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WO2008030925A2 - Colorants antimicrobiens - Google Patents

Colorants antimicrobiens Download PDF

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Publication number
WO2008030925A2
WO2008030925A2 PCT/US2007/077709 US2007077709W WO2008030925A2 WO 2008030925 A2 WO2008030925 A2 WO 2008030925A2 US 2007077709 W US2007077709 W US 2007077709W WO 2008030925 A2 WO2008030925 A2 WO 2008030925A2
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optionally substituted
group
polymer
compound
formula
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WO2008030925A3 (fr
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Gang Sun
Junshu Liu
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University of California Berkeley
University of California San Diego UCSD
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University of California Berkeley
University of California San Diego UCSD
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Priority to US11/870,391 priority Critical patent/US20080201871A1/en
Publication of WO2008030925A2 publication Critical patent/WO2008030925A2/fr
Publication of WO2008030925A3 publication Critical patent/WO2008030925A3/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
    • C07C225/34—Amino anthraquinones
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/002—Dyes with anthracene nucleus not condensed with any other ring containing onium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0036—Dyeing and sizing in one process
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/20—Anthraquinone dyes

Definitions

  • antimicrobial colorants are derivatives of triphenylmethane dyes such as gentian violet, brilliant green and malachite green, which have poor light stability and tend to be decolorized by bacteria ⁇ see, Jones, J.J. and Falkinham, J. Ill, Antimicrobial Agent and Chemotherapy, 47(7):2323 (2003)). Also, a high concentration of these dyes is needed to achieve the expected functions due to high minimum inhibition concentration (MIC) of the dyes, while a high concentration of the dyes creates concerns of staining. In recent decades, scores of new antimicrobial agents, especially quaternary ammonium compounds have been invented to substitute these antimicrobial dyes.
  • MIC minimum inhibition concentration
  • Quaternary ammonium salts are cationic surface active compounds that can provide combined effects of disinfection, surface-activation, and antistatic properties ⁇ see, Patrauchan, M. A. and Oriel, P. J., Journal of Applied Microbiology, 94:266 (2003)). Because they destroy microbes by a physical penetration mechanism ⁇ see, Russell, A.D. and Russell, NJ. , Symposium of the Society for General Microbiology, 53:327 (1995)), QAS are relatively mild in action and effective against a broad spectrum of microorganisms such as bacteria (both Gram-positive and Gram-negative), fungi and enveloped viruses.
  • QAS have been extensively employed as disinfectants in many fields such as chemical formulations, personal care products, surface cleaning spray, and dental products, ⁇ see, Russell, A.D. and Russell, N.J., Symposium of the Society for General Microbiology, 53:327 (1995); Broughton, R.M. Jr., Worley, S.D. et al, International Nonwovens Technical Conference, 131 '-47 (2001); Sun, G., ACS Symposium Series, 792:243 (2001)).
  • QAS are also applied in resins, textiles and other polymers to incorporate antimicrobial functions by chemical grafting or finishing ⁇ see, Destais, N., Ades, D. et al.
  • the present invention provides novel antimicrobial cationic dyes comprising a quaternary ammonium salt (QAS) group covalently attached to an aminoanthraquinioid dye optionally via a linker.
  • QAS quaternary ammonium salt
  • the dyes are particularly useful for imparting a functional property to a polymer, such as an antimicrobial functionality, and for simultaneously dyeing and finishing a polymer (e.g., textile).
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group
  • each Y 2 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group
  • m is an integer from 0 to 4
  • n is an integer from 1 to 4.
  • the present invention provides a compound of formula Ib:
  • R 2 and R 3 are each independently selected from an optionally substituted C 1 -
  • R 4 is an optionally substituted C 4 -C 18 alkyl group
  • R 10 is a member selected from the group of hydrogen, hydroxyl, an optionally substituted alkyl, an optionally substituted alkoxy, an optionally amino, an optionally substituted aryl, and an optionally substituted thiol, r and y are each independently 0 to 4; and X is a counter anion.
  • the present invention provides an antimicrobial composition, comprising:
  • a polymer wherein the polymer is a member selected from the group of a textile, a plastic, rubber, paint, a surface coating, a spray, an adhesive, and a combination thereof;
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group
  • each Y 2 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group
  • m is an integer from 0 to 4
  • n is an integer from 1 to 4.
  • the present invention provides a method for simultaneously dyeing and finishing a polymer, comprising:
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group
  • each Y 2 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group
  • m is an integer from 0 to 4
  • n is an integer from 1 to 4.
  • the present invention provides a method for preparing a colorant, comprising:
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group;
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group;
  • E is an electrophic group or a carbon capable of reacting with an amino group to form a nitrogen-carbon bond;
  • L is a bond or a linker selected from the group consisting of alkylene, heteroalkylene, cycloalkylene, cycloalkylalkyllene, arakylene, arylene, heteroarylene, heteroaralkylene, alkenylene, substituted alkylene and alknylene;
  • X is a halide;
  • m is an integer from 0 to 4; and
  • n is an integer from 1 to 4.
  • the present invention provides a method for preparing an antimicrobial colorant, comprising:
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group; each of R 2 , R 3 , and R 4 is independently selected from the group consisting of hydrogen, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted aralkyl, an optionally substituted cycloalkyl, and cycloalkylalkyl; L is a bond or a linker selected from the group consisting of an optionally substituted alkylene, an optionally substituted heteroalkylene, an optionally substituted cycloalkylene, an optionally substituted cycloalkylalkylene, an optionally substituted arakylene, an optionally substituted arylene, an optionally substituted heteroarylene, an optionally
  • the compounds i.e., the QAS-dyes
  • polymers e.g., textile materials
  • the QAS-dyes can be treated with the QAS-dyes to provide a biocidal protective coating on the polymers effective against a variety of microorganisms.
