Antimicrobial Coating Composition

Abstract

Described herein are quaternary ammonium polymers with broad-spectrum antimicrobial properties that produce fast-acting, long-lasting, non-toxic, non-allergenic, colorless, transparent, and durable surface coatings that are resistant to water and common solvents. The surface coatings are easy and cost-effective to produce from readily available materials using versatile synthesis, allowing for a wide range of chemical variations. Such coatings are easily applied to a wide range of surfaces and materials without leaching of materials from the coating.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 164,081, filed March 22, 2021, which is incorporated by reference in its entirety.

[0002] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate to broad-spectrum antimicrobial coating compositions and methods of using same. More specifically, embodiments of the present disclosure relate to quaternary ammonium polymers having broad-spectrum antibacterial and antiviral properties. [Background technology]

[0003] Infectious diseases, including influenza, kill millions of people and make hundreds of millions sick each year worldwide. In 2020, the world experienced the global COVID-19 pandemic caused by a highly contagious new coronavirus, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2).

[0004] SARS-CoV-2 coronavirus and other viruses before it have been shown to be transmitted from person to person as airborne droplets and also by contact with virus-contaminated surfaces. A 2020 study conducted at two major urban hospitals in the United States 1 concluded that when commonly touched surfaces (e.g., keyboards, countertops, handrails, chairs) were coated with disinfectants, healthcare-associated infections were reduced by 36%. Indeed, surface disinfection has been adopted as a widespread health safety practice during the COVID-19 pandemic, but its effectiveness is limited because antiviral coatings become ineffective after a short period of time, necessitating frequent reapplication, which is costly and labor-intensive.

[0005] Over the years, numerous antimicrobial polymers have been developed to provide more effective antibacterial / antiviral surface coatings. Jarach et al. (2020) 2 A recent review by highlights some of the different polymeric approaches to this problem. These polymers include nanoparticles with bound or adsorbed drugs, nanoparticles with embedded antiviral metals, naturally occurring polymers such as chitosan, silica particles with adsorbed quaternary ammonium salts and quaternary polyethyleneimine (PEI).

[0006] An optimal antimicrobial surface coating will have the following properties: (i) broad-spectrum antimicrobial activity with a low Minimum Inhibitory Concentration (MIC); (ii) fast acting; (iii) long-lasting; (iv) non-toxic and non-allergenic; (v) no materials will leach from the coating; (vi) acceptable color, transparency, and appearance for a surface coating; (vii) easy application to a wide range of surfaces and materials; (viii) producing a durable surface coating that is resistant to water, alcohol, and common solvents; and (ix) easy and cost-effective to produce.

[0007] As recognized by the inventors of the present application, prior art antimicrobial surface coatings lack many of the above characteristics. Thus, a need exists for improved antimicrobial surface coating compositions. Summary of the Invention

[0008] Embodiments of the present technology provide antimicrobial surface coatings that have three or more of the following properties: (i) broad spectrum antimicrobial activity with low minimum inhibitory concentration (MIC), (ii) fast acting, (iii) persistent, (iv) non-toxic and non-allergenic, (v) no materials leaching from the coating, (vi) acceptable color, transparency, and appearance for a surface coating, (vii) easy application to a wide range of surfaces and materials, (viii) producing a durable surface coating that is resistant to water, alcohol, and common solvents, and (ix) easy and cost-effective to produce. In some embodiments, the antimicrobial surface coatings of the present technology have four or more of these properties. In some embodiments, the antimicrobial surface coatings of the present technology have five or more of these properties. In some embodiments, the antimicrobial surface coatings of the present technology have six or more of these properties. In some embodiments, the antimicrobial surface coatings of the present technology have seven or more of these properties. In some embodiments, the antimicrobial surface coatings of the present technology have eight or more of these properties. In some embodiments, the antimicrobial surface coatings of the present technology have nine or more of these properties. In some embodiments, the antimicrobial surface coating of the present technology has all of these properties.

[0009] In one aspect, provided herein is an antimicrobial composition comprising a polymer, wherein the polymer comprises the reaction product of a polyethyleneimine oligomer, a multifunctional crosslinking agent, an alkylating agent, an optional monoisocyanate, and an optional catalyst, wherein the polyethyleneimine oligomer comprises an optionally substituted hydroxyethylene functional group that reacts with one or both of the optional monoisocyanate or the multifunctional crosslinking agent, and wherein nitrogen atoms present in the polyethyleneimine oligomer are at least partially quaternized by the alkylating agent.

[0010] In some embodiments, the hydroxyethylene functional group is C6-C 10C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and carboxy. In some embodiments, the polyethyleneimine oligomer comprises the reaction product of a polyethyleneimine and a monoepoxide, the monoepoxide being selected from C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10aryl; and C1-C6 alkyl optionally substituted with a substituent selected from carboxy. In some embodiments, the monoepoxide is a C1-C6 alkyl epoxide. In some embodiments, the C1-C6 alkyl epoxide is selected from the group consisting of propyl epoxide, butyl epoxide, and hexyl epoxide. In some embodiments, the polyethyleneimine has a molecular weight of about 600 to about 270,000 daltons, preferably a molecular weight of about 10,000 to about 200,000 daltons, more preferably a molecular weight of about 25,000 to about 120,000 daltons. In some embodiments, the polyethyleneimine is branched. In some embodiments, the polyethyleneimine is multi-branched. In some embodiments, the polyethyleneimine has a ratio of primary to secondary to tertiary amines of about 1:2:1 to about 1:1:1. In some embodiments, the polyethyleneimine has a ratio of primary to secondary to tertiary amines of about 1:1:0.7. In some embodiments, the polyfunctional crosslinker is a polyisocyanate. In some embodiments, the polyisocyanate has an average isocyanate functionality of 2 to 5, preferably an average isocyanate functionality of 3 or 4.In some embodiments, the polyisocyanate is prepared from a diisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI). In some embodiments, the polyisocyanate is selected from the group consisting of DESMODUR® N-3300, DESMODUR® N-100, DESMODUR® Z4470SN, WANNATE® T-series polyisocyanates, and LUPRANATE® M-series polyisocyanates. In some embodiments, at least 75% of the nitrogen atoms of the polyethyleneimine oligomer are quaternized with an alkylating agent. In some embodiments, the alkylating agent comprises one or more R2-LG, where each R2 is independently hydroxy, C1-C6 alkoxy, carboxy, C6-C. 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy, and each LG is a leaving group. In some embodiments, the alkylating agent is a benzyl halide or a hexyl halide. In some embodiments, the monoisocyanate comprises one or more R3-NCO, where each R3 is independently selected from: (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, and (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl). In some embodiments, the monoisocyanate comprises octyl isocyanate, octadecyl isocyanate, or a combination thereof. In some embodiments, at least 20%, preferably at least 45%, and even more preferably at least 75% of the optionally substituted hydroxyethylene functional groups react with the monoisocyanate, and no more than 25%, preferably no more than 10% of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate. In some embodiments, the polymer comprises the reaction product of a polyethyleneimine oligomer, a multifunctional crosslinker, an alkylating agent, and optionally a catalyst, in the absence of a monoisocyanate. In some embodiments, the optional catalyst comprises dibutyltin dilaurate or bismuth carboxylate.

[0011] In another aspect, the present invention relates to compound (IV): [ka] An antimicrobial composition comprising: Each A is independently [ka] and [ka] or a copolymer of any two or more thereof, wherein the bond of each A forms a carbamate bond; each Y is independently H or -C(O)-NHR; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000; Each R1 is independently hydrogen; C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and C1-C6 alkyl optionally substituted with substituents selected from carboxy; Each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy; Each R3 is independently: (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from10 Aryl, and (3) [ka] wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3; Each R4 is independently a C1-C1 optionally substituted with phenyl. 10 an alkylene or a 3- to 8-membered cycloalkyl ring; each X - is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphoric acid, phosphonic acid, carbonate, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and organic substituted derivatives thereof.

[0012] In some embodiments of compound (IV), at least 75% but not all of R are independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl; and halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl). In some embodiments of compound (IV), each R3 is independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 In some embodiments of compound (IV), R3 is selected from octyl, octadecyl, or a combination thereof. In some embodiments of compound (IV), each R3 is independently selected from halogen, C1-C6 alkyl, and -SiR a (OR b)( OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 In some embodiments of compound (IV), R3 is selected from: [ka] It is.

[0013] In another aspect, the present disclosure provides compound (V): [ka] An antimicrobial composition comprising: Each A is independently [ka] or a copolymer of any two or more thereof, wherein the bond of each A forms a carbamate bond; each Y is independently H or -C(O)-NHR; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000; Each R1 is independently hydrogen; C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and C1-C6 alkyl optionally substituted with substituents selected from carboxy; Each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy; Each R3 is independently: (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 Aryl, and (3) [ka] wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3; Each R4 is independently a C1-C1 optionally substituted with phenyl. 10 an alkylene or a 3- to 8-membered cycloalkyl ring; each X - is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphoric acid, phosphonic acid, carbonate, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and organic substituted derivatives thereof.

[0014] In some embodiments of compound (V), at least 75% but not all of R are independently selected from halogen, -SiR a (OR b )(ORc), and C6-C 10C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl; and halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl). In some embodiments of compound (V), each R3 is independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 In some embodiments of compound (V), R3 is selected from octyl, octadecyl, or a combination thereof. In some embodiments of compound (V), each R3 is independently selected from halogen, C1-C6 alkyl, and -SiR a (OR b)( OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 In some embodiments of compound (V), R3 is selected from: [ka] It is.

