,
substituted heterocycloalkyl, substituted aryl, and substituted
heteroaryl described herein as possible A, R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 moieties are substituted only with at least
one substituent independently selected from --OH, unsubstituted
(C.sub.1-C.sub.5)alkyl, unsubstituted (C.sub.5-C.sub.7) membered
cycloalkyl, and unsubstituted phenyl. In yet other implementations,
each substituted alkyl, substituted heteroalkyl, substituted
cycloalkyl, substituted heterocycloalkyl, substituted aryl, and
substituted heteroaryl described herein as possible A, R, R.sup.2,
R.sup.3, and R.sup.4 moieties are substituted only with at least
one unsubstituted (C.sub.1-C.sub.3)alkyl.
[0072] In another exemplary embodiment, each substituted alkylene,
substituted heteroalkylene, substituted cycloalkylene, substituted
heterocycloalkylene, substituted arylene, and substituted
heteroarylene described herein as possible R moieties are
substituted only with at least one substituent independently
selected from --OH, unsubstituted (C.sub.1-C.sub.5)alkyl,
unsubstituted 2 to 5 membered heteroalkyl, unsubstituted
(C.sub.5-C.sub.7) membered cycloalkyl, substituted 5 to 7 membered
heterocycloalkyl, unsubstituted aryl, and unsubstituted
heteroaryl.
[0073] In various implementations, each substituted alkylene,
substituted heteroalkylene, substituted cycloalkylene, substituted
heterocycloalkylene, substituted arylene, and substituted
heteroarylene described herein as possible R moieties are
substituted only with at least one substituent independently
selected from --OH, unsubstituted (C.sub.1-C.sub.5)alkyl,
unsubstituted 2 to 5 membered heteroalkyl, unsubstituted
(C.sub.5-C.sub.7) membered cycloalkyl, unsubstituted 5 to 7
membered heterocycloalkyl, unsubstituted aryl, and unsubstituted
heteroaryl. In other implementations, each substituted alkylene,
substituted heteroalkylene, substituted cycloalkylene, substituted
heterocycloalkylene, substituted arylene, and substituted
heteroarylene described herein as possible R moieties are
substituted only with at least one substituent independently
selected from --OH, unsubstituted (C.sub.1-C.sub.5)alkyl,
unsubstituted (C.sub.5-C.sub.7) membered cycloalkyl, and
unsubstituted phenyl. In yet other implementations, each
substituted alkylene, substituted heteroalkylene, substituted
cycloalkylene, substituted heterocycloalkylene, substituted
arylene, and substituted heteroarylene described herein as possible
R moieties are substituted only with at least one unsubstituted
(C.sub.1-C.sub.3)alkyl.
[0074] A may be selected from --OR.sup.4, substituted or
unsubstituted (C.sub.1-C.sub.10)alkyl, substituted or unsubstituted
2 to 12 membered heteroalkyl, substituted or unsubstituted
(C.sub.5-C.sub.7)cycloalkyl, substituted or unsubstituted 5 to 7
membered heterocycloalkyl, substituted or unsubstituted aryl, and
substituted or unsubstituted heteroaryl. R.sup.4 may be selected
from hydrogen, substituted or unsubstituted
(C.sub.1-C.sub.10)alkyl, substituted or unsubstituted 2 to 10
membered heteroalkyl, substituted or unsubstituted
(C.sub.5-C.sub.7)cycloalkyl, substituted or unsubstituted 5 to 7
membered heterocycloalkyl, substituted or unsubstituted aryl, and
substituted or unsubstituted heteroaryl.
[0075] In some implementations, A is selected from --OR.sup.4,
unsubstituted (C.sub.1-C.sub.10)alkyl, unsubstituted 2 to 12
membered heteroalkyl, unsubstituted (C.sub.5-C.sub.7)cycloalkyl,
unsubstituted 5 to 7 membered heterocycloalkyl, unsubstituted aryl,
and unsubstituted heteroaryl. In other implementations, A is
selected from --OR.sup.4, unsubstituted (C.sub.1-C.sub.10)alkyl,
unsubstituted 3 to 12 membered alkylether, unsubstituted
(C.sub.5-C.sub.7)cycloalkyl, and unsubstituted phenyl.
[0076] A may also be selected from --OR.sup.4, unsubstituted
(C.sup.1-C.sup.4)alkyl, unsubstituted 3 to 8 membered alkylether,
unsubstituted (C.sup.5-C.sup.7)cycloalkyl, and unsubstituted
phenyl. Alternatively, A is selected from --OR.sup.4, unsubstituted
(C.sub.1-C.sub.4)alkyl, and unsubstituted 3 to 8 membered
alkylether.
[0077] R.sup.4 may be selected from hydrogen, unsubstituted
(C.sub.1-C.sub.10)alkyl, unsubstituted 2 to 12 membered
heteroalkyl, unsubstituted (C.sub.5-C.sub.7)cycloalkyl,
unsubstituted 5 to 7 membered heterocycloalkyl, unsubstituted aryl,
and unsubstituted heteroaryl.
[0078] In some implementations, R.sup.4 is selected from hydrogen,
unsubstituted (C.sub.1-C.sub.10)alkyl, unsubstituted 3 to 12
membered alkylether, unsubstituted (C.sub.5-C.sub.7)cycloalkyl, and
unsubstituted phenyl. In a related embodiment, R.sup.4 is selected
from hydrogen, unsubstituted (C.sub.1-C.sub.5)alkyl, unsubstituted
3 to 8 membered alkyl ether, unsubstituted
(C.sub.5-C.sub.7)cycloalkyl, and unsubstituted phenyl.
Alternatively, R.sup.4 is selected from hydrogen, unsubstituted
(C.sub.1-C.sub.5)alkyl, and unsubstituted 3 to 8 membered alkyl
ether.
[0079] R.sup.4 may also be selected from phenyl, methylphenyl,
substituted or unsubstituted (C.sub.1-C.sub.5)alkyl, and
--(CH.sub.2).sub.x--O--(CH.sub.2).sub.yCH.sub.3. X and y are
integers independently selected from 1 to 10.
[0080] R may be selected from substituted or unsubstituted
(C.sub.1-C.sub.10) alkylene, substituted or unsubstituted 2 to 10
membered heteroalkylene, substituted or unsubstituted
(C.sub.5-C.sub.7)cycloalkylene, substituted or unsubstituted 2 to 7
membered heterocycloalkylene, substituted or unsubstituted arylene,
and substituted or unsubstituted heteroarylene.
[0081] In various implementations, R is a member selected from
unsubstituted (C.sub.1-C.sub.10)alkylene, unsubstituted 2 to 10
membered heteroalkylene, unsubstituted
(C.sub.5-C.sub.7)cycloalkylene, unsubstituted 5 to 7 membered
heterocycloalkylene, unsubstituted arylene, and unsubstituted
heteroarylene.
[0082] R may also be unsubstituted (C.sub.1-C.sub.10)alkylene.
[0083] R.sup.1, R.sup.2, and R.sup.3 may be selected from hydrogen,
substituted or unsubstituted (C.sub.1-C.sub.20)alkyl, substituted
or unsubstituted 2 to 20 membered heteroalkyl, substituted or
unsubstituted (C.sub.5-C.sub.7)cycloalkyl, substituted or
unsubstituted 5 to 7 membered heterocycloalkyl, substituted or
unsubstituted aryl, and substituted or unsubstituted
heteroaryl.
[0084] In some implementations, R, R.sup.2, and R.sup.3 are
independently selected from hydrogen, unsubstituted
(C.sub.1-C.sub.20)alkyl, hydroxy-substituted
(C.sub.1-C.sub.20)alkyl, amine-substituted (C.sub.1-C.sub.20)alkyl,
unsubstituted 2 to 20 membered heteroalkyl, unsubstituted
(C.sub.5-C.sub.7)cycloalkyl, unsubstituted 5 to 7 membered
heterocycloalkyl, unsubstituted aryl, and unsubstituted heteroaryl.
In a related embodiment, R.sup.1, R.sup.2, and R.sup.3 are
independently selected from hydrogen, unsubstituted
(C.sub.1-C.sub.20)alkyl, unsubstituted alkylether,
hydroxy-substituted (C.sub.1-C.sub.20)alkyl, amine-substituted
(C.sub.1-C.sub.20)alkyl, unsubstituted (C.sub.5-C.sub.7)cycloalkyl,
and unsubstituted phenyl.
[0085] R.sup.1, R.sup.2, and R.sup.3 may also be selected from
hydrogen, unsubstituted (C.sub.1-C.sub.20)alkyl, unsubstituted
alkylether, hydroxy-substituted (C.sub.1-C.sub.20)alkyl,
amine-substituted (C.sub.1-C.sub.20)alkyl, unsubstituted
(C.sub.5-C.sub.7)cycloalkyl, and unsubstituted phenyl.