  • the treated polymers are suitable for use as clothing in the medical field as well as in related healthcare and hygiene areas.
  • Treated polymers of the present invention can be fabricated into disposable or reusable textile materials.
  • the microbiocidal properties of the textiles of the present invention can be advantageously used for women's wear, underwear, socks, and other hygienic purposes such as upholsteries.
  • the microbiocidal properties can be imparted to carpeting materials to create odor-free and/or germ-free carpets.
  • all germ-free environments such as those required in biotechnology and the pharmaceutical industry, can benefit from the use of the microbiocidal textiles of the present invention to prevent any contamination from air, liquid, and/or solid media.
  • Figure 1 illustrates one embodiment of a synthesis route of antimicrobial colorants (wherein the alkylene chain length varies) of the present invention.
  • Figure 2 illustrates a FTIR spectra of certain embodiments of antimicrobial colorants of the present invention.
  • Figure 3 illustrates a 1 H NMR spectrum of one compound of the present invention.
  • Figure 4 illustrates a 1 H 1 H COSY spectrum of one compound of the present invention.
  • Figure 5 illustrates a UV vis absorbance spectra (concentration ⁇ 00 ppm) of compounds of the present invention.
  • Figure 6 illustrates a UV vis spectra of compounds of the present invention.
  • alkyl includes a saturated linear monovalent hydrocarbon radical or a saturated branched monovalent hydrocarbon radical containing from 1 to 20 carbon atoms.
  • the alkyl radical contains from 1 to 4 carbon atoms (i.e., C 1 -C 4 alkyl) or from 4 to 18 carbons atoms (i.e., C 4 -C 18 alkyl).
  • Exemplary alkyl groups include, but are not limited to, methyl, ethyl, ⁇ -propyl, 2-propyl, butyl, wo-butyl, sec-butyl, tert-butyl, pentyl, wo-amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like.
  • alkylene includes a saturated linear divalent hydrocarbon radical or a saturated branched divalent hydrocarbon radical containing from 1 to 20 carbon atoms.
  • the alkylene radical contains from 1 to 12 carbon atoms (i.e., Cj-Ci 2 alkylene).
  • Exemplary alkylene groups include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, and the like.
  • cycloalkyl includes a cyclic alkyl radical containing from 3 to 8, preferably from 3 to 6, carbon atoms.
  • exemplary cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • cycloalkylene includes a cyclic carbocycle radical containing from 4 to 8, preferably 5 or 6, carbon atoms and one or more double bonds.
  • exemplary cycloalkylene groups include, but are not limited to, cyclopentylene, cyclohexylene, cyclopentadienylene, and the like.
  • aryl includes a carbocyclic aromatic radical selected from the group consisting of phenyl, naphthyl, indenyl, indanyl, azulenyl, fluorenyl, anthracenyl, and the like; or a heterocyclic aromatic radical selected from the group consisting of furyl, thienyl, pyridyl, pyrrolyl, oxazolyly, thiazolyl, imidazolyl, pyrazolyl, 2-pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,3,5-trithianyl, indolizinyl, indolyl, isoindoly
  • the aryl group can also have from one to five substituents selected from the group consisting of hydrogen, halogen, hydroxyl, amino, nitro, trifluoromethyl, trifluoromethoxy, alkyl, alkylene, alkynyl, 1 ,2-dioxymethylene, 1 ,2-dioxyethylene, alkoxy, alkenoxy, alkynoxy, alkylamino, alkenylamino or alkynylamino, alkylcarbonyloxy, aliphatic or aromatic acyl, alkylcarbonylamino, alkoxycarbonylamino, alkylsulfonylamino, N-alkyl, N,N-dialkyl urea, and the like.
  • alkoxyl includes an alkyl ether radical containing from 1 to 20 carbon atoms.
  • exemplary alkoxyl groups include, but are not limited to, methoxyl, ethoxyl, n- propoxyl, /s ⁇ -propoxyl, «-butoxyl, wo-butoxyl, sec-butoxyl, f ⁇ rt-butoxyl, and the like.
  • alkylamino includes a mono- or di-alkyl-substituted amino radical (i.e., a radical having the formula: alkyl-NH- or (alkyl) 2 -N-), wherein the term “alkyl” is as defined above.
  • exemplary alkylamino groups include, but are not limited to, methylamino, ethylamino, propylamino, zs ⁇ -propylamino, t-butylamino, iV,jV-diethylamino, and the like.
  • aralkyl includes an aryl radical, as defined herein, attached to an alkyl radical, as defined herein.
  • amino protecting group includes a group which will decrease the reactivity of amine group, such as by converting it to an amide or a carbamate.
  • the carbonyl group effectively withdraws electron density from the nitrogen and renders it unreactive.
  • Formation of N-acyl derivatives such as benzyloxycarbonyl (Z or Cbz), t-butoxycarbonyl (t- BOC), 9- fluorenylmethoxycarbonyl (Fmoc) and phthalimides (Pht) are a few of the suitable amino protecting groups. Those of skill in the art will know of other amino protecting groups suitable for use in the present invention.