[0015] In some embodiments of Compound (IV) or Compound (V), each R is independently C-C alkyl. In some embodiments of Compound (IV) or Compound (V), each R is independently hydroxy, C-C alkoxy, carboxy, C-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10In some embodiments of compound (IV) or compound (V), R is selected from C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy. In some embodiments of compound (IV) or compound (V), each R is independently selected from methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of compound (IV) or compound (V), R is selected from C1-C6 alkyl optionally substituted with phenyl. 10 In some embodiments of compound (IV) or compound (V), R is C-C 10 In some embodiments of compound (IV) or compound (V), R4 is a 3- to 8-membered cycloalkyl ring.

[0016] In another aspect, the present disclosure provides compound (VI), compound (VII), or compound (VIII): [ka] or a combination of any two or more thereof, or a copolymer of any two or more thereof, wherein each Y is independently H or -C(O)-NHR; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000; Each R1 is independently hydrogen; C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and C1-C6 alkyl optionally substituted with substituents selected from carboxy; Each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy; Each R3 is independently: (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, and (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3; each X - is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphoric acid, phosphonic acid, carbonate, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and organic substituted derivatives thereof.

[0017] In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R is independently C-C alkyl. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R is independently hydroxy, C-C alkoxy, carboxy, C-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), at least 75% but not all of the R3 are independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl; and halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl). In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R3 is independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), R3 is selected from octyl, octadecyl, or a combination thereof. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R3 is independently selected from halogen, C1-C6 alkyl, and -SiR a (OR b)( OR cC6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl.

[0018] In another aspect, the antimicrobial surface coating of the present technology comprises a mono-urethane substituted alkyl quaternary polyethyleneimine (PEI)-A (MUA-Q-PEI-A) formed by reacting at least one monoisocyanate with a hydroxyl alkyl quaternary PEI (PEI-A, HA-Q-PEI). In some embodiments, 20%-100% of the hydroxyl groups of the HA-Q-PEI are converted to urethane groups by reacting with at least one monoisocyanate. In some embodiments, 50%-95% of the hydroxyl groups of the HA-Q-PEI are converted to urethane groups by reacting with at least one monoisocyanate. In some embodiments, the monoisocyanate is selected from an alkyl-, alkylaryl-, arylalkyl-, or aryl-monoisocyanate. In some embodiments, the monoisocyanate is a blend of octyl isocyanate and octadecyl isocyanate. In some embodiments, the molar ratio of octyl isocyanate to octadecyl isocyanate is 1 / 9 to 5 / 5. In some embodiments, the molar ratio of octyl isocyanate to octadecyl isocyanate is 2 / 8 to 4 / 6. In some embodiments, the monoisocyanate is a fluoro or organosilicone substituted monoisocyanate. In some embodiments, the polyethyleneimine has an average molecular weight of 600 to 1,000,000. In some embodiments, the polyethyleneimine has an average molecular weight of 25,000 to 270,000. In some embodiments, the polyethyleneimine is linear, branched, hyperbranched polyethyleneimine, or a blend thereof. In some embodiments, the MUA-Q-PEI-A has a counterion selected from halide, sulfate, sulfonate, phosphate, carbonate, and borate. In some embodiments, the counterion is chloride, bromide, iodide, or sulfate.In some embodiments, the reactant HA-Q-PEI is formed by reacting polyethyleneimine with a monoepoxide and quaternizing with a quaternizing agent. In some embodiments, the monoepoxide is an alkyl epoxide. In some embodiments, the alkyl epoxide is selected from propyl, butyl, or hexyl epoxide. In some embodiments, the alkyl epoxide is propyl epoxide. In some embodiments, the quaternizing agent is an alkyl halide or an aryl alkyl halide. In some embodiments, the quaternizing agent is a benzyl halide or a hexyl halide.

[0019] In another aspect, the antimicrobial surface coating of the present technology comprises a crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B) formed by crosslinking the above-mentioned HA-Q-PEI with at least one polyisocyanate. In some embodiments, the polyisocyanate has an average isocyanate functionality of 2 to 5. In some embodiments, the polyisocyanate has an average isocyanate functionality of 3 to 4. In some embodiments, the polyisocyanate is prepared from a diisocyanate selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexyl isocyanate) (H12MDI), meta-tetramethyl xylene diisocyanate (TMXDI), or trimethylhexamethylene diisocyanate (TMDI). In some embodiments, the polyisocyanate is an isocyanate end-capped oligomer prepared from a multifunctional isocyanate and a polyol. In some embodiments, the polyol is selected from a polyester polyol, a polyether polyol, a polysiloxane polyol, a polycaprolactone polyol, or a polybutadiene polyol.

[0020] In another aspect, the antimicrobial surface coating of the present technology comprises a crosslinked polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C), where PUA-Q-PEI-C is formed by reacting at least one polyisocyanate with HA-Q-PEI. In some embodiments, the polyisocyanate has an average isocyanate functionality of 2 to 5. In some embodiments, the polyisocyanate has an average isocyanate functionality of 3 to 4. In some embodiments, the polyisocyanate is prepared from a diisocyanate selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), meta-tetramethyl xylene diisocyanate (TMXDI), or trimethylhexamethylene diisocyanate (TMDI). In some embodiments, the polyisocyanate is an isocyanate end-capped oligomer prepared from a multifunctional isocyanate and a polyol. In some embodiments, the polyol is selected from a polyester polyol, a polyether polyol, a polysiloxane polyol, a polycaprolactone polyol, or a polybutadiene polyol.

[0021] In another aspect, the technology provides an antimicrobial coating, coating fluid, or spray fluid comprising any of the above antimicrobial compositions. In some embodiments, the HA-Q-PEI, MUA-Q-PEI-A, PUA-Q-PEI-B, or PUA-Q-PEI is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. In some embodiments, the coating fluid or spray fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. In some embodiments, the device, equipment, apparatus, or accessory is selected from a filter, air purifier, mask, or other personal protection device (PPD), respirator, and the like. In some embodiments, the device, equipment, apparatus, or accessory is selected from a keyboard, keypad, mouse, remote control, touch screen, phone, or display, or any device integrating any of the aforementioned components.

[0022] In another aspect, the present technology provides a personal care adjuvant comprising any of the above-mentioned coatings, coating fluids, or spray fluids. In some embodiments, the coating fluid or spray fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible.

[0023] In another aspect, provided herein is a method of disinfecting a surface, comprising applying a composition described herein. In another aspect, provided herein is a method of reducing antimicrobial growth on a surface, comprising applying a composition described herein. In another aspect, provided herein is a method of preventing antimicrobial growth on a surface, comprising applying a composition described herein. In some embodiments, the method further comprises forming a coating solution containing the composition. In some embodiments, the method further comprises directing the coating solution to the surface and providing a coating on the surface through application of the coating solution to the surface.

[0024] Other embodiments are also described and enumerated herein.

[0025] For illustrative purposes, specific embodiments of the technology are shown in the figures described below, however, it should be understood that the technology is not limited to the precise arrangements, dimensions, and apparatus shown. [Brief description of the drawings]

[0026] [Figure 1] 1 shows the structures of the starting polyethyleneimine (PEI) and the resulting hydroxyalkyl quaternary PEI (HA-Q-PEI) polymer after reaction with an alkyl epoxide followed by quaternization with an alkylating agent. [Diagram 2] 1 shows the structures of the starting HA-Q-PEI and the resulting mono-urethane substituted alkyl quaternary PEI-A (MUA-Q-PEI-A) after reaction with one or a blend of hydrophobic monoisocyanates. [Diagram 3] 1 shows the structure of mono-urethane substituted alkyl quaternary PEI-A100 (MUA-Q-PEI-A100), in which 100% of the free hydroxyl groups have reacted. [Figure 4] One of the structures of crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B) is provided. [Diagram 5] One of the structures of the crosslinked polymer network of polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C) is provided. [Figure 6A-6B] RT-qPCR testing is shown, with FIG. 6A showing the test plate setup and FIG. 6B illustrating the QuantStudio3 PCR procedure. [Figure 7] 1 shows a test plate used to evaluate the antiviral properties of composition (III). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The subject invention will now be described with reference to the drawings, in which like reference numerals are used to refer to like elements throughout. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present technology. However, it may be apparent that the present technology may be practiced without these specific details. In other instances, well-known structures and devices are shown in block diagram form to facilitate describing the present technology. It should be understood that certain aspects, modes, embodiments, variations, and features of the present technology are described below at various levels of detail in order to provide a substantial understanding of the present technology.

[0028] definition For convenience, the meanings of some terms and phrases used in the specification, examples, and appended claims are provided below. Unless otherwise stated or implied from the context, the following terms and phrases include the meanings provided below. The definitions are provided to help explain certain embodiments and are not intended to limit the claimed subject matter, as the scope of the technology is limited only by the claims. Unless otherwise expressly stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the technology belongs. In the event of an apparent discrepancy between the use of a term in the art and its definition provided herein, the definition provided herein shall prevail.

[0029] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly indicates otherwise. For example, reference to "a cell" includes a combination of two or more cells, and the like.