Alternatively, R.sup.1, R.sup.2, and R.sup.3 are selected from
hydrogen, unsubstituted (C.sub.1-C.sub.20)alkyl, unsubstituted
alkylether, hydroxy-substituted (C.sub.1-C.sub.20)alkyl, and
amine-substituted (C.sub.1-C.sub.20)alkyl.
[0086] In other exemplary embodiments, R.sup.1, R.sup.2, and
R.sup.3 are independently selected from
--(CH.sub.2).sub.qOCH.sub.3, --(CH.sub.2).sub.qOH,
--(CH.sub.2).sub.qO(CH.sub.2).sub.tCH.sub.3,
--(CH.sub.2).sub.qNHCH.sub.3, --(CH.sub.2).sub.qNH.sub.2,
--(CH.sub.2).sub.qN(CH.sub.3).sub.2 and
--(CH.sub.2).sub.qNH.sub.2(CH.sub.2).sub.tCH.sub.3, in which q and
t are integers independently selected from 0 to 10. R.sup.1,
R.sup.2, and R.sup.3 may also be independently selected from the
group consisting of --CH.sub.2CH.sub.2OCH.sub.3 and
--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.3. Alternatively,
R.sup.1, R.sup.2, and R.sup.3 may also be independently selected
from --CH.sub.2CH.sub.2OH and
--CH.sub.2CH.sub.2CH.sub.2CH(OH)CH.sub.3. R.sup.1, R.sup.2, and
R.sup.3 may also be independently selected from
--CH.sub.2CH.sub.2NH.sub.2 and --CH.sub.2CH.sub.2N(CH.sub.3).sub.2.
Finally, R.sup.1, R.sup.2, and R.sup.3 may be members independently
selected from methyl, octadecyl, didecyl, and tetradecyl.
[0087] In an exemplary embodiment, the quaternary ammonium
organosilane reagent is selected from
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3N+(CH.sub.3).sub.2(C.sub.18H.sub.37)
(Cl.sup.-);
(CH.sub.3CH.sub.2O).sub.3Si(CH.sub.2).sub.3N+(CH.sub.3).sub.2(C.sub.18H.s-
ub.37) (Cl.sup.-);
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3N+(CH.sub.3).sub.2(C.sub.18H.sub.37)
(Br.sup.-);
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3N+(C.sub.10H.sub.21).sub.2(CH.sub.3)
(Cl.sup.-);
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3N+(CH.sub.3).sub.2(C.sub.14H.sub.29)
(Cl.sup.-);
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3N+(CH.sub.3).sub.2(C.sub.14H.sub.29)
(Br.sup.-); and
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3N+(CH.sub.3).sub.2(C.sub.16H.sub.33)
(Cl.sup.-). In a related embodiment, the quaternary ammonium
organosilane reagent is selected from
3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride,
3-(trimethoxysilyl)propyldidecylmethyl ammonium chloride, and
3-(trimethoxysilyl)propyldimethyltetradecyl ammonium chloride.
[0088] In another exemplary embodiment, the quaternary ammonium
organosilane contains an ammonium halide and a hydrolyzable alkoxy
group bonded to silicon.
Quaternary Ammonium Organosilane Coatings
[0089] A variety of methods may be used to form the quaternary
ammonium organosilane coatings from quaternary ammonium
organosilane reagents. The quaternary ammonium organosilane reagent
may be applied to the solid phase carrier using any method known in
the art, including, for example, methods for covalently or
non-covalently binding the quaternary ammonium organosilane reagent
to the solid phase carrier to form a quaternary ammonium
organosilane coating.
[0090] Solid phase carriers may be contacted (e.g. sprayed, dipped,
or otherwise applied) with a solution preparation containing the
quaternary ammonium organosilane reagent. In some embodiments, the
quaternary ammonium organosilane reagent coated surfaces are
allowed to air dry at room temperatures for a sufficient period of
time to complete a condensation cure of the quaternary ammonium
organosilane coating. Alternatively, heat is applied to the coated
surfaces for a sufficient period of time to effect cure, the
duration and temperature of such is known to those skilled in the
art.
[0091] In various implementations, the quaternary ammonium
organosilane reagent is covalently bound to the solid phase
carrier. Typically, the quaternary ammonium organosilane reagent is
covalently bound to an accessible carrier reactive group that forms
a part of the solid phase carrier. A variety of reactive groups are
useful in covalently binding the quaternary ammonium organosilane
reagent. The quaternary ammonium organosilane reagent may be
covalently bound to the carrier reactive group through the silane
moiety of the quaternary ammonium organosilane reagent. The silane
moiety, as used herein, refers to the A.sub.4-n-Si-portion of the
compound Formula I.
[0092] The silane moiety may be covalently bound to the carrier
reactive group by allowing the carrier reactive group to covalently
bind to the silicon atom of the silane moiety. For example, where
the carrier reactive group is a hydroxyl, the oxygen atom may be
allowed to bind to the silicon atom to form a silicon-oxygen bond
thereby covalently attaching the quaternary ammonium organosilane
reagent to the carrier molecule. In a related embodiment, the
silane moiety includes at least one --OR.sup.4 that leaves upon
attack of a hydroxyl carrier reactive group. This reaction may be
referred to herein as a condensation reaction. Thus, the quaternary
ammonium organosilane reagent may be covalently attached to the
carrier molecule via a condensation reaction.
[0093] The silane moiety may also include an A group that contains
a reactive group, referred to herein as a silane reactive group.
The silane reactive group is capable of reacting with a carrier
reactive group to form a covalent bond.
[0094] Silane reactive groups, carrier reactive groups and classes
of reactions useful in covalently attaching quaternary ammonium
organosilane reagents to a solid phase carrier are generally those
that are well known in the art of bioconjugate chemistry. These
include, but are not limited to nucleophilic substitutions (e.g.
reactions of amines and alcohols with acyl halides, active esters),
electrophilic substitutions (e.g., enamine reactions) and additions
to carbon-carbon and carbon-heteroatom multiple bonds (e.g.,
Michael reaction, Diels-Alder addition). These and other useful
reactions are discussed in, for example, March, Advanced Organic
Chemistry, 3rd Ed., John Wiley & Sons, New York, 1985;
Hermanson, Bioconjugate Techniques, Academic Press, San Diego,
1996; and Feeney et al., Modification Of Proteins; Advances in
Chemistry Series, Vol. 198, American Chemical Society, Washington,
D.C., 1982 the disclosures of which are hereby incorporated herein
entirely by reference.
[0095] Useful silane and carrier reactive functional groups
include, for example:
[0096] (a) carboxyl groups and various derivatives thereof
including, but not limited to, N-hydroxysuccinimide esters,
N-hydroxybenztriazole esters, acid halides, acyl imidazoles,
thioesters, p-nitrophenyl esters, alkyl, alkenyl, alkynyl and
aromatic esters;
[0097] (b) hydroxyl groups which can be converted to esters,
ethers, aldehydes, etc.;
[0098] (c) haloalkyl groups wherein the halide can be later
displaced with a nucleophilic group such as, for example, an amine,
a carboxylate anion, thiol anion, carbanion, or an alkoxide ion,
thereby resulting in the covalent attachment of a new group at the
site of the halogen atom;
[0099] (d) dienophile groups which are capable of participating in
Diels-Alder reactions such as, for example, maleimido groups;
[0100] (e) aldehyde or ketone groups such that subsequent
derivatization is possible via formation of carbonyl derivatives
such as, for example, imines, hydrazones, semicarbazones or oximes,
or via such mechanisms as Grignard addition or alkyllithium
addition;
[0101] (f) sulfonyl halide groups for subsequent reaction with
amines, for example, to form sulfonamides;
[0102] (g) thiol groups, which can be converted to disulfides or
reacted with acyl halides;
[0103] (h) amine or sulfhydryl groups, which can be, for example,
acylated, alkylated or oxidized;
[0104] (i) alkenes, which can undergo, for example, cycloadditions,
acylation, Michael addition, etc.;
[0105] (j) epoxides, which can react with, for example, amines and
hydroxyl compounds; and
[0106] (k) phosphoramidites and other standard functional groups
useful in nucleic acid synthesis.
[0107] The reactive functional groups can be chosen such that they
do not participate in, or interfere with, the reactions necessary
to assemble the quaternary ammonium organosilane coating.
Alternatively, a silane or carrier reactive functional group can be
protected from participating in the reaction by the presence of a
protecting group. Those of skill in the art will understand how to
protect a particular functional group from interfering with a
chosen set of reaction conditions. For examples of useful
protecting groups, See Greene et al, Protective Groups In Organic
Synthesis, John Wiley & Sons, New York, 1991, the disclosure of
which is incorporated entirely herein by reference.