  • cycloalkylalkyl includes a cycloalkyl radical, as defined herein, attached to an alkyl radical, as defined herein.
  • optionally substituted includes both the "unsubstituted” and “substituted” substituent.
  • optionally substituted alkyl includes “unsubstituted alkyl” and “substituted alkyl,” the latter of which refers to moieties having substituents replacing one or more hydrogens on one or more carbons.
  • substituents can include, for example, alkyl groups, alkynyl groups, halogens, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,
  • heteroatom includes any atom that is not carbon or hydrogen.
  • exemplary heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, phosphorus, boron, and the like.
  • the term "functional finishing dye” includes a dye containing at least one functional finishing group covalently attached to the dye via a chemical linkage.
  • the term "functional finishing group” includes a moiety that is present in a functional finishing dye which imparts a particular functional property to the dye-treated polymer.
  • the term "functional property” or “functionality,” as used herein, includes a particular non-inherent and/or enhanced physical property of the polymer due to the presence of a functional finishing group.
  • exemplary functional properties include, but are not limited to, antimicrobial, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, and anti-chemical properties, as well as a combination of two or more properties thereof. Antimicrobial functionality is preferred.
  • leaving group has the meaning conventionally associated with it in synthetic organic chemistry, i.e., an atom or a group capable of being displaced by a nucleophile, and includes halo (such as chloro, bromo, and iodo), alkanesulfonyloxy, arenesulfonyloxy, alkylcarbonyloxy ⁇ e.g., acetoxy), arylcarbonyloxy, mesyloxy, tosyloxy, trifluoromethanesulfonyloxy, aryloxy (e.g., 2,4-dinitrophenoxy), methoxy, N,O- dimethylhydroxylamino, and the like.
  • halo such as chloro, bromo, and iodo
  • alkanesulfonyloxy arenesulfonyloxy
  • arylcarbonyloxy mesyloxy, tosyloxy
  • antimicrobial includes the ability to kill at least some types of microorganisms, or to inhibit the growth or reproduction of at least some types of microorganisms.
  • the polymers prepared in accordance with the present invention have microbicidal (i.e., antimicrobial) activity against a broad spectrum of pathogenic microorganisms.
  • the textiles, polymers and fibers have microbicidal activity against representative gram-positive (e.g., Staphylococcus aureus) and gram-negative (e.g., Escherichia coli) bacteria.
  • quaternary ammonium salt group includes an amphipathic molecule that contains both a hydrophilic portion and a hydrophobic portion and is covalently attached to a dye.
  • the quaternary ammonium salt group has the formula:
  • R 3 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group; each of R 4 , R 5 , and R 6 is independently selected from the group consisting of hydrogen, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted aralkyl, an optionally substituted cycloalkyl, and an optionally substituted cycloalkylalkyl; L is a linker comprising a 1-12 carbon atom chain; and X is a counter anion.
  • the term "treating,” “contacting,” or “reacting” includes adding or mixing two or more reagents under appropriate conditions to produce the indicated and/or the desired product. It should be appreciated that the reaction which produces the indicated and/or the desired product may not necessarily result directly from the combination of two reagents which were initially added, i.e., there may be one or more intermediates which are produced in the mixture which ultimately leads to the formation of the indicated and/or the desired product.
  • the present invention provides antimicrobial cationic colorants with high potency and good hydrolytic stability under light, heat, and pH conditions.
  • anthraquinone structures which have excellent light and heat stability, are chemically connected to biocidal QAS with different hydrocarbon chain lengths.
  • QAS with the chain length of about C 2 to about C 26 preferably about C 8 to about Ci 8 (e.g., C 8 , C 9 , C 10 , C 11 , C ]2 , Ci 3 , Ci 4 , Cj 5 , Ci 6 , Ci7, C J 8 ) show good antimicrobial properties.
  • the antimicrobial compounds of the present invention comprise a functional finishing group (e.g., QAS) covalently attached to a dye moiety optionally via a linker.
  • a functional finishing group e.g., QAS
  • Suitable dyes include, without limitation, cationic dyes such as basic red 9, basic blue 9, basic blue 69, basic blue 22, basic orange 14, basic green 1, basic yellow 1, basic violet 2, basic brown 1, and other basic dyes; acid dyes such as an Acid Black dye, an Acid Blue dye, an Acid Orange dye, an Acid Red dye, an Acid Violet dye, and an Acid Yellow dye; disperse dyes such as Disperse Blue 1, Disperse Yellow 7 and Disperse Yellow 9; and combinations thereof. Direct dyes and reactive dyes are also suitable for use in the present invention.
  • the dye is an aminoanthraquinioid dye such as 1- aminoanthraquinone and 1,4-diaminoanthraquinone. See, for example, U.S. Patent Application No. 10/804,354 filed on March 18, 2004, having U.S. Patent Publication No. US2005/0011012 and incorporated herein by reference in its entirety and for all purposes.
  • Suitable functional finishing groups are also well known to those skilled in the art.
  • the functional finishing group imparts a particular non-inherent and/or enhanced physical property, i.e., a functional property, to the polymer, textile or fiber.
  • exemplary functional properties include, but are not limited to, antimicrobial, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, and anti-chemical properties, as well as a combination of two or more properties thereof.
  • the functional finishing group is a quaternary ammonium salt group that imparts antimicrobial and/or antistatic properties to the polymer, textiles and fibers.
  • the presence of a linker between the dye and the functional finishing group can be optional depending on the reactive groups that are present on the dye and the functional finishing group.