[0030] As used herein, the term "approximately" or "about" in reference to a value or parameter is generally interpreted to include numerical values ​​that fall within 5%, 10%, 15%, or 20% in either direction of that numerical value (greater or less than), unless otherwise stated or clear from the context (except where such numerical value is less than 0% or greater than 100% of possible values). Reference to "approximately" or "about" a value or parameter includes (and describes) embodiments that are directed to that value or parameter. For example, a description that refers to "about X" includes a description of "X."

[0031] As used herein, the term "or" means "and / or." The term "and / or" as used in phrases such as "A and / or B" herein is intended to include A and B, A or B, A (alone), and B (alone). Similarly, the term "and / or" as used in phrases such as "A, B, and / or C" is intended to encompass each of the following embodiments: A, B, and C; A, B, or C; A or C; A or B; B or C; A and C; A and B; B and C; A (alone); B (alone); and C (alone).

[0032] As used herein, the term "comprising" means that other elements may be present in addition to the defined elements presented. The use of "comprising" indicates inclusion rather than limitation.

[0033] The term "consisting of" refers to compositions, methods, and their respective components described herein, excluding any element not recited in the description of the embodiment.

[0034] As used herein, the term "consisting essentially of" refers to elements required for a given embodiment. The term permits the presence of additional elements that do not materially affect the basic and novel or functional characteristics of that embodiment of the technology.

[0035] As used herein, "aryl" refers to a carbocyclic (all carbon) ring that is fully aromatized. An "aryl" group may be composed of two or more fused rings (rings that share two adjacent carbon atoms). When an aryl group is a fused ring system, the ring that is connected to the rest of the molecule is fully aromatized. The other rings in the fused ring system may or may not be fully aromatized. Examples of aryl groups include, but are not limited to, benzene, naphthalene, and azulene radicals.

[0036] As used herein, "alkyl" refers to a straight or branched chain, fully saturated (no double or triple bonds) hydrocarbon group. The alkyl groups of the compounds disclosed herein may contain 1-15 carbon atoms. The alkyl groups herein may have 1-4 carbon atoms, 1-5 carbon atoms, 1-6 carbon atoms, 1-7 carbon atoms, 1-8 carbon atoms, 1-9 carbon atoms, 1-10 carbon atoms, 1-11 carbon atoms, 1-12 carbon atoms, 1-13 carbon atoms, 1-14 carbon atoms, or 1-15 carbon atoms. As used herein, C1-C6 alkyl represents an alkyl group having 1-6 carbon atoms, C1-C4 alkyl represents an alkyl group having 1-4 carbon atoms, and C1-C3 alkyl represents an alkyl group having 1-3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0037] As used herein, "alkoxy" refers to an alkyl group, as defined above, appended to the parent molecular moiety through an oxy group -O-. As used herein, C1-C6 alkoxy represents an alkoxy group containing 1 to 6 carbon atoms, and C1-C3 alkoxy represents an alkoxy group containing 1 to 3 carbon atoms. Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, and the like.

[0038] As used herein, unless otherwise stated, "independently selected" indicates that each specified group is independently selected from the succeeding list of species.

[0039] The terms "statistically significant" or "significantly" refer to statistical significance, generally meaning a difference of two standard deviations (2SD) or greater.

[0040] The terms "reduce", "reduced", "reduction", or "inhibit" are all used herein to mean a statistically significant amount of reduction. In some embodiments, "reduce", "reduction", or "reduce" or "inhibit" typically means a reduction of at least 10% compared to a reference level (e.g., the absence of a given treatment or agent), and can include, for example, a reduction of at least about 10%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or more. As used herein, "reduce" or "inhibit" does not encompass complete inhibition or reduction compared to a reference level. "Complete inhibition" is 100% inhibition compared to a reference level. The decrease may preferably be down to a level that is accepted as being within the normal range for individuals without a given disorder.

[0041] The terms "increased," "increase," "enhance," or "activate" are all used herein to mean a statically significant amount of increase. In some embodiments, the terms "increased," "increase," "enhance," or "activate" can mean an increase of at least 10% compared to a reference level, e.g., at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90%, or up to 100%, including 100%, or any increase between 10-100% compared to a reference level, or at least about 2-fold, or at least about 3-fold, or at least about 4-fold, or at least about 5-fold, or at least about 10-fold increase compared to a reference level, or any increase between 2-fold and 10-fold or more. In the context of a marker or condition, an "increase" is a statistically significant increase in such level.

[0042] As used herein, the term "quaternary ammonium polymer antiviral composition" generally refers to a family of quaternary ammonium polymer compositions in which the tertiary nitrogen moiety is quaternized using an alkylating agent such as benzyl chloride.

[0043] As used herein, the term "polyethylenimine" generally refers to a family of polymers containing primary, secondary, and tertiary amino groups, such as PEI 70KDa (also known as average molecular weight).

[0044] As used herein, the term "monoisocyanate" generally refers to a family of monoisocyanates that are hydrophobic in nature, such as alkyl, aryl, alkylaryl, or arylalkyl monoisocyanates, preferably those having a carbon number of ≧6, more preferably ≧8. Useful examples include, but are not limited to, octadecyl isocyanate, dodecyl isocyanate, and octyl isocyanate.

[0045] As used herein, the term "polyisocyanate" generally refers to a family of polyisocyanates containing two or more isocyanate-reactive groups, such as, but not limited to, DESMODUR® N3300 and N100, which are aliphatic polyisocyanates based on HDI (hexamethylene diisocyanate) trimer (made by Covestro Deutschland AG of Leverkusen, Germany), or DESMODUR® Z4470SN, a multifunctional polyisocyanate based on IPDI (isophorone diisocyanate) (made by Covestro Deutschland AG of Leverkusen, Germany).

[0046] As used herein, the term "antimicrobial" is generally used to indicate that at least some level of pathogens are killed by a composition or coating of a portion of a surface. For example, antimicrobial can be used to indicate biocontrol effectiveness, a kill level (3 log, or 99.9%) reduction in at least one organism, or a disinfection level (5 log, or 99.999%) reduction in at least one organism, or sterilization (no detectable organisms). Pathogens, or microorganisms, can include any species of bacteria, viruses, fungi, including molds and yeasts, or spores. Thus, antimicrobial herein includes antiviral, antibacterial, and antifungal.

[0047] As used herein, the terms "residual antimicrobial," "residual self-sterilizing," and "self-decontaminating surface" are used interchangeably to refer to a surface that maintains antimicrobial effectiveness over a certain period of time under certain conditions once the surface is coated with an antimicrobial coating composition and the composition is dried on the surface as a thin film. The coated surface may maintain residual antimicrobial effectiveness indefinitely, or the coating may eventually "wear off" and lose its residual antimicrobial effectiveness. The antimicrobial coating composition may function as a contact germicide, bacteriostatic material, disinfectant, or sterilant (e.g., as a liquid antimicrobial applied to a contaminated surface), and may also have the ability to leave a residual antimicrobial coating on the surface once dried or cured that can continue to inactivate new microorganisms that come into contact with the coated surface. In various embodiments, the coating composition may not have antimicrobial properties until it dries or cures on the surface, but is still referred to as an antimicrobial coating composition due to its ability to produce a residual antimicrobial coating on the surface. The antimicrobial coating composition for use in various embodiments may provide a residual antimicrobial effectiveness to the surface, meaning that microorganisms that are later inoculated onto or otherwise come into contact with the coated surface may experience cell death, destruction, or inactivation. The residual antimicrobial effect enabled by the coatings herein is not limited by a particular mechanism of action, and no theory is provided as such. For example, the antimicrobial effect measured on the surface may be the result of intracellular mutation, inhibition of certain cellular processes, rupture of cell walls, or inactivation of undescribed organisms, such as in the case of viruses. Other antimicrobial effects may include inhibiting the reproduction of organisms or inhibiting the ability of organisms to accumulate in biofilms.

[0048] As used herein, the term "antimicrobial coating composition" refers to a chemical composition comprising at least one chemical species that is used to generate a residual antimicrobial coating on a surface after the composition is applied and then dried, allowed to dry, or cured in some manner. The term is also used for liquid compositions that can then be used as germicidal sprays (disinfectants or sanitizers) since the composition can then dry into an antimicrobial coating. The term also extends to include compositions that can be applied sequentially (e.g., above or below) or simultaneously with the application of the antimicrobial coating composition to help bond the residual antimicrobial coating to the surface, improve the durability of the overall coating, and / or provide a catalytic effect or some kind of enhancing or synergistic effect with the residual antimicrobial coating that includes an antimicrobial active agent. For the sake of simplicity herein, each of the multiple compositions used sequentially or contemporaneously to generate an overall residual antimicrobial coating on a portion of a surface will be referred to as an "antimicrobial coating composition" even if one or more of the compositions used in the coating does not have a discernible antimicrobial activity or the active agent is unclear. The antimicrobial coating composition may contain pure 100% active chemical species or may be a solution or suspension of a single chemical species in a solvent. In other aspects, the composition may contain a complex mixture of chemicals, some of which may chemically react (hydrolyze, self-condense, etc.) within the composition to produce identifiable or indistinguishable reaction products. For example, monomeric species in the antimicrobial coating composition may be partially or fully polymerized or copolymerized to produce polymers, including homopolymers and copolymers, with a distribution of molecular weights, comonomer ratios, or molecular architectures in solution prior to the coating process using the composition. In other embodiments, the chemical components within the antimicrobial coating composition may chemically react, graft, or form an interpenetrating network on the surface or interphase to which the composition is applied, such as while the composition is drying and concentrating on the surface, or while the coating composition is cured by various methods.In various embodiments, the solution containing the polymer distribution may further polymerize or harden, such as to longer chain lengths or to form a polymer network, while the solution is drying on the surface. Antimicrobial coating compositions for use in various embodiments may further include any number and combination of inert excipients, such as, for example, solvents, buffers, acids, alkalis, surfactants, emulsifiers, stabilizers, UV absorbers, thickeners, free radical initiators, fillers, pigments or colorants, catalysts, and the like.