[0108] Linkers may also be employed to attach the quaternary
ammonium organosilane reagent to the solid phase carrier. Linkers
may include reactive groups at the point of attachment to the
quaternary ammonium organosilane reagent and/or the solid phase
carrier. Any appropriate linker may be used in the present
invention, including substituted or unsubstituted alkylene,
substituted or unsubstituted heteroalkylene, substituted or
unsubstituted cycloalkylene, substituted or unsubstituted
heterocycloalkylene, substituted or unsubstituted arylene, and
substituted or unsubstituted heteroarylene. In an exemplary
embodiment, the linker group is selected from substituted or
unsubstituted alkylene, and substituted or unsubstituted
heteroalkylene. In a related embodiment, the linker is selected
from unsubstituted alkylene, alkylene substituted with at least one
oxy, unsubstituted heteroalkylene, and heteroalkylene substituted
with at least one oxy. In another related embodiment, the linker is
selected from unsubstituted (C.sub.1-C.sub.25) alkylene,
(C.sub.1-C.sub.25) alkylene substituted with at least one oxy,
unsubstituted 2 to 26 membered heteroalkylene, and 2 to 26 membered
heteroalkylene substituted with at least one oxy.
[0109] Other useful linkers include those having a polyester
backbone (e.g. polyethylene glycol), and derivatives thereof. A
wide variety of useful linkers are commercially available (e.g.
polyethylene glycol based linkers such as those available from
Nektar, Inc. of Huntsville, Ala.).
[0110] The quaternary ammonium organosilane reagent may also be
non-covalently attached to the solid phase carrier using any
interaction, such as Van der Waals interactions, hydrophobic
interactions, dipole-dipole interactions, electrostatic
interactions, and/or hydrogen bonding interactions.
[0111] In an exemplary embodiment, the quaternary ammonium
organosilane reagent forms a polymeric network that partially or
wholly covers the solid phase carrier. Where the quaternary
ammonium organosilane reagent forms a polymeric network, the
quaternary ammonium organosilane reagent may additionally from a
covalent and/or non-covalent bond with the solid phase carrier.
[0112] The quaternary ammonium organosilane reagent typically forms
a polymeric network by covalently binding through the silane
moiety. Where the silane moiety includes at least one --OR.sup.4
group, the quaternary ammonium organosilane reagent may form a
silicone polymer having a series of silicon-oxygen-silicon bonds.
The silicones may be linear polymers or cross-linked polymers. For
example, where the silane moiety includes at least two --OR.sup.4
groups, the quaternary ammonium organosilane reagent may form a
cross-linked silicone polymer wherein each silica atom forms part
of at least two silicon-oxygen-silicon bonds. Thus, polymerization
may be achieved using silane reactive groups capable of forming
intermolecular covalent bonds with other silane reactive
groups.
[0113] In an exemplary embodiment, the quaternary ammonium
organosilane reagent is contacted with an aqueous liquid prior to
application to the solid phase carrier. As discussed above, useful
quaternary ammonium organosilane reagents include those containing
hydrolyzable alkoxy groups bound to the silicon atom. Upon contact
with a water molecule, the alkoxy groups (e.g. methoxy) may
hydrolyze to form hydroxy substituted silicon atoms (also referred
to herein as "silanols") with simultaneous liberation of alcohol as
a by-product of the hydrolysis (also referred to herein as
condensation). The resultant compound formed on addition of
quaternary ammonium organosilanes of the above compositions are the
corresponding mono-, di-, or tri-silanol species. The reactive
silanol species prepared upon hydrolysis may form covalent
silicon-oxygen-silicon bonds with other silanol species resulting
in polymeric coatings as described above. The resultant polymeric
coating may be a molecular network non-covalently and/or covalently
bonded to the solid phase carrier.
[0114] It will be understood by those skilled in the art that the
quaternary ammonium organosilane coating may form three
dimensional, cross-linked, water-insoluble, polymeric coatings
which may contain some uncondensed silanol or alkoxy moieties.
Monomeric, dimeric and oligomeric species may be present on the
solid phase carrier following application of an aqueous solution
containing quaternary ammonium organosilane reagent, and these may
bond to the solid phase carrier, whether by covalent or
non-covalent mechanisms.
[0115] The quaternary ammonium organosilane coatings formed on the
solid phase carriers retain their antimicrobial activity. They are
substantive to the solid phase carriers and largely insoluble in
aqueous liquid. For example, in some embodiments, less than 10 ppb
of quaternary ammonium organosilane reagents is detectable in water
after Standard 42 testing as performed by NSF International, Ann
Arbor, Mich.
[0116] In an exemplary embodiment, the quaternary ammonium
organosilane coating has the formula:
##STR00004##
[0117] In Formula II, A, R, R.sup.1, R.sup.2, and R.sup.3 are as
defined above in Formula I. W is a solid phase carrier as described
above. The solid phase carrier W may include a linker moiety and/or
the remnant of a reactive group. The symbol 1 represents an integer
selected from 1, 2, or 3. The symbols m and j represent integers
independently selected from 0, 1, 2, and 3, wherein both m and j
are not simultaneously 0. The sum of m, j, and 1 is not greater
than four. In a related embodiment, 1 is 1, 2, or 3; m is 1, 2, or
3, and j is 1, 2, or 3. In another related embodiment, 1 is 1; m is
1, 2, or 3, and j is 1, 2, or 3.
Microorganisms
[0118] The term "microorganism," as used herein, means an organism
that, individually, can only be seen through a microscope. The term
microorganism includes, for example, bacteria, fungi,
actinomycetes, algae, protozoa, yeast, germs, ground pearls,
nematodes, viruses, prions, and algae. Thus, in an exemplary
embodiment, the microorganism is selected from bacteria, viruses
(also referred to herein as bacteriophages), fungi, algae, mold,
yeast, spores, and protozoa parasites. The term "bacteria" includes
both gram positive and gram negative bacteria.
[0119] Gram positive bacteria include, for example, Bacillus sp.
(vegetative cell), Corynebacterium diptheriae, Micrococcus lutea,
Micrococcus sp., Mycobacterium tuberculosis, Mycobacterium
smegmatis, Propionibacterium acnes, Staphylococcus aureus,
Staphylococcus epidermidis, Streptococcus faecalis, Streptococcus
mutans, Streptococcus pneumonia, and Streptococcus pyogenes.
[0120] Gram negative bacteria include, for example, Acinetobacter
calcoaceticus, Aeromonas hydrophilia, Citrobacter deversus,
Citrobacter feundi, Enterobacter aerogenes, Enterobacter aglomera,
Escherichia coli, Klebsiella oxytoca, Klebsiella pneumoniae,
Klebsiella terriena, Legionella pneumophila, Morganella morganii,
Proteus mirabilis, Proteus vulgaris, Pseudomonas aeruginosa,
Pseudomonas fluorscens, Salmonella cholera suis, Salmonella typhi,
Salmonella typhimurium, Serratia liquifaciens, and Xanthomonas
campestris.
[0121] Viruses include, for example, Adenovirus Type II & IV,
Bovine Adenovirus Type I & IV, Feline pneumonitis, Herpes
Simplex Type I, Herpes Simplex Type II, HIV-1 (AIDS), Influenza A2
(Aichi), Influenza A2 (Asian), Influenza B, Mumps, Parinfluenza
(Sendai), Reovirus Type I, Simian Virus 40, Vaccinia, MS2, T2
(non-enveloped virus) and PRD1.
[0122] Fungi, algae, mold, yeast, and spores include, for example,
Alterania alternate, Aspergillus flavus, Aspergillus niger.
Aspergillus sydowii, Aspergillus terreus, Aspergillus versicolor,
Aspergillus verrucaria, Aureobasidium pullans, Candida albicans,
Candida pseudotropocalis, Chaetomium globsum, Cladosporium
cladosporioides, Chlorella vulgaris, Dreschslera australiensis,
Epidermophyton sp., Gliomasta cerealis, Gloeophyllum trabeum,
Microsporum sp., Microsporum audouinii, Monilia grisea,
Oscillatoria, Penicillium chrysogenum, Pencillium commune,
Penicillium funiculosum, Penicillium pinophiliumm, Penicillium
variable, Phoma fimeti, Pithomyces chartarum, Poria placenta,
Scenedesmus, Saccharonyces cerevisiae, Scolecobasidium humicola,
Trichoderma viride, Trichophyton interdigitale, Trichophyton
maidson, Trichophyton mentogrophytes, and Trichophyton sp.
[0123] Protozoa parasites include, for example, Cryptosporidium
parvum (oocysts) and Giardia.
[0124] For more detailed information regarding antimicrobial
activity against gram positive bacteria, gram negative bacteria,
viruses, fungi, algae, mold, yeast, spores and protozoa parasites,
see Hsiao, Y. Chinese Pat. Appl., PCT/CN98/00207 (1998); Malek, J.
et at., U.S. Pat. No. 4,259,103 (1981); Klein, S., U.S. Pat. No.
4,394,378 (1983); Eudy, W., U.S. Pat. No. 4,406,892 (1983);
Gettings, R. et al., U.S. Pat. No. 4,908,355 (1990) and U.S. Pat.