  • complementary reactive groups are present on the dye and the functional finishing group, they can be covalently attached without the need for any additional linker.
  • the reactive groups that are present on the dye and the functional finishing group are not complementary reactive groups, one of the reactive groups can be converted to a complementary reactive group, or a linker having appropriate complementary reactive groups can be used to covalently link the dye and the functional finishing group.
  • the linker comprises an optionally substituted 1- 12 carbon atom chain which is optionally interrupted with one or more heteroatoms.
  • Suitable carbon atom chains include, without limitation, an optionally substituted alkylene group, a - C(O)R group, wherein R is an optionally substituted alkylene group, and an alkylamino group.
  • the linker is stable to hydrolysis.
  • the antimicrobial colorant is a QAS-aminoanthraquinioid dye conjugate, i.e., QAS-dye, having the formula I:
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group;
  • each Y 2 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group; m is an integer from 0 to 4; and n is an integer from 1 to 4.
  • the quaternary ammonium salt group has formula Ia:
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group; each of R 2 , R 3 , and R 4 is independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted cycloalkyl, and optionally substituted cycloalkylalkyl; L is a linker selected from the group consisting of an optionally substituted alkylene, an optionally substituted heteroalkylene, an optionally substituted cycloalkylene, an optionally substituted cycloalkylalkylene, an optionally substituted arakylene, an optionally substituted arylene, an optionally substituted heteroarylene, an optionally substituted heteroaralkylene, an optionally substituted alkenylene, and an optionally substituted alknylene; and X is a counter anion.
  • L is an optionally substituted Ci -6 alkylene, an optionally substituted Ci -6 heteroalkylene or an optionally substituted C 7 .i 0 arakylene. More preferably, L is an optionally substituted Ci. 4 alkylene or an optionally substituted Ci ⁇ heteroalkylene. In a most preferred embodiment, L is an optionally substituted [0048] In another embodiment, R and R are each independently selected from an optionally substituted Cj-C 4 alkyl group, and R 4 is an optionally substituted C 4 -Ci 8 alkyl group. In a preferred embodiment, the R and R groups are methyl groups, and R 4 is an optionally substituted C 4 -Ci 8 alkyl group.
  • Suitable R 4 groups include, for example, an optionally substituted butyl, an optionally substituted pentyl, an optionally substituted hexyl, an optionally substituted heptyl, an optionally substituted octyl, an optionally substituted nonyl, an optionally substituted decyl, an optionally substituted undecyl, an optionally substituted dodecyl and an optionally substituted hexadecyl groups.
  • the R 4 group is an optionally substituted butyl, an optionally substituted octyl, an optionally substituted dodecyl or an optionally substituted hexadecyl group.
  • X is independently selected from the group consisting of F “ , Cl “ , Br ' , I " , and combinations thereof.
  • the substituent group is independently selected from the group consisting of hydrogen, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted aralkyl, an optionally substituted cycloalkyl, an optionally substituted cycloalkylalkyl, an optionally substituted sulfonate, hydroxyl, an optionally substituted alkoxyl, an optionally substituted amino, and an optionally substituted alkylamino groups.
  • m is 0.
  • the present invention provides a compound of formula Ib
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group;
  • Y 2 is -H or -N(RVL-N + (R 2 )(R 3 )(R 4 )-X " ;
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl, and an amino protecting group;
  • R 2 and R 3 are each independently selected from an optionally substituted Ci- C 4 alkyl groups
  • R 4 is an optionally substituted C 4 -C 18 alkyl group
  • R 10 is a member selected from the group consisting of hydrogen, hydroxyl, an optionally substituted alkyl, an optionally substituted alkoxy, an optionally amino, an optionally substituted aryl, and an optionally substituted thiol; r and y are each independently 0 to 4; m is 0 to 4; and X is a counter anion.
  • r is 0, 1, 2, 3 or 4.
  • y is 0, 1, 2, 3 or 4.
  • compounds of formula Ib have the following structure: wherein:
  • Y 1 is -H or -N(R')-L-N + (R 2 )(R 3 )(R 4 )-X-;
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group
  • R 2 and R 3 are each independently selected C 1 -C 4 alkyl groups
  • R 4 is an optionally substituted C 4 -Cj 8 alkyl group
  • X is a counter anion
  • r and y are 1 or 2.
  • a particularly preferred compounds of formula I have the following structures:
  • the compound of formula I has the following structure:
  • R 2 and R 3 are each independently selected an optionally substituted Ci-C 4 alkyl groups
  • R 4 is a C 4 -Cj 8 an optionally substituted alkyl group
  • L is an optionally substituted Ci-Ci 2 alkylene group optionally interrupted with a heteroatom; an optionally substituted Ci-i 2 heteroalkylene; or an optionally substituted -C(O)R 5 group, wherein R 5 is an optionally substituted C J -C J2 alkylene group
  • X is a counter anion.
  • L is an optionally substituted Q ⁇ alkylene. More preferably, L is an optionally substituted C 3 alkylene, for example, 2-hyxdroxypropylene.
  • alkylene chain of L examples include, for example, alkyl groups, alkynyl groups, halogens, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio
  • R 2 and R 3 are methyl groups.
  • R 4 is an octyl, a dodecyl or a hexadecyl group.
  • L is a -CH 2 or a -C(O)CH 2 - group.
  • X is independently selected from the group consisting of F “ , Cl “ , Br “ , I “ , and combinations thereof.