[0049] As used herein, the term "homopolymer" has its usual meaning in organic chemistry of a molecule having repeating and identical monomer units. For simplicity, the term homopolymer herein includes each of the smaller oligomers, i.e., dimers, trimers, tetramers, dendrimers, dendrons, etc., unless otherwise indicated. For example, a homopolymer distribution herein may include dimers or more, or trimers or more, as indicated. In some cases, the homopolymer chain length distribution may be well defined and characterized, while in other cases, the distribution may not be characterizable at all and may remain unknown. The term copolymer herein includes random copolymers, block copolymers, graft copolymers, interpolymer complexes, interpenetrating networks, etc., and blends thereof.

[0050] As used herein, the term "wt %" has its usual meaning of weight percent (%) of a component in a chemical composition, based on the total weight of the composition "as made." For example, an aqueous composition containing 1 wt % amine "based on the total weight of the composition" corresponds to a composition containing 99.0 grams of water and 1.0 grams of amine. Weight % in a composition refers to the weight % of active material, unless otherwise specified. "As made" means that the written composition refers to what was added to the mixing container, and not to what may ultimately become of the mixture after a particular component reacts, such as when the component hydrolyzes or polymerizes.

[0051] Unless otherwise defined herein, scientific and technical terms used in connection with this application shall have the meanings commonly understood by one of ordinary skill in the art to which this disclosure belongs. It is to be understood that the present technology is not limited to the particular methodology, protocols, and reagents, etc. described herein, as such may vary. The terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present technology, which is defined solely by the claims. Definitions of common terms in immunology and molecular biology are provided in The Merck Manual of Diagnosis and Therapy. 3 , The Encyclopedia of Molecular Cell Biology and Molecular Medicine 4 , Molecular Biology and Biotechnology: a Comprehensive Desk Reference 5 , Immunology 6 , Janeway's Immunobiology 7 , Lewin's Genes XI 8 , Molecular Cloning: A Laboratory Manual 9 , Basic Methods in Molecular Biology 10 , Laboratory Methods in Enzymology 11 ,Current Protocols in Molecular Biology(CPMB) 12 ,Current Protocols in Protein Science(CPPS) 13 , and Current Protocols in Immunology (CPI) 14 can be seen in.

[0052] Other terms are defined herein within the description of various aspects of the technology.

[0053] Antibacterial Coating Surfaces of objects that are in direct or indirect contact with humans and animals are exposed to high microbial loads and have a demonstrable impact on the transmission of disease and infection. The antimicrobial coating of the present technology can be particularly useful because it can be applied to almost any surface and can significantly reduce the microbial load. Surfaces that can be treated with antimicrobial coatings include, but are not limited to, interior and exterior building components such as handrails, fixtures, fixture knobs, pull handles, grips, kitchens, washrooms, bathrooms, toilets, personal items, telephones, computers, door handles, counters, furniture, walls, ticket machines, parts such as faucet handles in high-touch areas (e.g., building lounges, public payment means, public transportation), and other hard-to-clean / access areas such as mechanical equipment and HVAC systems. Additionally, these coatings can be applied to medical devices and accessories, implants, and instruments, laboratory equipment, factories, water purification equipment, hospitals, schools / childcare facilities, airports, restaurants, gyms, etc.

[0054] Bacteria of particular concern include, but are not limited to, Staphylococcus aureus (Staph), Escherichia coli (E. coli), Methicillin-Resistant Staphylococcus aureus (MRSA), and Vancomycin-Resistant Enterococcus faecalis and Enterobacter aerogenes (VRE). Staph is a group of over 30 strains that cause many different types of infections, including skin infections, food and blood poisoning. Most strains of E. coli are not harmful but are part of the healthy flora in the human gut. However, some strains can cause a variety of illnesses, including pneumonia, urinary tract infections, diarrhea, and meningitis. Some strains of E. coli can cause nausea, vomiting, and fever. MRSA is a type of bacteria that causes infections in different parts of the body. It is relatively more difficult to treat than most other strains of Staph because it is resistant to antibiotics. It can cause severe skin, bloodstream, lung, or urinary tract infections. VRE is a type of bacteria called Enterococci that, as the name suggests, have developed resistance to many antibiotics, especially vancomycin. These bacteria can cause serious infections, especially in people who are already sick, weak, and / or immunocompromised. VRE can cause bloodstream infections (sepsis), urinary tract infections, pneumonia, heart infections (endocarditis), or meningitis.

[0055] Viruses of particular concern include, but are not limited to, influenza A and B viruses, respiratory syncytial virus, adenovirus, rhinovirus, and coronaviruses (229E, HKU1, NL63, OC43, and more recently, SARS-CoV-2), which have been demonstrated to have long survival times on many surfaces. For example, a recent study of an airport 15Detection of pathogen viral nucleic acid indicated viral surface contamination at multiple sites associated with high contact rates, suggesting a potential risk in standard passenger pathways at airport sites. These viruses have the potential to cause serious infections, especially in people who are already sick, vulnerable, and / or immunocompromised.

[0056] In the chemical coatings industry, a 99.9% reduction in bacteria or viruses translates to a three order of magnitude reduction in microbial risk (i.e., 3 log). However, there are several physical and chemical requirements that an antimicrobial coating must meet to be a fully effective and widely applicable antiviral / antibacterial / antifungal agent and surface coating. These properties include: 1.Highly antibacterial against a broad spectrum of viruses, bacteria, and fungi. 2. Extremely fast-acting, killing over 99.9% of viruses with less than 10 minutes of contact time and killing bacteria overnight. 3. Long-lasting, maintains at least 98% bacterial or viral killing efficiency after 100 days storage under ambient conditions or 72 hours storage at 40℃ / 85%RH humidity. 4. Non-toxic and non-allergenic based on recognized standard testing procedures. 5. The material will not leach over time or when exposed to typical liquids used in cleaning. 6. Visibly colorless and transparent as a surface coating. 7. Easy to apply to a wide range of surfaces and materials by painting, spraying, dipping, or other commonly used application methods. 8. A durable surface coating that is resistant to peeling off or visibly degrading from the surface upon contact with water, alcohol, and common solvents. 9. Easy and cost effective to produce from readily available materials. 10. They can be produced by versatile synthesis, allowing a wide range of chemical variations to fine-tune their properties (i.e., solubility, etc.) for different applications.

[0057] To the inventor's knowledge, no antimicrobial coating is yet available that meets most or all of these requirements. Many of the existing antimicrobial coatings tend to degrade over time and lose effectiveness after repeated contamination.

[0058] Conventional coating products that claim to provide antibacterial properties include PAINTGUARD / PAINTSHIELD® from Sherwin Williams Company (Cleveland, Ohio), ALESTA® AM and ALESTA® Ralguard from Axalta (Philadelphia, PA), and SILVERSAN™ from PPG Industrial Coatings (Pittsburgh, PA). However, while these products generally claim to be 99.9% effective, they require more than 5 hours after application to reach maximum efficiency. Furthermore, existing solutions tend to degrade over time, so that their activity performance falls below 90% after recontamination (i.e., repeated exposure to pathogens combined with periodic environmental exposure and / or scrubbing / washing over an extended period of time). With only 90% protection, bacteria and germs have the ability to grow and respire, eventually multiplying to the point of survival of existing pathogens on the substrate layer, thereby reducing the effectiveness of these coatings.

[0059] Antimicrobial polymers have been reported for implants containing metals such as silver. 16 However, these suffer from the fact that the embedded antimicrobial agent may leach over time and the polymer coating may lose its antimicrobial activity. Moreover, such formulations are not entirely satisfactory as they only result in a 3 log reduction that fails to completely inhibit bacterial regrowth. This lack of effectiveness may possibly be due to the fact that the silver is used in insufficient amounts and / or is unevenly dispersed throughout the composition, resulting in inconsistent and ultimately ineffective distribution of the antimicrobial particles within the composition / coating.

[0060] Park et al. (2006) 17 reported antimicrobially active polymers made by reacting polyethyleneimine with hydrophobic long-chain hydrocarbon alkylating agents followed by quaternization by methylation. These polymers have antibacterial and antiviral activity as surface coatings, but the coatings are not colorless, are not durable, and are not resistant to contact with water and other common solvents with which surfaces may come into regular contact.

[0061] Many speculate that the antiviral activity of quaternary ammonium polymers is due to interactions between the hydrophobic quaternary ammonium groups and the negatively charged membrane of the virus, causing membrane disruption that inactivates microorganisms such as viruses. Indeed, the active ingredients in many commercially available antiviral surface sprays are low molecular weight quaternary ammonium surfactant-like materials that are postulated to act by this mechanism, but do not form long-lasting, durable surface coatings.