No. 5,013,459 (1991); Blank, L. et al., U.S. Pat. No. 5,145,596
(1992); Avery, R. U.S. Pat. No. 5,411,585 (1995); Blank, L. et al.,
U.S. Pat. No. 4,865,844 (1989); Battice, D. et al., U.S. Pat. No.
4,631,297 (1986); Higgs, B. et al., U.S. Pat. No. 5,359,104 (1994);
Avery, R et al., U.S. Pat. No. 5,411,585 (1995); White, W. et al.,
Book of Papers, 12th Annual Nonwovens Tech. Symposium, pp. 13-46
(1984); McGee, J. et al, Am. Dyestuff Rep. 6: 56-59 (1983); Dow
Corning Technical Brochure; 22-994-83 (1983); Gettings, R. et al.,
Book of Papers, American Association of Textile Chemists and
Colorists National Technical Conference, pp. 259-261 (1978); Dow
Corning Technical Brochure, 24-095-85 (1985); Tsao, I. et al.,
Biotechnol. Bioeng., 34: 639-46 (1989); Tsao, I et al., ACS Symp.
Ser. 419: 250-67 (1990); Klein, M. et al, Principles of Viral
Inactivation, 3.sup.rd Ed., S. Block, Ed., (Lea & Febiger,
Philadelphia, Pa.) pp. 422-434 (1983); Peterson, W. et al, U.S.
Pat. No. 6,613,755; each of which is incorporated entirely by
reference herein.
[0125] Conventional quaternary ammonium organosilanes are available
as 42% active material in methanol under the trademark DOW
CORNING.RTM. 5700 (3-(trimethoxy-silyl)propyldimethyloctadecyl
ammonium chloride) by Aegis Environmental Management, Inc. of
Midland, Mich. and Requat 1977
(3-(trimethoxysilyl)-propyldidecylmethyl ammonium chloride) by
Sanitized Inc. of New Preston, Conn.
Octadecyldimethyl(3-trimethoxysilylpropyl) ammonium chloride (Cat.
No. SI06620.0) as a 60% active solution in methanol,
tetradecyldimethyl(3-tri-methoxysilylpropyl) ammonium chloride
(Cat. No. SIT7090.0) as a 50% solution in methanol and
didecylmethyl(3-trimethoxysilylpropyl) ammonium chloride (Cat. No.
SID3392.0) as a 42% solution in methanol are offered by Gelest,
Inc. of Tullytown, P A. They are often applied from solvent
solutions such as lower alcohols.
EXAMPLES
[0126] The following examples are provided by way of illustration
only and not by way of limitation. Those of skill in the art will
readily recognize a variety of non-critical parameters that can be
changed or modified to yield similar results.
[0127] ODTA: Octadecyldimethyl(3-trimethoxysilyl)propyl ammonium
chloride. Obtained from Wright Chemical Corp., Wilmington, N.C. as
a 42% active material in methanol. This material may also be named
as 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride.
Also available as a 42% active material from Aegis Environmental
Management, Inc., Midland, Mich. marketed as DOW CORNING.RTM.
5700.
[0128] REQUAT: 3-(trimethoxysilyl)propyldidecylmethyl ammonium
chloride. Obtained from Sanitized Inc., New Preston, Conn.; Requat
1977 as a 42% active material in methanol.
[0129] TDTA: 3-(trimethoxysilyl)propyltetradecyldimethyl ammonium
chloride obtained from Gelest, Inc., Tullytown, P A, Cat. No.
SIT7090.0 as a 50% solution in methanol.
Example 1
[0130] A solution suitable for application was prepared by adding 4
parts ODTA to 100 parts deionized water with stirring. The
resulting clear solution was applied to an open, polyvinyl chloride
(PVC) flat-type evaporation pan by atomized spray, insuring that
all surfaces were thoroughly wetted. The pan is allowed to air dry
for 24 hours to cure the quaternary ammonium organosilane reagents
to the container surface to form a quaternary ammonium organosilane
coating. Water containing bacteria level previously measured at
10.sup.7 total bacteria/ml using a BIOSPERSE.RTM. Test Kit was
added to the pan in a ratio of 4.6 grams of water per square inch
of surface area. After 30 minutes the water is sampled using a
BIOSPERSE.RTM. test kit. After incubation, 10.sup.5 bacteria/ml was
measured. Resampling of the test water at 1 hour and 4 hours gave
bacterial counts of 10.sup.4 and <10.sup.3, respectively.
Example 2
[0131] A 4 oz. solution prepared according to Example 1 was added
to a 1 pint tin-plated metal test container having 3/4 inch screw
top. The solution was agitated to completely wet the inside surface
of the container for 1 minute and then decanted. The test container
was allowed to air dry for one hour. Residual vapors were removed
by an air purge for 5 minutes and the container was then heated to
105.degree. C. for one hour to cure the quaternary ammonium
organosilane reagents to the container surface to form a quaternary
ammonium organosilane coating. Water (300 g) having a high
bacterial count of 10.sup.7 bacteria/ml was added to the test
container. The test container was allowed to stand one hour at room
temperature. After two hours, the test water bacterial level was
measured at 10.sup.3 bacteria/ml using a BIOSPERSE.RTM. test
kit.
Example 3
[0132] Two ounce containers of glass, high density polyethylene
(HDPE), polypropylene (PP) or polyvinyl chloride (PVC) were treated
with an aqueous solution containing 1.5% TDTA. The containers were
heated to 100 C for one hour to cure the quaternary ammonium
organosilane reagent to the container surfaces to form a quaternary
ammonium organosilane coating. Each container was then rinsed with
one oz. of deionized water. One ounce of water containing 10.sup.5
bacteria/ml was added to each container and capped. After 24 hours
at room temperature, each container was sampled and bacteria
measured with a BIOSPERSE.RTM. test kit. All containers indicated
bacteria counts of 10.sup.3 bacteria/ml following incubation for 24
hours.
Example 4
[0133] Coiled aluminum test tubing 8 ft. in length and having an
internal diameter of 1/4 inch was treated with a solution of 8
parts REQUAT to 100 parts isopropanol. The tube was filled with the
solution, sealed and allowed to stand for 15 minutes. The tube was
drained and air dried with a stream of compressed air passing
through the tube at a rate of 100 ml/minute for 24 hours to cure
the quaternary ammonium organosilane reagent to the tubing surfaces
to form a quaternary ammonium organosilane coating. An aqueous
liquid containing 10.sup.7 units/ml of bacteria and algae was
passed through the coiled aluminum tubing. The aqueous liquid was
gravity circulated through the tubing at a rate of 5 ml/minute
resulting in contamination of <10.sup.3 bacteria/ml.
Example 5
[0134] An antimicrobial solution suitable for treatment of
silicaeous surfaces including sand and zeolites was prepared by
adding 67.5 grams REQUAT to a stirred solution containing 3.375 kg
deionized water and 3 grams of 3-aminopropyltrimethoxysilane. One
kg of the clear solution was sprayed onto 50 pounds of #20 white
silica pool filter sand over 5 minutes in a rotary mixer. The
wetted material was mixed with agitation for an additional hour and
allowed to air dry 24 hrs to cure the quaternary ammonium
organosilane reagent to the sand surface to form a quaternary
ammonium organosilane coating. The treated sand was employed in a
recirculating water system to reduce microbial contamination from
10.sup.7 bacteria/ml to <10.sup.3 bacteria/ml in 30 minutes of
operation as measured by a BIOSPERSE.RTM. test kit.
Example 6
[0135] Zeolites containing approximately 90% clinoptilolite (Ash
Meadows Zeolites, LLC) of 20-40 mesh were thoroughly wetted with a
solution containing 7 parts ODTA and 93 parts water. The wet
zeolites were allowed to air dry 24 hours and then heated 2 hours
at 110.degree. C. in a forced air oven to cure the quaternary
ammonium organosilane reagent to the zeolite surfaces to form a
quaternary ammonium organosilane coating. The treated zeolites were
placed in a 2 inch PVC pipe having an overall length of 38 inches.
As described below, dechlorinated water containing known quantities
of bacteriophages, bacteria, algae and protozoa were passed through
the PVC pipe containing the quaternary ammonium organosilane coated
zeolites.
[0136] The experimental apparatus consisted of a set of three
filters (filter 1, 2 and 3) attached to a manifold, which included
fittings for hose connections, and sample ports at the inlet and
outlet for each filter (see FIG. 6). An inline mixer was included
in the pipe assembly before inlet port to maximize microbial
monodispersity. The challenge test water was pumped into each
filter at a flow rate of 330 ml/min using a thermally protected
pump.
[0137] Prior to each microbial challenge, the filters were flushed
for 25 minutes with dechlorinated tap water. The flush water was
dechlorinated using granular activated carbon filter and chlorine
residual was measured before and after the dechlorination using
Hach method 8167.