  • the compound of formula IVb has the following structure:
  • R 2 , R 3 , R 6 , and R 7 are each independently an optionally substituted Cj-C 4 alkyl group
  • R 4 and R 8 are each independently an optionally substituted C 4 -Ci 8 alkyl groups
  • L 1 and L 2 are each independently selected from an optionally substituted Ci- C] 2 alkylene group, which is optionally interrupted with a heteroatom, an optionally substituted Ci -12 heteroalkylene or an optionally substituted - C(O)R 9 group, wherein R 9 is an optionally substituted Ci-C 12 alkylene group
  • each of Xi and X 2 is an independently selected from a counter anion.
  • R 2 , R 3 , R 6 , and R 7 are an optionally substituted methyl group.
  • R 4 and R 8 are each independently selected from the group consisting of an optionally substituted butyl, an optionally substituted octyl, an optionally substituted dodecyl and an optionally substituted hexadecyl group.
  • L 1 and L 2 are each independently selected -CH 2 - or -C(O)CH 2 - groups.
  • Xi " and X 2 " are each independently selected from the group consisting of F ' , Cl “ , Br " , I " , and combinations thereof.
  • the compounds of the present invention can be made using a variety of methods known by those of skill in the art, such as for example, solid-phase, solution-phase, and combinatorial synthesis. It should be appreciated that although the following schemes and figures for producing compounds of formula I often indicate exact structures, methods of the present invention apply widely to analogous compounds of formula I as well as to other dyes known to one skilled in the art given an appropriate consideration to protection and deprotection of reactive functional groups by methods standard to the art of organic chemistry. For example, in order to prevent unwanted side reactions, hydroxyl groups sometimes need to be converted to ethers or esters during chemical reactions at other sites in the molecule. The hydroxyl protecting group is then removed to provide the free hydroxyl group.
  • amino groups and carboxylic acid groups can be derivatized to protect against unwanted side reactions.
  • Typical protecting groups, and methods for attaching and cleaving them, are described fully in, for example, T. W. Greene and P.G.M. Wuts, Protective Groups in Organic Synthesis, 3 rd edition, John Wiley & Sons, New York, 1999, and Harrison and Harrison et ah, Compendium of Synthetic Organic Methods, VoIs. 1-8 (John Wiley and Sons, 1971-1996), which are incorporated herein by reference in their entirety.
  • the presence of a linker between the dye and the functional finishing group is optional depending on the reactive groups that are present on the dye and the functional finishing group.
  • the linker compound 2 may comprise two different reactive functional groups such that one of the reactive functional group reacts preferentially with the amino group of the anthraquinone compound 1.
  • the linker compound 2 can comprise an activated acyl group, e.g., acyl halide, alkyl halide, epoxide, or anhydride, and a leaving group for a nucleophilic substitution reaction, or an electrophilic site for nucleophilic addition reactions.
  • the activated acyl group i.e., E, reacts preferentially with the amino group.
  • Suitable reaction conditions for coupling an amino group with an activated acyl group are well known to one skilled in the art and typically involve reacting the two groups at reduced temperature, e.g., 0 °C.
  • a base and/or a coupling catalyst can optionally be added to the reaction mixture to neutralize any acid that may be generated and/or to facilitate the coupling reaction, respectively.
  • An acid can also be used to facilitate the nucleophilic addition reactions.
  • the substituted aminoanthraquinone 3, such as a disubstituted aminoanthroquinone can optionally be purified prior to reacting with a tri-substituted amine compound 4 to produce a quaternary ammonium salt substituted anthraquinone 5.
  • this second coupling reaction typically involves a nucleophilic substitution reaction where the amino group of the tri-substituted amine compound 4 displaces the leaving group X on the substituted aminoanthraquinone 3.
  • Suitable reaction conditions for a nucleophilic substitution reaction are known to one skilled in the art and often involve elevated reaction temperatures, i.e., >25°C and preferably >50°C.
  • the first step of the synthesis involves, for example, alkylation of an amino group(s) on the anthraquinone scaffold with a chlorinated epoxide.
  • the second step involves nucleophilic substitution with a tri-substituted amine compound to produce a quaternary ammonium salt substituted anthraquinone of the present invention.
  • the present invention also provides methods for preparing a colorant, comprising:
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group;
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group;
  • E is an electrophic group or a carbon capable of reacting with an amino group to form a nitrogen-carbon bond;
  • L is a bond or a linker selected from the group consisting of alkylene, heteroalkylene, cycloalkylene, cycloalkylalkyllene, arakylene, arylene, heteroarylene, heteroaralkylene, alkenylene, substituted alkylene and alknylene;
  • X is a halide;
  • m is an integer from 0 to 4; and
  • n is an integer from 1 to 4.
  • the present invention provides an antimicrobial colorant, comprising: contacting a compound of formula III:
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group; each of R 2 , R 3 , and R 4 is independently selected from the group consisting of hydrogen, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted aralkyl, an optionally substituted cycloalkyl, and cycloalkylalkyl; L is a bond or a linker selected from the group consisting of an optionally substituted alkylene, an optionally substituted heteroalkylene, an optionally substituted cycloalkylene, an optionally substituted cycloalkylalkylene, an optionally substituted arakylene, an optionally substituted arylene, an optionally substituted heteroarylene, an optionally substituted heteroaralkylene, an optionally substituted alkenylene, and an optionally substituted alknylene; and X is a counter anion.