[0062] Researchers have reported acrylic or methacrylic copolymers with quaternary ammonium functional groups that have antibacterial activity. 18、19 However, they do not produce durable water- and solvent-resistant coatings, and some exhibit some degree of toxicity.

[0063] Several researchers have reported antibacterial polyurethane polymers with quaternary ammonium functional groups. 20、21、22 However, these have several drawbacks. Some are water soluble and therefore not suitable for durable surface coatings. Others have not reported testing of the durability of the coating or the toxicity of the materials. Some are rather tedious to synthesize, requiring somewhat expensive materials and up to four synthetic steps including amine blocking and deblocking reactions.

[0064] Gao et al. (2007) 23reported the synthesis and antibacterial activity of polymers synthesized by alkylating polyethyleneimine with propyl epoxide and then quaternizing with benzyl chloride. Although these polymers are reported to be highly antibacterial at contact times as short as 4 minutes, they are water-soluble and therefore not suitable for producing durable surface coatings. Furthermore, no tests against viruses and toxicity were reported for these polymers.

[0065] Although antimicrobial quaternary ammonium compounds and polymers have been known previously, simple coatings of these materials have not been optically transparent or highly antimicrobial or durable, and the simple step of crosslinking the coating to achieve durability is insufficient to simultaneously achieve these properties.

[0066] Polymer of this technology The particular polymer chemistry of the present technology is new and novel in that non-obvious chemical modifications to the basic polyethyleneimine quaternary ammonium polymer structure have been developed to optimize the overall properties of the polymer by controlling the molecular weight of the polymer, the nature of the polymer quaternary ammonium group, the use of hydroxyalkylated PEI hydroxyl groups to fine-tune the hydrophilic-hydrophobic properties of the polymer by partial reaction with selected monoisocyanates, as well as the type and extent of polymer crosslinking to produce coatings having the above properties and more specifically exhibiting both high antimicrobial efficiency and good durability at the same time.

[0067] In one aspect, provided herein are several novel quaternary ammonium polymers that meet substantially all of the requirements listed above. The general process for producing these polymers begins with reacting polyethyleneimine (PEI) with an alkyl epoxide in a one-pot reaction, followed by quaternization with an alkylating agent to produce a polymer of the general structure of Figure 1, referred to as hydroxyalkyl quaternary PEI (HA-Q-PEI). These polymers are generally water-soluble or water-dispersible.

[0068] In the second step, the above polymer is reacted with one or a blend of hydrophobic monoisocyanates, in one case reacting less than 100% of the free hydroxyl groups to give the polymer of FIG. 2, designated mono-urethane substituted alkyl quaternary PEI-A (MUA-Q-PEI-A).

[0069] In an alternative embodiment, 100% of the free hydroxyl groups are reacted to give the polymer of Figure 3, designated mono-urethane substituted alkyl quaternary PEI-A100 (MUA-Q-PEI-A100). Both of these polymers (A and A100) are generally water insoluble and, in some embodiments, suitable for surface coating.

[0070] In another embodiment, to produce a more durable surface coating, the MUA-Q-PEI-A type polymer is dissolved in a solvent along with a polyisocyanate and coated onto a surface, whereby some of the remaining unreacted free hydroxyl groups react with the polyisocyanate to form a very durable crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B) coating after drying (see FIG. 4).

[0071] In yet another embodiment, the surface coating can be produced by applying a solution of HA-Q-PEI type polymer with polyisocyanate to produce a crosslinked polymer polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C), as shown in FIG. 5.

[0072] The synthesis of these antimicrobial polymers is relatively easy using only commercially available materials. It will be appreciated that this new family of antimicrobial polymers and the general method for their preparation offers a great deal of versatility to tailor and fine-tune the physical and chemical properties as well as their antimicrobial properties for various surfaces and applications. Examples of variables available for this fine-tuning include, but are not limited to, the molecular weight of the PEI, whether the PEI is linear, branched, or hyperbranched, the ratio of primary, secondary, and tertiary amines, the R group on the epoxide used, the alkylating agent used to quaternize the PEI, the degree of quaternization, the monoisocyanate used, the % of hydroxyl groups reacted with the monoisocyanate (including 0%), the polyisocyanate used, and the degree of crosslinking. It will also be appreciated that other means of crosslinking may be used other than using polyisocyanates.

[0073] Some embodiments of the technology described herein can be defined according to any of the following numbered paragraphs: 1. An antimicrobial composition comprising a mono-urethane substituted alkyl quaternary polyethyleneimine (PEl)-A (MUA-Q-PEI-A), wherein MUA-Q-PEI-A is formed by reacting at least one monoisocyanate with a hydroxyl alkyl quaternary PEI (HA-Q-PEI). 2. The antimicrobial composition of paragraph 1, wherein 20% to 100% of the hydroxyl groups of HA-Q-PEI are converted to urethane groups by reacting with at least one monoisocyanate. 3. The antimicrobial composition of paragraph 1, wherein 50% to 95% of the hydroxyl groups of HA-Q-PEI are converted to urethane groups by reacting with at least one monoisocyanate. 4. The antimicrobial composition of any one of paragraphs 1 to 3, wherein the monoisocyanate is selected from the group comprising alkyl-, alkylaryl-, arylalkyl-, and aryl-monoisocyanates. 5. The antimicrobial composition of any one of paragraphs 1-3, wherein the monoisocyanate is a blend of octyl isocyanate and octadecyl isocyanate. 6. The antibacterial composition according to paragraph 5, wherein the molar ratio of octyl isocyanate to octadecyl isocyanate is 1 / 9 to 5 / 5. 7. The antibacterial composition according to paragraph 5, wherein the molar ratio of octyl isocyanate to octadecyl isocyanate is 2 / 8 to 4 / 6. 8. The antimicrobial composition of any one of paragraphs 1-3, wherein the monoisocyanate is a fluoro- or organosilicone-substituted monoisocyanate. 9. The antimicrobial composition of any one of paragraphs 1 to 3, wherein the polyethyleneimine has an average molecular weight of 600 to 1,000,000. 10. The antimicrobial composition of any one of paragraphs 1 to 3, wherein the polyethyleneimine has an average molecular weight of 25,000 to 270,000. 11. The antimicrobial composition of any one of paragraphs 1 to 3, wherein the polyethyleneimine is a linear, branched, hyperbranched polyethyleneimine, or a blend thereof (i.e., a combination of two or more thereof). 12. The antimicrobial composition of any one of paragraphs 1-3, wherein MUA-Q-PEI-A has a counterion selected from the group consisting of halide, sulfate, sulfonate, phosphate, carbonate, and borate. 13. The antimicrobial composition of paragraph 12, wherein the counterion is chloride, bromide, iodide, or sulfate. 14. The antimicrobial composition of paragraph 1, wherein the reactant HA-Q-PEI is formed by reacting polyethyleneimine with a monoepoxide and quaternizing it with a quaternizing agent. 15. The antimicrobial composition of paragraph 14, wherein the monoepoxide is an alkyl epoxide. 16. The antimicrobial composition of paragraph 15, wherein the alkyl epoxide is selected from the group consisting of propyl epoxide, butyl epoxide, and hexyl epoxide. 17. The antimicrobial composition of paragraph 15, wherein the alkyl epoxide is propyl epoxide. 18. The antimicrobial composition of paragraph 14, wherein the quaternizing agent is an alkyl halide or an aryl alkyl halide. 19. The antimicrobial composition of paragraph 14, wherein the quaternizing agent is a benzyl halide or a hexyl halide. 20. An antimicrobial composition comprising a crosslinked polyurethane alkyl quaternary PEI-B (PUA-Q-PEI-B), wherein PUA-Q-PEI-B is formed by crosslinking the MUA-Q-PEI described in paragraph 1 with at least one polyisocyanate. 21. The antimicrobial composition of paragraph 20, wherein the polyisocyanate has an average isocyanate functionality of 2 to 5. 22. The antimicrobial composition of paragraph 20, wherein the polyisocyanate has an average isocyanate functionality of 3 to 4. 23. The antimicrobial composition of any one of paragraphs 20 to 22, wherein the polyisocyanate is prepared from a diisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI). 24. The antimicrobial composition of any one of paragraphs 20 to 22, wherein the polyisocyanate is an isocyanate end-capped oligomer prepared from a multifunctional isocyanate and a polyol. 25. The antimicrobial composition according to paragraph 24, wherein the polyol is selected from the group consisting of polyester polyols, polyether polyols, polysiloxane polyols, polycaprolactone polyols, and polybutadiene polyols. 26. An antimicrobial composition comprising a crosslinked polyurethane alkyl quaternary PEI-C (PUA-Q-PEI-C), wherein PUA-Q-PEI-C is formed by reacting at least one polyisocyanate with HA-Q-PEI. 27. The antimicrobial composition of paragraph 26, wherein the polyisocyanate has an average isocyanate functionality of 2 to 5. 28. The antimicrobial composition of paragraph 26, wherein the polyisocyanate has an average isocyanate functionality of 3 to 4. 29. The antimicrobial composition of any one of paragraphs 26 to 28, wherein the polyisocyanate is prepared from a diisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI). 30. The antimicrobial composition of paragraph 29, wherein the polyisocyanate is an isocyanate end-capped oligomer prepared from a multifunctional isocyanate and a polyol. 31. The antimicrobial composition according to paragraph 29, wherein the polyol is selected from the group consisting of polyester polyols, polyether polyols, polysiloxane polyols, polycaprolactone polyols, and polybutadiene polyols. 32. An antimicrobial coating, coating fluid, or spray fluid comprising the composition of any one of paragraphs 1 to 31. 33. The antimicrobial coating, coating fluid, or spray fluid of paragraph 32, wherein HA-Q-PEI, MUA-Q-PEI-A, PUA-Q-PEI-B, or PUA-Q-PEI-C is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. 34. A device, apparatus, equipment or accessory comprising a coating, coating fluid or spray fluid according to paragraph 32. 35. The device, apparatus, equipment, or accessory of paragraph 34, wherein the coating or spraying fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible. 36. The device, equipment, apparatus, or accessory of paragraphs 34 or 35, wherein the device, equipment, apparatus, or accessory is selected from the group consisting of a filter, an air purifier, and a mask. 37. The device, equipment, apparatus or accessory of paragraph 34 or 35, wherein the device, equipment, apparatus or accessory is selected from the group consisting of a keyboard, a keypad, a mouse, a remote control, a touch screen, a telephone and a display. 38. A personal care product comprising a coating, coating fluid, or spray fluid according to paragraph 32. 39. The personal care article of paragraph 38, wherein the coating or spraying fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible.