[0138] The challenge test water was prepared by adding known number
of microorganisms into 20 liters of dechlorinated tap water in a
polypropylene container (Nalgene, Rochester, N.Y.). Microbes were
washed with 1.times. phosphate buffered saline just before spiking
in the container. The challenge test water container was placed on
a stir plate with a Teflon coated stir bar and continuously mixed
to provide homogenous distribution of microbes in the influent
water. The challenge test water was pumped into each filter using a
thermally protected pump (Little Giant Potent Pump, Okla. City,
Okla.). The pump was primed prior to use by recirculating the
microbial stock solution. The hose was connected to the inlet
fitting of each filter. The pump was operated for twelve minutes
for each filter. The flow rate was measured using a 1000 ml
graduated cylinder and adjusted to 330 ml/min as recommended by
CSL. Based on the hydraulic parameters of the system, each filter
needed a 12-minute-run to stabilize. The effluent samples were
taken from each filter after twelve minutes and a single influent
sample was collected from the second filter after eight minutes,
which represented influent concentration for the complete run. Once
the experiment was complete, the filters were again flushed for 30
minutes with dechlorinated tap water.
Example 6.1 Bacteriophages
[0139] A series of experiments were conducted with the
bacteriophages MS2 and PRD1. The effluent and influent samples were
taken and diluted as described above. The samples for MS2 and PRD1
were serially diluted and assayed using their respective bacterial
hosts by double layer agar method (Adams, M. H., Bacteriophages,
Interscience, New York (1959)). The plates were incubated at 37 C
for 24 hours, at which time clear virus plaques were counted. The
results are presented in FIG. 1. The log removal and inactivation
for MS2 and PRD1 ranged between 2.40 to 2.96, and 1.50 to 2.27 log,
respectively. The over average removal for MS2 and PRD1 were 2.8
and 2.0 log, respectively. The data shows that quaternary ammonium
organosilane coated zeolite can reduce the viable number of
bacteriophages in aqueous liquid.
Example 6.2 Bacteria
[0140] An independent series of experiments were conducted with the
bacteria Klebsiella terriena and E. Coli (ATCC 25922). The effluent
and influent samples were taken and diluted as described above. The
samples were assayed by membrane filtration techniques using 0.4 m
pore size membrane filter. The membrane filter was placed on a
selective medium and incubated at 37 C for 24 hours, at which time
bacterial colonies were counted. The results are presented in FIGS.
2(A) and (B). As shown in FIG. 2(A) and FIG. 3, consistent removal
for Klebsiella was observed in all the filters, which ranged from
99.37% (2.2 log) to 99.60% (2.4 log) with an average of 99.50% (2.3
log). As shown in FIG. 2(B), the removal for E. coli ranged from
99.96% (3.50 log) to 99.99% (4.39 log) with an average of 99.98%
(3.88 log). This study shows that quaternary ammonium organosilane
coated zeolite can effectively reduce the viable number bacteria in
aqueous liquid.
Example 6.3 Algae
[0141] Experiments were conducted with Chorella vulgaris to
determine both the removal as well as inactivation effects of the
media against algae. The effluent and influent samples were taken
and diluted as described above. The samples were concentrated by
centrifugation before assaying for total removal and inactivation.
Removal was determined by total volumetric counts under microscope.
The inactivation rate was determined by viability test. The algal
cells were digested with 2% trypsin (in hanks balanced salt
solution) and stained with Fluorescein Diacetate (Sigma Chemicals
F-7378). Fluorescein Diacetate (FDA) is a non-polar ester that
passes through cell membranes. Once inside the cell, FDA is
hydrolyzed by esterases (an enzyme present in viable cells) to
produce fluorescein, which accumulates inside viable cell walls and
fluoresce under UV light. A microscope equipped with both white and
ultraviolet light, was used to quantify live and dead algal cells.
The results are presented in FIG. 4. The average removal of 99.11%
(2.05 log), 98.74% (1.90 log) and 98.74% (1.90 log) were observed
for filter 1, 2, and 3, respectively. The average of three
inactivation measurements for filter 1, 2, and 3 were 11% (0.05%),
12% (0.06 log) and 22% (0.11 log), respectively. However, based on
individual measurements the overall range of inactivation for the
three filters was 5% (0.02 log) to 46% (0.27 log) and averaged at
15% (0.07 log). It is clear that quaternary ammonium organosilane
coated zeolite can effectively reduce the viable number of algae in
aqueous liquid.
Example 6.4 Protozoa Parasites
[0142] Cryptosporidium parvum oocysts were obtained from the
Sterling Parasitology Laboratory at the University of Arizona,
Tucson, Ariz., and were used to determine the efficacy of removal
or inactivation of infectious oocysts. The removal of
Cryptosporidium parvum oocysts was determined by Hemacytometer
counts on concentrated samples, whereas, the number of infectious
oocysts were determined by infection foci detection method using
cell culture technique with the most-probable-number assay
(FDM-MPN) (Slifko et al., Applied Environmental Microbiology,
65:3936-3941 (1999)). The results are presented in FIG. 5.
[0143] The cumulative removal/inactivation of infectious C. parvum
oocysts averaged at 97.9% (1.68 log) for all three filters. The
removal and inactivation performance by each filter were 95.4%
(1.34 log), 99.3% (2.15 log), and 98.9% (1.96 log) for filters 1,
2, and 3, respectively. The removal (only) of oocysts averaged at
71.3% (0.54 log) with an individual removal of 75.9% (0.62 log),
65.5% (0.46 log), and 72.4% (0.56) for filters 1, 2, and 3,
respectively. The study indicates that quaternary ammonium
organosilane coated zeolite can effectively reduce the viable
number pf protozoa parasites in aqueous liquid.
Open Cell Substrates
[0144] Various implementations of static fluid disinfecting systems
my utilize open-cell (reticulated) foams (both synthetic and
natural). In particular implementations, by non-limiting example,
the open-cell foam (foam) is composed of one or more cells with
structures of, by non-limiting example, tetrakaihedral, fullerene
("bucky-ball"), dodecahedron, tetrakaidecahedron, Weaire-Phelan
structures, honeycomb, bitruncated cubic honeycomb (Kelvin
structure), octahedral, any combination of the foregoing, and any
other polyhedral shape. Implementations utilizing Weaire-Phelan
structures may incorporate any of the structures disclosed in D.
Weaire et al., "A Counter-Example to Kelvin's Conjecture on Minimal
Surfaces," Phil. Mag. Let. 69:107-110 (1994), the disclosure of
which is incorporated herein entirely by reference. The open-cell
foams form an interconnected network of solid struts. In particular
implementations, the foam cells are arranged like soap suds,
forming a three dimensional, packed array of similarly sized
bubble-like structures. These structures may have theoretically
maximum volume and minimal surface area for a given volume. When
filled with liquid, the resulting structure is similar to an
interpenetrating network of polymers.
[0145] Foams containing any of the above structures are available
in a variety of pore structures as measured in pores per inch
(PPI). In various implementations, the pore size in PPI may range
from about 10 to about 110. In particular implementations, the pore
size may be about 20 to about 40 PPI. In other implementations, the
pore size may be 30 PPI and lower. It has been observed that, as
the pore size decreases above 110 PPI that the speed and
effectiveness of the disinfection decreases. In various open-cell
foam materials such as natural open cell foam materials such as
sponges, the actual cell size may vary significantly throughout the
material (they may have an average PPI within this ranges above),
but will also perform in this application following treatment with
organosilane quaternary compounds. In various implementations, the
open-cell foams are compressible structures and will conform to the
shape of the container when suitably sized. In particular
implementations, the foam will displace less than about 5% of the
liquid volume enclosed in a container when the foam is dimensioned
to fill substantially the entire volume of the container. After
treatment with organosilane quaternary compounds, the treated foam
may be compressed to less than about 25% of their original volume
without observable loss of antimicrobial activity.
[0146] Foams utilized in implementations of static fluid
disinfecting systems disclosed herein may be made of materials
including plastics, polymeric materials, stainless steel, copper,
silicon, carbon and silicon carbide. In particular implementation,
the plastic foams may be composed of virgin or recycled
polyethylene terephthalate (PET), polymethylmethacrylate (PMMA). In
various implementations carbon foams may compose at least a portion
of activated carbon. In implementations where the foam is made of a
metallic, semi-metallic, or composite material, the foam may take
the form of a mesh structure. Where the foams are made of
polyethylene and other plastic materials, they may be those
manufactured by New England Foam Products, LLC of Hartford, Conn.
In various implementations where the foam takes the form of a mesh,
the mesh treated with organosilane quaternary compounds could also
be arranged in a three dimensional shape like a mechanical stirring
device.