  • the present invention provides intermediate compounds of formula III:
  • each Y 1 which may be the same or different, is independently selected from a quaternary ammonium salt group and a substituent group;
  • R 1 is a member selected from the group consisting of hydrogen, an optionally substituted alkyl group, and an amino protecting group
  • L is a linker selected from the group consisting of an optionally substituted alkylene, an optionally substituted heteroalkylene, an optionally substituted cycloalkylene, an optionally substituted cycloalkylalkylene, an optionally substituted arakylene, an optionally substituted arylene, an optionally substituted heteroarylene, an optionally substituted heteroaralkylene, an optionally substituted alkenylene, and an optionally substituted alknylene;
  • X is a halide
  • m is an integer from 0 to 4
  • n is an integer from 1 to 4.
  • Quaternary ammonium salts are antimicrobial compounds. QAS inactivate microorganisms by disturbing their cytoplasmic membrane and have been widely used as surface disinfectants and antimicrobial finishing agents in textiles. See, for example, Kim et al, Textile Res. J; 70:728 (2000); Kim et al, Textile Res. J; 71 :318 (2001); and Latlief et al., J. Pediatrics; 39:730 (1951). Meanwhile, anthraquinioid structures are excellent chromophores and have been widely used as dyes. Therefore, by incorporating both QAS and anthraquinone structures, compounds of formula I can be used simultaneously as dyes and functional finishing groups.
  • the polymers, fibers and textiles treated with a compound of formula I have microbiocidal activity against a broad spectrum of pathogenic microorganisms.
  • such polymers, textiles and fibers have microbiocidal activity against representative gram-positive (e.g., Staphylococcus aureus) and gram-negative bacteria (e.g., Escherichia col ⁇ ).
  • finished textiles prepared according to the methods and compositions set forth herein
  • those of skill in the art will readily appreciate that such finished textiles can advantageously be used in the preparation of the following articles/garments: surgeon's gowns, caps, masks, surgical covers, patient drapes, carpeting, bedding materials, underwear, socks, uniforms, and the like.
  • the finished textiles of the present invention can advantageously be used for a variety of other purposes, such as in hotel-use towels, bedding materials, hygienic products, clothing to protect against pesticides and other toxic chemicals, and the like.
  • the polymers of the present invention can be used as microbiocidal protective clothing for personnel in the medical field as well as in related healthcare and hygiene areas.
  • the functional properties of the dyes of the present invention can be imparted to carpeting materials to create odor-free and germ-free carpets.
  • all germ-free environments such as those required in biotechnology and in the pharmaceutical industry, can benefit from the use of the microbicidal polymers of the present invention to prevent any contamination from air, liquid, and/or solid media.
  • the treated polymers, textiles and fibers of the present invention are effective against a wide range of microorganisms including, but not limited to, bacteria, protozoa, fungi, viruses and algae.
  • the treated polymers described herein can be employed in a variety of disinfecting applications, such as water purification. They will be of importance in controlling microbiological contamination or growth of undesirable organisms in the medical and food industries.
  • they can be used as preservatives and preventatives against microbiological contamination in paints, coatings, and on surfaces.
  • Polymers suitable for use in the present invention include, but are not limited to, textiles.
  • Suitable textiles include, without limitation, fibers from plants, polymers from animals, natural organic polymers, synthetic organic polymers, inorganic substances, and combinations thereof.
  • the textile is selected from the group consisting of fibers from plants such as cellulose, cotton, linen, hemp, jute, wood pulp, paper, and ramie; polymers derived from animals such as wool, mohair, vicuna, and silk; manufactured fibers that are based on natural organic polymers such as rayon, lyocell, acetate, triacetate, and azlon; synthetic organic polymers such as nylon, polyester, a polyester/cellulose blend, acrylic, aramid, olefin, spandex, vinyon, vinyl, graphite, an aromatic polyamide; inorganic substances such as glass, a metallic material, and a ceramic material; and combinations thereof.
  • plants such as cellulose, cotton, linen, hemp, jute, wood pulp, paper, and ramie
  • polymers derived from animals such as wool, mohair, vicuna, and silk
  • manufactured fibers that are based on natural organic polymers such as rayon, lyocell, acetate, triacetate, and azl
  • Various textiles are preferred to practice the invention. These include, but are not limited to, a fiber, a yarn, or a natural or synthetic fabric.
  • Various fabrics include, but are not limited to, a nylon fabric, a polyester fabric, an acrylic fabric, NOMEX ® , KEVLAR ® , a triacetate fabric, an acetate fabric, a cotton fabric, a wool fabric, and a fabric that is made from a combination of two or more materials thereof.
  • NOMEX ® is made of an aromatic polyamide material and is available from DuPont (Wilmington, Delaware). NOMEX ® is used in fire fighting equipment.
  • acrylic fiber refers to any manmade fiber derived from acrylic resins comprising a minimum of 85% acrylonitrile.
  • Acrylic fiber is a manufactured fiber in which the fiber forming substance is any long-chain synthetic polymer comprising at least 85% by weight of acrylonitrile units (-CH 2 -CH[CN]-) X .
  • Suitable acrylic fibers for use in the present invention include, but are not limited to, Orion ® , Micro Supreme ® , CresloftTM, Creslan ® Plus, BioFreshTM, WeatherBlocTM (commercially available from Sterling Fibers, Inc.), DralonTM (commercially available from Bayer Inc.), Acrilan ® , Bounce-Back ® , Duraspun ® , Pil-Trol ® , Sayelle ® , Sno-BriteTM, The Smart Yarns ® , Wear-Dated ® , Wintuk ® (commercially available from Solutia Inc.), Acrilin ® acrylic, Dolan ® , Dralon ® , Vinyon N ® , Dynel ® , Verel ® , and SEF modacrylic ® . Those of skill in the art will know of other manufactures and trade names of acrylic fibers suitable for use in the present invention.