[0074] In another aspect, provided herein is a polymer comprising, consisting essentially of, or consisting of the reaction product of a polyethyleneimine oligomer, a multifunctional crosslinker, an alkylating agent, an optional monoisocyanate, and an optional catalyst, wherein the polyethyleneimine oligomer comprises an optionally substituted hydroxyethylene functional group that reacts with one or both of the optional monoisocyanate or the multifunctional crosslinker, and wherein nitrogen atoms present in the polyethyleneimine oligomer are at least partially quaternized by the alkylating agent.

[0075] Hydroxyethylene functionality on the polyethyleneimine oligomer can be introduced by reaction of the polyethyleneimine with a monoepoxide: thus, secondary and / or primary amines on the polyethyleneimine are alkylated with the monoepoxide to form hydroxyethylene functionality.

[0076] The hydroxyethylene functional group is C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10aryl; and carboxy. In some embodiments, the hydroxyethylene functional group is a C6-C6 alkyl optionally substituted with a substituent selected from 10 In some embodiments, the hydroxyethylene functional group is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with hydroxy. In some embodiments, the hydroxyethylene functional group is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with C1-C6 alkoxy. In some embodiments, the hydroxyethylene functional group is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with C1-C6 alkoxy. In some embodiments, the hydroxyethylene functional group is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with C1-C6 alkoxy. 10 Optionally substituted with aryl, C6-C 10 The aryl is optionally substituted with C1-C6 alkyl. In some embodiments, the hydroxyethylene functional group is substituted with C1-C6 alkyl, which is optionally substituted with C1-C6 alkoxy, which is optionally substituted with carboxy. In some embodiments, the hydroxyethylene functional group is substituted with C1-C6 alkyl.

[0077] The polyethyleneimine oligomer may comprise, consist essentially of, or consist of the reaction product of polyethyleneimine and a monoepoxide, the monoepoxide being a C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and carboxy. In some embodiments, the monoepoxide is optionally substituted with a C6-C6 alkyl, optionally substituted with a substituent selected from: 10In some embodiments, the monoepoxide is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with hydroxy. In some embodiments, the monoepoxide is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with C1-C6 alkoxy. In some embodiments, the monoepoxide is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with C1-C6 alkoxy. In some embodiments, the monoepoxide is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with C1-C6 alkoxy. 10 Optionally substituted with aryl, C6-C 10 The aryl is optionally substituted with C1-C6 alkyl. In some embodiments, the monoepoxide is substituted with C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with carboxy. In some embodiments, the monoepoxide is a C1-C6 alkyl epoxide. In some embodiments, the C1-C6 alkyl epoxide is selected from the group consisting of propyl epoxide, butyl epoxide, and hexyl epoxide.

[0078] The polyethyleneimine can have a molecular weight of about 600 to about 270,000 Daltons, or any range therebetween, including 600, 800, 1000, 5000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, 70000, 75000, 80000, 85000, 90000, 95000, 100000, 105000, 110000, 115000, 120000, 125000, 130000, 135000, 140000, 145000, 15000, 160000, 170000, 180000, 190000, 210000, 220000, 230000, 240000, 25000, 260000, 270000, 28000, 29000, 30000, 310000, 320000, 330000, 340000, 35000, 36000, 37000, 38000, 39000, 40000, 410000, 42000, 43000, 44000, 45000, 46000, 47000, 48000 The polyethylenimine may comprise a molecular weight of 50000, 155000, 160000, 165000, 170000, 175000, 180000, 185000, 190000, 195000, 200000, 205000, 210000, 215000, 220000, 225000, 230000, 235000, 240000, 245000, 250000, 255000, 260000, 265000, or 270000 Daltons, or any value therebetween. In some embodiments, the polyethylenimine has a molecular weight of about 10,000 to about 200,000 Daltons. In some embodiments, the polyethylenimine has a molecular weight of about 25,000 to about 120,000 Daltons. The polyethyleneimine may be branched or hyperbranched.

[0079] In some embodiments, the polyethyleneimine has a ratio of primary to secondary to tertiary amines of about 1:2:1 to about 1:1:1. In some embodiments, the polyethyleneimine has a ratio of primary to secondary to tertiary amines of about 1:1:0.7.

[0080] The multifunctional crosslinker can be a polyisocyanate. In some embodiments, the polyisocyanate has an average isocyanate functionality of 2 to 5. This includes an average isocyanate functionality of 2, 3, 4, or 5. In some embodiments, the polyisocyanate has an average isocyanate functionality of 3 or 4.

[0081] The polyisocyanate may be prepared from a diisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI).

[0082] In some embodiments, the polyisocyanate is selected from the group consisting of DESMODUR® N-3300, DESMODUR® N-100, DESMODUR® Z4470SN, WANNATE® T-series polyisocyanates, and LUPRANATE® M-series polyisocyanates. DESMODUR® N-3300 and DESMODUR® N-100 are aliphatic polyisocyanates based on HDI (hexamethylene diisocyanate) trimer. DESMODUR® Z4470SN is a multifunctional polyisocyanate based on IPDI (isophorone diisocyanate). WANNATE® T-series polyisocyanates are aromatic polyisocyanates based on toluene diisocyanate (TDI). LUPRANATE® M series polyisocyanates are aromatic polyisocyanates based on 4,4-diphenylmethane diisocyanate (MDI).

[0083] At least 75% of the nitrogen atoms of the polyethyleneimine oligomer may be quaternized with the alkylating agent, including 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100% of the nitrogen atoms of the polyethyleneimine oligomer are quaternized with the alkylating agent.

[0084] The alkylating agent can comprise, consist essentially of, or consist of one or more R2-LG, where each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkoxy optionally substituted with hydroxy, and each LG is a leaving group. As used herein, "leaving group" refers to a halide (e.g., chloride, bromide, or iodide), a sulfonate (e.g., mesylate, tosylate, triflate, nonaflate), a fluorosulfate, or an acetate. In some embodiments, each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy. In some embodiments, the alkylating agent is a benzyl halide or a hexyl halide. In some embodiments, the alkylating agent is a hexyl halide. In some embodiments, the alkylating agent is a benzyl halide.

[0085] The monoisocyanate can comprise, consist essentially of, or consist of one or more R3-NCO, where each R3 is independently: (1) a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, and (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl). In some embodiments, the monoisocyanate comprises one or more R3-NCO, where each R3 is independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 In some embodiments, the monoisocyanate comprises one or more R-NCO, where each R is independently selected from halogen, C-C alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3. In some embodiments, the monoisocyanate comprises octyl isocyanate, octadecyl isocyanate, or a combination thereof.

[0086] In some embodiments, at least 20% of the optionally substituted hydroxyethylene functional groups react with a monoisocyanate and no more than 25% of the optionally substituted hydroxyethylene functional groups react with a polyisocyanate, including 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 1010, 109, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 109, 102, 104 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more but less than 100%. In some embodiments, at least 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 1000, 1001, 104, 105, 106, 107, 108, 109, 109, 1000, 109, 1001, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, At least 8, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% but less than 100% react with the monoisocyanate. In some embodiments, no more than 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% but greater than 0% of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate. In some embodiments, no more than 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2%, or no more than 1% but greater than 0% of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate.

[0087] In some embodiments, 100% of the optionally substituted hydroxyethylene functional groups react with the polyisocyanate.

[0088] In some embodiments, the polymer comprises, consists essentially of, or consists of the reaction product of a polyethyleneimine oligomer, a polyisocyanate, an alkylating agent, and optionally a catalyst, in the absence of a monoisocyanate.

[0089] The catalyst may comprise, consist essentially of, or consist of dibutyltin dilaurate or bismuth carboxylate. In some embodiments, the catalyst comprises, consist essentially of, or consist of dibutyltin dilaurate. In some embodiments, the catalyst comprises, consist essentially of, or consist of bismuth carboxylate.

[0090] In another aspect, the present invention relates to compound (IV): [ka] A polymer having the formula: Each A is independently [ka] and [ka] or a copolymer of any two or more thereof, wherein the bond of each A forms a carbamate bond; each Y is independently H or -C(O)-NHR; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000; Each R1 is independently hydrogen; C6-C 10C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and C1-C6 alkyl optionally substituted with substituents selected from carboxy; Each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy; Each R3 is independently: (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 Aryl, and (3) [ka] wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3; Each R4 is independently a C1-C1 optionally substituted with phenyl. 10 an alkylene or a 3- to 8-membered cycloalkyl ring; each X -is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphoric acid, phosphonic acid, carbonate, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and organic substituted derivatives thereof.