[0147] Implementations of antimicrobial foams like those disclosed
herein are prepared by applying an aqueous or alcoholic solution
containing about 0.1% to about 5.0% by weight of an organosilane
quaternary ammonium halide compound to the foam substrate by
immersion, pressure spray, electrostatic spray methods, and other
methods disclosed in this document. The wetted foams are allowed to
air dry or are heated to approximately 120 C to complete curing of
the antimicrobial film to the surfaces of the foam cells. When
dried/cured, the surface of the foam cell structures contains a
substantially uniform film of the organosilane material bonded to
the surface through silsesquioxane-like structures. The resultant
bonded film is insoluble in water and common solvents and is not
removed or leached off during operation in aqueous environments.
The coverage of the bonded film on the structure of the foam can be
evaluated visually by performing a blue dye test using bromophenol
blue. The test is carried out by applying a quantity of bromophenol
blue solution to the foam, and after allowing the solution to rest
on the foam for about 30 seconds, washing the bromophenol blue
solution out of the foam. The portions of the structure of the foam
that retain the blue color are those that contain bonded film, as
the bromophenol blue couples to the organosilane material and not
to the foam material.
[0148] In various implementations, the organosilane quaternary
compound used for treating may be
octadecyldimethyl-(3-trihydroxsilylypropyl) ammonium chloride. In
other implementations, organosilane starting materials for
formation of films may include one, all, or any of the
following:
[0149] Octadecyldimethyl-(3-methoxysilyslpropyl)ammonium chloride:
C.sub.18H.sub.35(CH.sub.3).sub.2N.sup.+(CH.sub.3O).sub.3SiC.sub.3H.sub.7
Cl.sup.-
[0150] Tetradecyldimethyl-(3-trimethoxysilylpropyl)ammonium
chloride:
C.sub.14H.sub.29(CH.sub.3).sub.2N+(CH.sub.3O).sub.3SiC.sub.3H.sub.7
Cl.sup.-
[0151] Didecylmethyl-(3-trimethoxysilylpropyl)ammonium chloride
(C.sub.10H.sub.21).sub.2CH.sub.3N+(CH.sub.3O).sub.3SiC.sub.3H.sub.7
Cl.sup.-
[0152] In various implementations, other substrate reactive
organosilanes including ammonium chloride moieties may be utilized.
Any of the organosilane compounds disclosed in this document may be
employed in various implementations.
[0153] In this document, filter media treated with organosilane
quaternary ammonium materials are disclosed that remove pathogens
from water passing through the filter media of 2 log for bacteria
and up to 98% for parasitic protozoa such as Cryptosporidium
parvum. It was previously theorized that the increased surface area
of a media, especially in the case of filter media such as sand or
zeolites, would result in increased elimination and inactivation of
pathogens dispersed in the water. The foams disclosed herein have a
greatly reduced surface area (less than or equal to about 1
m.sup.2/gram) when compared with filter media such as filter sand
(tens of m.sup.2/gram) or zeolites (hundreds of m.sup.2/gram), but
also demonstrate significant antimicrobial activity when placed in
a static container of liquid sufficient to disinfect the fluid. The
open-cell foams have a minimal surface area as the foam, during
manufacture, seeks to create a maximum volume with a minimum
surface area and resulting surface energy (driven by surface
tension and surface free energy effects).
[0154] It has been observed that organosilane quaternary treated
foams manufactured according the principles in this disclosure
eliminate and inactivate bacterial, viral and parasitic protozoa
pathogens up to 6 log in 10 minutes of static exposure of the
pathogen containing liquid to the submerged foam in a container for
an effective period of time. Such foams treated with organosilane
quaternary compounds have been demonstrated to rapidly and
effectively disinfect fluids in which they are in contact by
inactivating and eliminating a wide variety of pathogens including
viruses (encapsulated and non-encapsulated), algae, gram positive
bacteria, gram negative bacteria and parasitic protozoa including
Cryptosporidium parvum and Giardia. Similar to the other
antimicrobial compounds disclosed herein, the disinfection process
is non-leaching and imparts no detectable antimicrobial agent or
compounds into the contacting fluid. An example of the performance
of an implementation of a treated foam is found below:
Example 7
[0155] Twenty samples of water containing bacteria, viruses, and
Cryptosporidium oocytes were treated according to the standards in
the NSF International P248 test for Military Operations
Microbiological Water Purifiers. Passage of the test requires that
within a maximum of 20 minutes for all 20 samples, the bacterial
population decrease by 6 log, the viral population decrease by 4
log, and the Cryptosporidium oocytes be reduced by 3 log. When
foams treated with 1-Octadecanaminium,
N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)-chloride were placed in
the twenty samples, remaining in static contact with the water, in
10 minutes 18 of the 20 samples met the test criteria, and by 15
minutes, all 20 samples had experienced microbe reduction to the
desired testing levels. In this case, the effective period of time
was reached when residual microorganism levels in all the samples
reached the desired reduced level, in 15 minutes.
[0156] Unlike the use of treated filter media discussed earlier in
this document, the disinfection process occurs under static
conditions of little to no fluid flow over the treated surface of
the foam and is accordingly not a filtration process for pathogen
removal. Because the foams are suitable for use in non-flowing,
fluid conditions they may be useful for antimicrobial stabilization
of fluids for extended periods in containers. Fluids in contact
with treated foams may be stored for extended periods without
microbial growth or the need for external influences such as
refrigeration. Because of this, implementations of treated foams
like those disclosed herein may be incorporated in fluid transport
vehicles, such as milk tanker trailers, and other bulk foodstuff
transport vehicles and systems. An additional benefit for vehicles
like milk tanker trailers is that if the foams are attached at
regular intervals along the internal circumference of the tank with
a dimension extending radially into the milk payload, they will
have a baffling effect, reducing momentum flow effects of the milk
moving around during transport. However, because the foams are
antimicrobial, the problems of trying to clean a conventional tank
with metal baffles may be eliminated. In some implementations,
gravity fed flow filtration using treated foams may be used,
provided it is carried out at low pressures that do not
mechanically harm the films.
[0157] This result of increased efficacy of the open-cell treated
substrate when compared with the performance of organosilane
treated filter media is unexpected. This is because the surface
area of foam media contacting the contaminated fluid is far less
than filter media. For example, the surface area per volume of the
foam implementations when compared with the surface of zeolite and
sand is millions of times smaller. For example, the surface area of
a zeolite ranges in the hundreds of square meters per gram. In
contrast, a treated foam with a surface area of just 36.4 square
feet can disinfect a water bladder that holds 2.5 liters of water.
This disinfection using foams takes place rapidly (90 seconds-15
minutes) compared to previous systems that involved coating the
interior surface of a bottle with organosilane materials (3 hours).
Being able to obtain orders of magnitude improved inactivation or
similar inactivation of microbes as with use of treated filter
media from a foam with orders of magnitude less surface area
employed in a non-forced flow, static fluid operating condition is
an unexpected result which runs contrary to conventional knowledge
of those of ordinary skill in the art.
[0158] Once prepared by coating with organosilane quaternary
ammonium compounds, the treated foams can be stored outside liquid
for greater than 5 years and still retain their antimicrobial
activity. Because of this, the effective antimicrobial lifetime of
a treated foam is determined by the ability of the particular
underlying foam material to withstand prolonged exposure to the
fluid without beginning to shed or otherwise breakdown mechanically
within the fluid. This means that the limit to the volume of liquid
that could be potentially treated by a coated foam is the
mechanical lifetime/stability of the foam.
[0159] Implementations of foams like those disclosed herein are
capable of disinfection of clear and turbid water as well as
visually opaque fluids including food juices, plant extracts, milk,
and milk products. These foams may be particularly useful for
visually opaque fluids as conventional methods of fluid
disinfection include widespread use of energy intensive ultraviolet
(UV) radiation for which the fluid must be transparent. Because the
foams do not require adding any liquid matter to the liquid or
leach into the fluid, they contrast with other conventional methods
which require the addition of toxic, fluid soluble compounds
including energy intensive and toxic ozone or equally toxic,
carcinogen-producing chlorine, iodine, chlorine dioxide and
chloramines. Implementations of foams like these disclosed may be
used to disinfect cutting or fracking fluids (hydrocarbon [oil] and
water mixtures) as well as any other flowable liquid that does not
contain particulates that would clog the foam. Implementations of
foams like those disclosed herein may also be employed to disinfect
solid materials, such as powders that are dispersable and can
contact the foam. In other implementations, implementations of the
foams may be used to provide disinfection of solids and liquids
through surface contact. For example, in meat packaging, the meat
may be laid down on a piece of treated foam (which may be the
packaging container in particular implementations), which will act
to kill microbes in the meat and in liquids associated with the
meat during transport and storage prior to food preparation. In
such implementations, one or more surface of the meat (or other
solid) are contacted by the foam.
[0160] Implementations of static fluid disinfecting systems
employing open-cell foams like those disclosed herein may employ
various implementations of a method of disinfecting a fluid.
Implementations of the method include statically contacting a fluid
containing one or more microorganisms with a foam coated with any
one of the quaternary organosilanes disclosed herein in a container
that encloses the foam and holds the fluid. The fluid may contain
one or more of any of the microorganisms disclosed herein. In
various implementations of the method, the method may include
statically contacting one or more surfaces of a solid included in
the container with the foam. This solid could be any disclosed in
this document, including foodstuffs and other solid materials that
contain one or more microorganisms.