  • Additional polymers suitable for use in the present invention include, but are not limited to, plastics, rubber, paint, a surface coating, an adhesive, and a combination of two or more thereof.
  • Suitable plastics include, without limitation, polyethylene, polypropylene, polystyrene, polyvinylchloride, polyamideimide, polyethersulfone, polyarylsulfone, polyetherimide, polyarylate, polysulfone, polycarbonate, polyetherketone, polyetheretherketone, polytetrafluoroethylene, nylon-6,6, nylon-6,12, nylon- 11, nylon- 12, and acetal resin plastic materials, as well as combinations thereof.
  • the present invention also provides a polymer that is coated with the functionalized finishing dyes described above.
  • the present invention provides a polymer composition comprising:
  • a polymer wherein the polymer is a member selected from the group consisting of a textile, a plastic, rubber, paint, a surface coating, an adhesive, and a combination thereof;
  • a polymer to be treated is immersed in a treating solution, typically an aqueous solution.
  • the treating solution comprises a functional finishing dye of the present invention.
  • the polymer is immersed in the treating solution for a period of time and under conditions appropriate to achieve a sufficient amount of polymer coating to produce a desired or favorable functional finishing dye-coated polymer, i.e., dye-treated polymer.
  • the treated polymer is removed from the treating solution and dried.
  • the present invention provides a method for simultaneously dyeing and finishing a polymer, the method comprising: immersing the polymer in an aqueous treating solution which comprises a compound having a compound of formula I.
  • the method further comprises removing excess aqueous treating solution from the polymer.
  • the excess aqueous treating solution can be removed with or without washing the polymer.
  • the method further comprises drying the article after removing excess aqueous treating solution to produce a dried polymer.
  • the aqueous treating solution further comprises a wetting agent.
  • wetting agent refers to a substance that increases the rate at which a liquid spreads across the polymer surface, i.e., it renders the polymer surface nonrepellent to a liquid.
  • suitable wetting agents include, but are not limited to, Triton X-100 (Sigma Chemical Co., St. Louis, Mo.), SEQUA WET ® (Sequa Chemical Inc., Chester, S. C), and AMWET ® (American Emulsions Co., Dalton, Ga.).
  • Other wetting agents suitable for use in the present invention will be known to and used by those of skill in the art.
  • additives can also be present in the aqueous treating solution to impart additional characteristics to the polymer.
  • additives include, but are not limited to, antistatic, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, anti-chemical, and other antimicrobial agents, as well as a combination of two or more agents thereof.
  • agents known to and used by those of skill in the art are also suitable additives.
  • softeners which can be added to the aqueous treating solution include, but are not limited to, MYKON ® and SEQUASOFT ® , both of which are commercially available from Sequa Chemical Inc. (Chester, S.
  • water-repellent agents which can be added to the aqueous treating solution include, but are not limited to, SEQU APEL ® (Sequal Chemical Inc., Chester, S.C.), SCOTCHGARD (3M, St. Paul, Minn.), and other water-repellent finishing solutions known to and used by those of skill in the art.
  • the concentration of the various components of the treating solution can be varied widely depending on the particular components employed and the results desired.
  • the functional finishing dye is present at a concentration of at least about 0.5% wt/vol. (g/mL). More typically, the functional finishing dye is present at a concentration ranging from about 0.1% wt/vol. to about 10% wt/vol., preferably at a concentration ranging from about 0.5% to about 5%, and more preferably at a concentration ranging from about 0.5% to about 2%. It will be readily apparent to those of skill in the art that higher functional finishing dye concentrations (e.g., 50% or more) can be employed, but such higher concentrations are not required to impart functionality to the polymer.
  • the wetting agent is typically present at a concentration ranging from about 0.1% to about 3%, preferably at a concentration ranging from about 0.2% to about 1%.
  • the pH of the treating solution will typically range from apH of about 2 to about 6 and, preferably, from a pH of about 2.5 to about 4.5. In a particularly preferred embodiment, the pH of the treating solution is about 3.
  • the polymer is preferably a textile.
  • the textile can be roving, yarn, or fabric regardless of whether spun, knit, or woven, or can be non- woven sheets or webs.
  • the textile can be made of cellulosic fibers, polyester fibers, or a blend of these.
  • other polymer materials having reactive functional groups e.g., -OH groups
  • Such polymer materials include, but are not limited to, polyvinyl alcohol (PVA), starches, and proteins.
  • PVA polyvinyl alcohol
  • ordinary textile equipment and methods suitable for batchwise or continuous passage of roving, yarns, or fabrics through an aqueous solution can be used, at any speed permitting thorough and uniform wetting of the textile material.
  • the excess treating solution can be removed by ordinary mechanical methods such as by passing the treated polymer between squeeze rolls, by centrifugation, by draining, or by padding. In a preferred embodiment, the excess treating solution is removed by padding.
  • the treated polymer is then typically dried at a temperature ranging from about 5O 0 C to about 9O 0 C, and more preferably at a temperature ranging from about 75°C to about 85 0 C for a period of time ranging from about 3 to about 8 minutes, preferably for about 5 minutes. Drying of treated polymer can be carried out using any ordinary means such as oven drying, line drying, or tumble drying in a mechanical clothes dryer.