[0091] In another aspect, the present disclosure provides compound (V): [ka] A polymer having the formula: Each A is independently [ka] or a copolymer of any two or more thereof, wherein the bond of each A forms a carbamate bond; each Y is independently H or -C(O)-NHR; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000; Each R1 is independently hydrogen; C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and C1-C6 alkyl optionally substituted with substituents selected from carboxy; Each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy; Each R3 is independently: (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 Aryl, and (3) [ka] wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3; Each R4 is independently a C1-C1 optionally substituted with phenyl. 10 an alkylene or a 3- to 8-membered cycloalkyl ring; each X - is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphoric acid, phosphonic acid, carbonate, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and organic substituted derivatives thereof.

[0092] In some embodiments of Compound (IV) or Compound (V), at least 75% but not all of R are independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl; and halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl;b and each R c are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl), including 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more, but not all, of R3 are independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl; and halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3.

[0093] In some embodiments of compound (IV) or compound (V), each R is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 In some embodiments of compound (IV) or compound (V), each R is selected from C-C alkyl. 20 In some embodiments of Compound (IV) or Compound (V), R3 is independently selected from halogen, C1-C6 alkyl, and -SiR3. In some embodiments of Compound (IV) or Compound (V), R3 is independently selected from octyl, octadecyl, or a combination thereof. In some embodiments of Compound (IV) or Compound (V), each R3 is independently selected from halogen, C1-C6 alkyl, and -SiR3. a (OR b)( OR cC6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl.

[0094] In some embodiments of compound (IV), R3 is [ka] It is.

[0095] In some embodiments of compound (V), R3 is [ka] It is.

[0096] In some embodiments of compound (IV) or compound (V), each R1 is independently C1-C6 alkyl.

[0097] In some embodiments of compound (IV) or compound (V), each R is independently selected from hydroxy, C-C alkoxy, carboxy, C-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 In some embodiments of Compound (IV) or Compound (V), each R2 is independently selected from C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy, optionally substituted with hydroxy. In some embodiments of Compound (IV) or Compound (V), each R2 is independently selected from C1-C6 alkyl optionally substituted with C1-C6 alkoxy. In some embodiments of Compound (IV) or Compound (V), each R2 is independently selected from C1-C6 alkyl optionally substituted with carboxy. In some embodiments of Compound (IV) or Compound (V), each R2 is independently selected from C6-C6 alkyl optionally substituted with hydroxy. 10In some embodiments of Compound (IV) or Compound (V), each R2 is independently selected from C1-C6 alkyl optionally substituted with C1-C6 alkoxy, which is optionally substituted with hydroxy. In some embodiments of Compound (IV) or Compound (V), each R2 is independently selected from -C(O)O(C1-C6 alkyl) or -C(O)-(C6-C 10 In some embodiments of Compound (IV) or Compound (V), each R2 is independently selected from methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of Compound (IV) or Compound (V), R2 is hexyl or benzyl. In some embodiments of Compound (IV) or Compound (V), R2 is hexyl. In some embodiments of Compound (IV) or Compound (V), R2 is benzyl.

[0098] In some embodiments of compound (IV) or compound (V), R is a C-C optionally substituted phenyl. 10 In some embodiments of compound (IV) or compound (V), R4 is C 1- C 10 In some embodiments of compound (IV) or compound (V), R4 is a 3- to 8-membered cycloalkyl ring.

[0099] In another aspect, the present disclosure provides compound (VI), compound (VII), or compound (VIII): [ka] or a combination of any two or more thereof, or a copolymer of any two or more thereof, wherein each Y is independently H or -C(O)-NHR; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 100 to 1000; Each R1 is independently hydrogen; C6-C 10 C1-C6 alkoxy optionally substituted with aryl and hydroxy; C1-C6 alkoxy; C6-C6 alkyl optionally substituted with C1-C6 alkyl 10 aryl; and C1-C6 alkyl optionally substituted with substituents selected from carboxy; Each R2 is independently selected from hydroxy, C1-C6 alkoxy, carboxy, C6-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 aryl), and C1-C6 alkyl optionally substituted with a substituent selected from C1-C6 alkoxy optionally substituted with hydroxy; Each R3 is independently: (1) halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl, and (2) halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3; each X - is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphoric acid, phosphonic acid, carbonate, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and organic substituted derivatives thereof.

[0100] In some embodiments of compound (VI), compound (VII), or compound (VIII), each R1 is independently C1-C6 alkyl.

[0101] In some embodiments of compound (VI), compound (VII), or compound (VIII), each R is independently selected from hydroxy, C-C alkoxy, carboxy, C-C 10 Aryl, -C(O)O(C1-C6 alkyl), -C(O)-(C6-C 10 In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from C1-C6 alkyl optionally substituted with hydroxy. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from C1-C6 alkyl optionally substituted with C1-C6 alkoxy. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from C1-C6 alkyl optionally substituted with C1-C6 alkoxy. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from C1-C6 alkyl optionally substituted with carboxy. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from C6-C6 alkyl optionally substituted with carboxy. 10 In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from C1-C6 alkyl, optionally substituted with aryl. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from -C(O)O(C1-C6 alkyl), or -C(O)-(C6-C 10In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from C1-C6 alkyl optionally substituted with C1-C6 alkoxy, where C1-C6 alkoxy is optionally substituted with hydroxy. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), each R2 is independently selected from methyl, butyl, hexyl, benzyl, -CH2C(O)Ph, and -CH2C(O)OCH2CH3. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), R2 is hexyl or benzyl. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), R2 is hexyl. In some embodiments of compound (VI), compound (VII), or compound (VIII), R2 is benzyl.

[0102] In some embodiments of compound (VI), compound (VII), or compound (VIII), each R is independently a halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 In some embodiments of compound (VI), compound (VII), or compound (VIII), each R is independently selected from C-C 20 In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), R3 is independently selected from halogen, C1-C6 alkyl, and -SiR3. In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), R3 is independently selected from halogen, C1-C6 alkyl, and -SiR3. a (OR b)( OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl.

[0103] In some embodiments of Compound (VI), Compound (VII), or Compound (VIII), at least 75% but not all of R are independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl; and halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c are independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl), including 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more, but not all, of R3 are independently selected from halogen, -SiR a (OR b )(OR c ), and C6-C 10 C6-C optionally substituted with 1 to 3 substituents independently selected from aryl 20 Alkyl; and halogen, C1-C6 alkyl, and -SiR a (OR b )(OR c C6-C optionally substituted with 1 to 3 substituents independently selected from 10 aryl, wherein each R a is independently C1-C6 alkyl; b and each R c is independently selected from C1-C6 alkyl and -Si(C1-C6 alkyl)3.

[0104] For compound (IV), compound (V), compound (VI), compound (VII), or compound (VIII), each X - are independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphoric acid, phosphonic acid, carbonate, silicic acid, hexafluorophosphate, hexafluoroantimonic acid, and borate, and organically substituted derivatives thereof. As used herein and unless otherwise specified, "organically substituted derivative" refers to an anion in which the sulfur atom, phosphorus atom, boron atom, silicon atom, or carbonyl group is replaced with either an alkyl group or an aryl group. Non-limiting examples include methyl sulfate, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethylsulfonic acid, and trifluoroacetic acid.

[0105] In another aspect, provided herein is an antimicrobial composition comprising, consisting essentially of, or consisting of a polymer disclosed herein. In some embodiments, the polymer comprises, consists essentially of, or consists of compound (IV). In some embodiments, the polymer comprises, consists essentially of, or consists of compound (V). In some embodiments, the polymer comprises, consists essentially of, or consists of compound (VI), compound (VII), or compound (VIII), or a combination of any two or more thereof, or a copolymer of any two or more thereof.

[0106] In another aspect, provided herein is an antimicrobial coating, coating fluid, or spray fluid comprising, consisting essentially of, or consisting of the antimicrobial composition described herein. In some embodiments, the coating fluid or spray fluid is water soluble, water dispersible, alcohol soluble, or alcohol dispersible. In some embodiments, the coating fluid or spray fluid is water soluble or water dispersible. In some embodiments, the coating fluid or spray fluid is alcohol soluble or alcohol dispersible.

[0107] In another aspect, provided herein is a device, equipment, apparatus, or accessory comprising the antimicrobial coating, coating fluid, or spray fluid described herein. Non-limiting examples of devices, equipment, apparatus, or accessories include filters, air purifiers, masks or other personal protective devices (PPDs), respirators, etc. Other non-limiting examples include keyboards, keypads, mice, remote controls, touch screens, phones, and displays, or any device integrating any of the aforementioned components.

[0108] In another aspect, provided herein is a personal care product comprising the coating, coating fluid, or spray fluid described herein. Non-limiting examples of personal care products include facial tissues, hand soaps, and cleansing pads.

[0109] How to use In another aspect, provided herein is a method of disinfecting a surface comprising, consisting essentially of, or consisting of applying to the surface a composition disclosed herein.