[0161] Implementations of ballast water treatment systems are
disclosed in this document. Ballast water treatment systems are
used in ships and vessels traveling via water that retain or store
water for stabilization as ballast.
[0162] In 2004, the International Convention for the Control and
Management of Ships' Ballast Water and Sediments (the Convention)
was adopted and has been ratified by sufficient states to go into
effect in 2016. The Convention includes basic standards controlling
the amount of harmful aquatic organisms and pathogens found in
ballast water that may be released by a ship of any size. The
ballast water is taken up typically at the beginning of a ship's
voyage to a new port and, accordingly, is composed of those aquatic
organisms and pathogens that are present in the water in the port
of origin. When reaching the destination, release of some or all of
the stored ballast water is generally done as part of preparation
of the ship for its next voyage. Since the ship is now at its port
of destination, the aquatic organisms present in the ballast water
are potentially not native to that area. Since these non-native
aquatic organisms enter the environment of the port of destination
separate from their natural predators, they can rapidly become an
invasive species and destroy the ecological variety of the
destination port. Zebra mussels are an example of a non-native,
invasive species that has traveled to North America through ballast
water.
[0163] A summary of the Convention standards is found in Appendix C
of the U.S.
[0164] Provisional Patent Application 62/040,348 to William R.
Peterson II, et al., entitled "Ballast Water Treatment Systems,"
which was filed on Aug. 21, 2014 (the '348 Provisional), the
disclosure of which was previously incorporated entirely herein by
reference. To reach these standards for discharged ballast water
from the ship at the port of destination, various conventional
ballast water treatment systems have been devised. In the United
States, regulations regarding management of ballast water and
associated penalties may be found in 33 C.F.R. .sctn.151.1500 et.
seq. (2012) and the regulations regarding the approval of ballast
water management systems (BWMS) may be found in 46 C.F.R.
.sctn.162.060 et seq. (2012) the disclosures of which are
incorporated entirely herein by reference.
[0165] Various implementation of BWMS using quaternary ammonium
organosilane compounds are disclosed in this document. Referring to
FIG. 7, an implementation of a BWMS 2 is illustrated that utilizing
quaternary ammonium organosilanes to destroy microorganisms in
ballast water. As shown, water (whether fresh or sea water) for use
as ballast water enters through an intake screen, being drawn in
through the main ballast water intake pump. The water then is
passed passes through one or more screen filters (varying sizes of
screens may be used). The ballast water is then passed through one
or more multi-cartridge filter devices (in series or parallel)
containing cartridges (cartridge filters) that contain quaternary
ammonium organosilane coatings. The resulting filtered ballast
water then enters the ballast tank (one or more ballast tanks may
be used, located various places on a ship or vessel).
[0166] Depending upon the antimicrobial performance of the BWMS, in
some implementations, the filtered sea water may be sufficiently
filtered and/or purified to be stored and subsequently released
from the ballast tanks following one pass through the one or more
multi-cartridge filters without requiring further treatment to meet
the regulatory standards disclosed. In other implementations, while
the filtered sea water is residing in the one or more ballast
tanks, the filtered sea water is drawn into a recirculation loop
through use of one or more recirculation pumps and into one or more
recirculation filters containing one or more cartridges treated to
form a coating of quaternary ammonium organosilanes on the material
of the one or more cartridges. The recirculated water then
circulates back into the one or more ballast tanks. When changes in
the amount ballast water in the ballast tanks need to be made,
water from the ballast tanks is drawn out using the ballast water
dump pump and discharged into the ambient sea water surrounding the
ship. As required by various regulations, the crew of the ship will
have completed testing of the ballast water in the ballast tanks to
determine the organism and pathogen levels prior to discharging any
of the water.
[0167] The foregoing high level review of the process shows the
overall flow of sea water into and out of the ballast tanks.
Various implementations of the system will employ various
filtration, intake, and pumping components to perform the various
functions of the system. Various system implementations operate
identically using fresh water as in sea water.
[0168] In various implementations, and for the exemplary purposes
of this disclosure, the intake screen may be any of the
self-cleaning suction screens disclosed in Appendix E of the '348
Provisional manufactured by VAF Filtration Systems of Arvada, Colo.
Many other intake screen designs may be utilized in various
implementations which are adapted to such factors as the required
volume of water, the cleanliness of the sea water surrounding the
vessel, and the size of the intake piping. In the implementations
disclosed in Appendix E, the interior of the screen is washed
continuously using rotating water jets while intake water is being
simultaneously drawn into the screen preventing particles from
between about 710 microns to about 1680 microns from being able to
enter with the intake water.
[0169] The one or more screen filters for processing the intake sea
water may be, in various implementations, any of the LPV-Series
automatic screen filters manufactured by VAF Filtration Systems of
Arvada, Colo. These screen filters permit filtration of matter and
organisms down to 80 microns at varying flow rate while allowing
for cleaning of the filtered material from the filter without
stopping of the operation of the screen filter system. The filter
material drawn from the screen filter can be, in various
implementations, discharged directly into the water surrounding the
vessel, as the filtered organisms are the same as those in the
intake water and no contamination issues exist with these
organisms. While in various implementations, screen filters could
be used, in others, other passive or automatic filtration systems
could be employed, including, by non-limiting example, membrane,
sand, zeolite, and other filter media systems. In all
implementations, one or more filter screens/membranes/stages may be
included in each filter, and, where more than one filter is used,
they may be arranged to treat the intake water in parallel or in
series or in series/parallel combinations as desired.
[0170] Intake water leaving the screen filter is then processed by
a multi-cartridge filter system containing many cartridges
(cartridge filters) that have been treated with quaternary ammonium
organosilanes to form a coating on the material of filters. A wide
variety of filter systems capable of including multiple cartridges
may be included in various systems implementations. For the
exemplary purposes of this disclosure, the multi-cartridge systems
disclosed in Appendix G of the '348 Provisional manufactured by
HARMSCO Filtration Products of North Palm Beach, Fla. may be used
in particular implementations. Appendix G also discloses examples
of filter cartridge types that may be treated and used to filter
the intake water. Referring to FIG. 9, an example of filter
cartridge that can be treated with quaternary ammonium
organosilanes is illustrated (see also those in Appendix H of the
'348 Provisional). In various implementations, many different
filter types (wound filters, sand filters, zeolite filters, etc.)
may be treated with quaternary ammonium organosilanes and placed in
a multi-cartridge system like those in disclosed in Appendix G (or
other systems) and used for filtration. Various combinations of
different filters types may be also used in the same multi-filter
cartridge filter system. Bag filters may also be employed in
particular implementations. The systems in illustrated in Appendix
G of the '348 Provisional may have improved filtration
characteristics because they employ cyclonic movement of the water
within the filter vessel over and through the plurality of filter
cartridges contained therein.
[0171] A wide variety of quaternary ammonium organosilane compounds
may be employed in various implementations of ballast water
treatment systems like those disclosed herein. For example, the
compounds could be any of those disclosed in this document and in
any of the references incorporated by reference herein, including
the '348 Provisional.
[0172] Particular implementations of systems may utilize any one or
any combination of the following quaternary ammonium organosilanes:
Tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (CAS
No. 41591-87-1); Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium
chloride (CAS No. 27668-52-6); and
Didecylmethyl-N-(3-trimethoxysilylpropyl)ammonium chloride (CAS No.
68959-20-6). Implementations of various systems may employ
quaternary ammonium organosilanes which may include silanes
represented by the formula:
A.sub.4-nSi(R NHaR.sup.1.sub.b Z).sub.n
[0173] A, R, a, n, R.sup.1, b, and z may be any chemical structural
moiety (element) identified by the same notation in U.S. Pat. No.
6,613,755 to William R. Petersen II et al., entitled "Antimicrobial
skin preparations containing organosilane quaternaries," filed Mar.
29, 2002 and issued Sep. 2, 2003, the disclosure of which is
incorporated entirely herein by reference. Furthermore,
implementations of various ballast water treatment systems may
employ quaternary ammonium organosilanes which may include silanes
represented by the formula:
##STR00005##
[0174] In these implementations, A, n, R, R.sup.1, R.sup.2,
R.sup.3, and Z may be any chemical structural moiety identified by
the same notation in the '121 utility, '429 provisional, the '720
utility, and the '348 Provisional.
[0175] Any of the methods of treating filter media, filter
cartridges, and disinfecting foams disclosed in the '121 utility,
'429 provisional, '720 utility, the '477 provisional, and the '348
provisional with quaternary ammonium organosilane compounds may be
employed to treat the filter cartridges and/or filter media
included in the filter cartridges that are included in the
multi-cartridge filter system and form a coating thereon. As
disclosed in the foregoing applications, the quaternary
organosilane compounds are non-leaching, meaning that there is no
detectable active agent present in water leaving the filters. The
life span of the coating of quaternary ammonium organosilane
compound on the filter media may be about 5 years.