  • FT-IR spectra were taken on a Nicolet 6700 spectrometer (Thermo, USA) using KBr pellets.
  • 1 H-NMR, 13 C-NMR and COSY NMR spectra were recorded on a Bruker DRX 500 spectrometer (Bruker, USA).
  • Electronic absorption spectra were recorded on a HITACHI U-2000 spectrophotometer (Hitachi, Japan) with a concentration of 100 ppm in distilled water solution.
  • M-16 was prepared by the same procedures. Yield: 70%.
  • MIC minimum inhibitory concentration
  • coli, K- 12, Gram-negative were placed into 9 mL aqueous solutions containing different concentrations of the agents for a contact time of 24 hours. After the contact, a lOO ⁇ L aliquot of the resultant solution was serially diluted by sterilized distilled water to 10 1 , 10 2 , 10 3 , 10 4 and 10 5 . lOO ⁇ L of the last four dilutions were placed onto a nutrient agar plate and incubated at 37°C for 24 hours. The same procedure was applied to a distilled water solution without the antimicrobial agents as a control. In this paper, the reported MIC of the antimicrobial colorants is the minimum concentrations that can eliminate more than 4 log reductions of bacteria (1 log reduction is 90%, 2 log reduction is 99%, and so forth).
  • FT-IR spectra of the mono-substituted dyes are shown in FIG. 2.
  • the UV-vis spectra of the synthesized QAS were measured to identify the absorbance-structure relationship and are revealed in FIG. 5.
  • the di-substituted anthraquinone dyes show greater bathochromicity compared with the mono-substituted series as a result of the increasing of p- ⁇ conjugation between the aromatic ring and amino groups.
  • the additional auxochromic groups such as -NH, -OH and Cl in the di-substituted series further enhance this effect.
  • the mono-substituted QAS show the same maximum absorption wavelength (X m2x ) at 503 nm, while the di-substituted series present a bathochromic shift from 628 run to 631.5 nm.
  • This phenomenon can be interpreted by two factors: Steric hindrance and possible intramolecular hydrogen bonding.
  • the longer alkane chains in the di-substituted QAS render relatively greater steric hindrance effect, which induces a red shift.
  • Possible intramolecular hydrogen bonding within the dye molecules may also leads to bathochromic shift by holding the groups in a planar configuration (Ma, M., Sun, Y. et al. , Dyes and Pigments, 58(1):27 (2003)).
  • the colorants Di-12 and M-12 are compared with several traditional QAS as disinfectants: Cetyltrimethyl ammonium bromide (CTAB), N-cetylpyridinium chloride (CPC) and Benzyldimethyl-hexadecylammonium chloride (Benzalkonium chloride). As shown in Table 6, Di-12 and M-12 are both more efficient in biocidal activity than the other three bactericides.
  • CTC N-cetylpyridinium chloride
  • Benzyldimethyl-hexadecylammonium chloride Benzalkonium chloride
  • E. coli concentration 10 -10 CFU/ml; M-12 is 14 ppm, which is equivalent to Di-12
  • the stability of the antimicrobial colorants is of great importance because they are mostly applied in aqueous solutions as biocides or dyes. All stability tests were conducted at a concentration of 100 ppm. UV-vis absorbance of the colorant solutions was observed to examine their stability under different conditions. The UV-vis spectra before and after light exposure showed no appreciable difference, indicating excellent stability of the colorants under visible light. Compared with triphenylmethane dyes that could degrade in half an hour under unfiltered daylight (Alderman, D. J., J Fish Dis., 8:289 (1985); Allen, N.S., Dyes and Pigments, 1(1):49 (1980)), this colorant showed outstanding stability against daylight.
  • these colorants could be used under either acidic or basic conditions, particularly in coloration of acrylics, nylon and wool.
  • acidic dye bath is preferred for dyeing wool fabrics.
  • the stability of the colorants in low or high pH solution is more important for textile applications.
  • the colorants prepared previously exhibited very disappointing hydrolytic stability, particularly under alkaline conditions (Ma, M. and Sun, G., Dyes and Pigments, 63(1):39 (2004)).
  • the low stability of those colorants was caused by hydrolysis of an amide linkage between QAS and aminoanthraquinone.
  • the amide bond is replaced by alkyl amino structures that are resistant to both acidic and alkaline hydrolysis.
  • the colorant solutions were adjusted to pH 4 and pH 10 by using pH buffers at the concentration of 100 ppm for 24 hours. UV -vis spectra of the solutions were compared with the solution prepared at neutral. No any dramatic shift of both wavelengths and absorbance was observed, indicating that the colorants were stable under pH conditions. The results strongly supported the expectation of the new structures.

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Abstract

L'invention concerne des sels d'ammonium quaternaire incorporés dans des colorants anthraquinone via une liaison stable. La structure des colorants antimicrobiens est caractérisée par infrarouge à transformée de Fourier (FTIR), résonance magnétique nucléaire (RMN) et spectroscopie UV/vis. Les colorants présentent une excellente capacité antimicrobienne contre les bactéries à gram négatif et à gram positif en solution aqueuse, comme l'indique la concentration inhibitrice minimale (CIM) très basse. Les colorants présentent une excellente stabilité dans l'eau à la lumière, le chauffage continu, ainsi que les conditions acides et alcalines.
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