[0176] The filters employed may filter pathogens and organisms
sized from about 0.2 microns to about 25 microns to about 50
microns. In particular implementations, the filters may be about
3-4 inches in diameter and about 40 inches long. In other
implementations, the filters may be about 3 inches long. Depending
upon the amount of intake water needing to be processed, the number
of filters included in the multi-cartridge system may be just a few
to greater than 160 filters. In various implementations, cartridge
filters like those disclosed herein may not be used, but the
multi-cartridge filter system may be adapted for using treated
filter sand, treated zeolite, or other treated filter media that
has been treated to form a coated quaternary organosilane coating
like any of those disclosed in this document and the references
incorporated herein using any reagent disclosed therein. In other
implementations, a combination of cartridge filter(s) and treated
filter sand, treated zeolite, or other treated filter media coated
with a quaternary organosilane coating like those disclosed herein
may also be used. Any of the treated filter sand, treated zeolite,
or other treated filter media disclosed in this document any in any
of the references incorporated herein by reference may be used in
various implementations.
[0177] As disclosed and discussed at length in the '348 provisional
and the references incorporated herein by reference, as the
effectiveness of the quaternary ammonium organosilane compounds for
killing and/or deactivating viruses, bacteria, cysts, spores,
yeasts, fungus, eggs, and other microscopic organisms and pathogens
is very high, in ballast water treatment systems like those
disclosed herein, the intake water may be cleaned to at least the
regulatory standards in Appendix C of the '348 provisional after
just a single pass through the multi-cartridge filter system.
Accordingly, the water entering the ballast tanks could be
immediately discharged following testing without requiring any
additional filtration.
[0178] Since the filtered water in the ballast tanks has the
potential to remain in the tanks for an extended period of time
during various voyages, the use of a recirculation loop as
illustrated FIGS. 7 and 8 as an aid in maintaining the filtered
water in the ballast tanks at the desired cleanliness standard may
be important in various system implementations. In such systems,
the recirculation system can operate continuously or periodically
on a desired interval, using the recirculation pump to draw water
from the ballast tanks and pass it through the recirculation
filter. In various implementations, the recirculation filter may be
a multi-cartridge filter system (though sized proportionally
smaller to the lower flow), may be a single filter system, or a
series and/or parallel set of two or more filters. Any of the
multi-cartridge filter systems disclosed herein may be employed in
various implementations.
[0179] In particular implementations of the system, in addition to
the filter cartridges and/or filter media being treated with
quaternary ammonium organosilane compounds, the other components of
the system that contact the ballast water may also be coated with a
layer of quaternary ammonium organosilanes. Depending upon the
implementation, the intake screen components, pumps and pump
impellers, interior components of the screen filter, the
water-contacting surfaces of the multi-cartridge filter system and
recirculation filter, all piping, and the interior surfaces of the
ballast tanks (walls, floors, or any surface and/or any combination
of surfaces thereof) can be coated with a layer of quaternary
ammonium organosilane compounds like those selected herein. Any of
the coating techniques disclosed in any of the references
incorporated by reference herein may be employed. Also, in various
implementations, the quaternary ammonium organosilane compound
precursor materials may be applied to the desired surfaces of the
various system components using electrostatic spraying to prevent
domain formation behavior and beading of the film. In particular
implementations, two rounds of spraying may be carried out
following which a curing process is employed to transition the
precursor material sprayed from a monomeric material to
self-assembling layers to form a fully cured silsesquioxane
(organosilsesquioxane) structured film. Following use of the
system, the various system components may need the film reapplied
periodically to keep the film actively able to kill and destroy
organisms and pathogens. Because the various system components may
also be treated with the quaternary ammonium organosilane
compounds, several beneficial effects may exist, including the
elimination/minimization of the formation of biofilms in various
parts of the system which create sources of continuous
contamination and making it easier to treat and maintain the
ballast water at the desired cleanliness standards.
[0180] Implementations of ballast water management systems like
those disclosed herein may be employed in a wide variety of
watercraft including those subject to the regulations in the
Convention and those which are not. Implementations of the system
may be used for both fresh and marine (salt water) applications,
and may, in various system implementations, be equally successful
in both fresh and marine applications without requiring any
operational changes. Smaller systems may be included in water craft
that operate in fresh waters only and which do not include ballast
tanks, but take on water during normal operation or during storage
at a dock in the form of bilge water. Because of the single pass
kill capabilities of the systems disclosed herein employing
quaternary ammonium organosilanes, such smaller systems may be
developed to treat bilge water at the time it is released. Because
of this, regulations for smaller craft that currently require
draining and drying before transferring the smaller craft from one
body of water to another may be unnecessary, as the system is
capable of treating any bilge water released from the vessel in the
new body of water sufficiently to eliminate the pathogens/organisms
present in the bilge water that came from the previous body of
water.
[0181] Furthermore, in various ballast water management systems,
static disinfection systems and methods like those described in the
'720 utility, and the '477 provisional may be employed. For
example, in smaller ships where the ballast tanks are small, there
may not be much space for piping for a recirculation loop.
Accordingly, the ballast tanks could be at least partially filled
with/contain an open-celled foam material coated with the
quaternary ammonium organosilane compounds and, while the ballast
water resides in the ballast tanks, static disinfection using the
foam may take place as disclosed in the references incorporated
herein by reference. An implementation of such a ballast water
management system is illustrated in FIG. 8, which shows a ballast
tank partially filled with a static disinfecting foam in
combination with a recirculation loop. However, in other
implementations, the recirculation loop may not be included due to
size/complexity restrictions and/or may not be needed in view of
the presence of the foam.
[0182] Furthermore, in system implementations that do not employ a
recirculation loop, the system may be designed to pass the ballast
water back through the multi-cartridge filter system for a second
pass prior to being discharged. A wide variety of system
implementations are possible using the principles disclosed herein,
including various recycle, multiple pass, recirculation systems
that filter between ballast tanks, and others. Those of ordinary
skill in the art will readily be able to construct system
implementations using the principles disclosed herein.
Example 7
[0183] A sample of the marine salt water (Pacific Ocean, San Diego
Bay, Calif.) was used with a test apparatus to determine microbial
reduction utilizing treated cartridge filter systems. The test
apparatus consisted of stainless steel and PVC piping 0.75 inches
in diameter. Pumping through the system was accomplished utilizing
an air-actuated diaphragm pump with an adjusted flow rate of 1-2
gallons per minute through two types of test cartridge filters.
Test cartridges were Parker Fulflo Poly-Mate (#PM600-10AE-DO) and
Parker Fulflo Glass-Mate (#PMG400-10FE-DO) filters. Filters were
utilized in testing as untreated (as received) or treated with a
quaternary ammonium organosilane compound marketed under the
tradename Z71 by Zoono of New Zealand (Coating Systems
Laboratories, Inc., EPA Reg. No. 008007-1, 3-trimethoxysilyl propyl
dimethyl octadecyl ammonium choride) solution through immersion and
oven drying at 120.degree. C. Flow rates were measured utilizing
PVDF Flowmeter/Totalizer (GPI, Great Plains Industries) calibrated
for flow rates of 1.2-12.0 gallon per minute. Microbial testing was
performed using a Hygiena ATP meter in conjunction with Hygiena
Aquasnaps (#AQ-100). A test apparatus was assembled and testing
performed for four filter systems. Filter system A consisted of
untreated Poly-Mate filter. Filter system B consisted of Z71
treated Poly-Mate cartridge filter. Filter system C contained the
untreated Glass-Mate cartridge and Filter system D contained the
Z71 treated Glass-Mate cartridge. The units were assembled
individually by placing each designated filter system into the
cartridge holder within the test apparatus. The assembled units
were tested individual at a flow rate of 1.0-1.2 gpm. Initial
microbial count of the San Diego seawater before testing was
measured at 720 utilizing Hygiena test meter and Hygiena Aquasanp.
Results of the testing using the four systems are summarized in
Table 1:
TABLE-US-00001 TABLE 1 Initial Microbial Count After Filter System
Count Filtration Reduction (%) A 720 646 10.3 B 720 12 98.3 C 720
664 7.8 D 720 6 99.1
[0184] As can be observed, filter systems B and D that were coated
with a quaternary ammonium organosilane material achieved a greater
than 95% reduction in microbes through only one pass through the
filter.
[0185] In places where the description above refers to particular
implementations of ballast water treatment systems and implementing
components, sub-components, methods and sub-methods, it should be
readily apparent that a number of modifications may be made without
departing from the spirit thereof and that these implementations,
implementing components, sub-components, methods and sub-methods
may be applied to other ballast water treatment systems. For
example, the features of the reagents of the various
implementations are equally applicable to the coatings of the
implementations described herein.
* * * * *