[0110] In another aspect, provided herein is a method of reducing (e.g., minimizing) antimicrobial growth on a surface, the method comprising, consisting essentially of, or consisting of applying to the surface a composition disclosed herein. In some embodiments, the method comprises forming a coating solution containing a composition according to any of the embodiments described herein. The method further comprises directing the coating solution to the surface via an applicator (e.g., a sprayer) and providing a coating on the surface through application of the coating solution to the surface.

[0111] In another aspect, provided herein is a method of preventing antimicrobial growth on a surface comprising, consisting essentially of, or consisting of applying to the surface a composition disclosed herein.

[0112] In some embodiments of the above-mentioned method, the applying step comprises, consists essentially of, or consists of spraying or brushing the surface with the composition. In some embodiments of the above-mentioned method, the applying step comprises, consists essentially of, or consists of immersing the surface in a coating solution containing a composition according to any of the embodiments described herein. In some embodiments of the above-mentioned method, the applying step comprises, consists essentially of, or consists of applying the composition to the surface by an electrostatic process.

[0113] The description of the embodiments of the present disclosure is not intended to be exhaustive or to limit the present disclosure to the exact form disclosed. Specific embodiments and examples of the present disclosure are described herein for illustrative purposes, but as one of ordinary skill in the relevant art will recognize, various equivalent modifications are possible within the scope of the present disclosure. For example, while method steps or functions are presented in a given order, alternative embodiments may perform the functions in a different order, or the functions may be performed substantially simultaneously. The teachings of the present disclosure provided herein can be applied to other procedures or methods, where appropriate. The various embodiments described herein can be combined to provide further embodiments. Aspects of the present disclosure can be modified, as appropriate, to adopt compositions, functions, and concepts of the above-mentioned references and applications to provide still further embodiments of the present disclosure. Furthermore, some changes can be made in protein structure without affecting the type or amount of biological or chemical activity, due to considerations of biological functional equivalence. These and other changes can be made to the present disclosure in light of the detailed description. All such modifications are intended to be within the scope of the appended claims.

[0114] Particular elements of any of the foregoing embodiments may be combined with or substituted for elements of other embodiments. Furthermore, although advantages associated with particular embodiments of the present disclosure are described in the context of those embodiments, other embodiments may also exhibit such advantages, and not all embodiments necessarily exhibit such advantages to fall within the scope of the present technology.

[0115] The technology described herein is further illustrated by the following examples, which should not be construed as further limiting in any way. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, suitable methods and materials are described below. EXAMPLES

[0116] The present technology, now generally described, will be more readily understood by reference to the following examples, the first three of which describe general synthetic procedures for synthesizing HA-Q-PEI polymers, reacting them with monoisocyanates to produce MUA-Q-PEI-A polymers, and preparing crosslinked MUA-Q-PEI-B polymer coatings, which are included solely for purposes of illustration of certain aspects and embodiments of the present technology and are not intended to limit the present technology.

[0117] Example 1 Synthesis of Hydroxypropyl Quaternary Ammonium PEI For the purposes of the chemistry described herein, the ratio of primary, secondary, and tertiary amines in branched PEI is assumed to be 1:2:1, as reported in the literature. 24、25 .

[0118] The procedure used was essentially as described by Gao et al. (2007). 26 The structure of polymeric compound (I), as shown below, is intended to be an approximation indicating that most of the primary and secondary amines have been reacted with the epoxide and most of the tertiary amines have been quaternized by alkylation with benzyl chloride. [ka]

[0119] To a 25 mL two-neck flask under nitrogen was added 3.33 g of 70 kDa PEI solution (30% / 1 g PEI in water, mw=43.1 g / mol, assuming 23.2 mmol) and cooled to 0°C. To this mixture was added 5.4 g (92.8 mmol) of propylene oxide dropwise at 0-3°C. After the addition was complete, the reaction mixture was stirred at 0-3°C for 7 hours. The temperature of the reaction mixture was then raised to 35°C and the unreacted propylene oxide was distilled (approximately 3.60 mL). To the resulting solution was added 11.75 g (10.6 mL, 92.8 mmol) of benzyl chloride and the reaction was heated to 50°C for 30 hours. The reaction was extracted with diethyl ether (3 x 20 mL) to remove unreacted benzyl chloride, residual propylene oxide, and lipophilic by-products or impurities (if present). The aqueous phase was separated, evaporated under vacuum, and dried by lyophilization to leave Compound (I) as a clear solid (2.85 g). The product was characterized by proton NMR and infrared (IR) spectroscopy.

[0120] Example 2 Process of reaction of hydroxypropyl quaternary ammonium PEI with monoisocyanate (approximately 85% of free OH groups) As shown below, the structure of the polymer product is intended to be an approximation indicating that the majority of the hydroxyl groups (approximately 85% molar equivalents) react with the blend of monoisocyanates to form a urethane, with some hydroxyl groups remaining unreacted. [ka]

[0121] The concentration of reactive hydroxyl groups (mmol / gram of dry polymer) was determined by titrating a known amount (grams) of dry HA-Q-PEI polymer with a known excess (grams, mmol) of octadecyl isocyanate. The percentage of monoisocyanate consumed in the reaction was monitored using infrared (IR) spectroscopy to determine the reaction progress at 2263 cm -1 The isocyanate concentration was determined by monitoring the decline of the isocyanate peak at 100° C. From the percentage decline of this peak, the number of millimoles of isocyanate consumed was estimated. This value corresponded to the number of millimoles of polymer hydroxyl groups that reacted with isocyanate. In this way, the hydroxyl group concentration of the polymer (mmoles reactive hydroxyl groups / g dry polymer) was calculated and then used in subsequent reactions to determine the amount of monoisocyanate needed to functionalize a specific percentage of reactive hydroxyl groups in the polymer, and thereby fine-tune the hydrophilic / hydrophobic properties of the polymer.

[0122] Using the procedure described in Example 1, 2.0 g (2.27 mmol assuming a molecular weight of 881 g / mol for the polymer unit cell) of hydroxypropyl quaternary ammonium PEI compound (I) was prepared and then dried under vacuum at 60° C. for 2 hours, followed by storage in a desiccator at room temperature overnight. To the dried polymer, 13.8 g of t-butyl alcohol and 9.2 g of dimethylacetamide were added. The resulting mixture was stirred under nitrogen until the polymer was completely dissolved. Both of these solvents were thoroughly dried over molecular sieves 4 Å before use. A mixture of 1.6 g (5.41 mmol) of octadecyl isocyanate and 0.36 g (2.32 mmol) of octyl isocyanate was added dropwise to the polymer solution. This mixture totaled 7.73 mmol of monoisocyanate, which corresponds to approximately 85% of the available hydroxyl groups. The reaction mixture became slightly cloudy. The resulting reaction mixture was stirred under nitrogen at room temperature for 12 hours. The resulting reaction mixture was filtered through a PTFE filter (1μ) to give 20.83 grams of compound (II) as a 12.19% solid solution. IR spectroscopy showed the expected new peaks corresponding to the urethane carbonyl and no residual isocyanate peaks.

[0123] In some embodiments, after the reaction with the monoisocyanate was complete, the reaction mixture was added to water to precipitate the MUA-Q-PEI-A product. The product was isolated, washed with water to remove any water-soluble impurities, and then dried for use in the next step. This water precipitation step was useful for removing any water-soluble impurities that may contribute to toxicity.

[0124] Example 3 Process for the crosslinking and coating reaction of octadecyl / octadyl urethane quaternary ammonium PEI As shown below, the structure of polymeric compound (III) is intended to be an approximation indicating that some of the unreacted hydroxyl groups in compound (II) have reacted with polyisocyanate to form urethane crosslinks. [ka] TIFF2024510790000025.tif141157

[0125] 20 g of octadecyl / octyl urethane quaternary ammonium PEI was prepared using the procedure described in Example 2, to which 1.25 g of Desmodur N3300 (50% solution in anhydrous acetone) and 0.18 g of dibutyltin dilaurate 1% solution in dry toluene were added. The resulting mixture was thoroughly mixed and immediately coated with a #36 Mayer rod onto corona pretreated white PET (2 mil, Milenex 339) supported on a stainless steel plate. The coated film was heated in an oven at 60° C. for 30 minutes without vacuum. The dried film was used to measure antimicrobial activity. IR spectroscopy showed no residual isocyanate.

[0126] It should be noted that the above crosslinking procedure has also been carried out without the dibutyltin dilaurate catalyst, and the resulting dry films provided reasonable coatings, albeit somewhat less durable than when the catalyst was used.

[0127] It will also be appreciated that several variations, including but not limited to those described below, may be used in the above-described process to tailor the physical, chemical, and mechanical properties of the polymer, as needed, to the range of possible applications: Different average molecular weight PEI and PEI with different degrees of branching. • Different epoxides other than propyl epoxide. • Different quaternizing groups other than benzyl. - The degree of hydroxyalkylation and quaternization can be varied. • The extent of oligomer formation in hydroalkylation reactions with alkyl epoxides. Different monoisocyanates can be used; these can be a single monoisocyanate or a blend of monoisocyanates. • The reaction with monoisocyanates to form urethanes can be varied so that less than 100% of the hydroxyl groups react or 100% of the hydroxyl groups react. ●Polyisocyanates other than N3300 can be used for crosslinking. • Different solvents may be used for chemical reactions depending on the solubility of the PEI derived polymer, which may be affected by the above mentioned variations. • Reactants other than monoisocyanates and polyisocyanates can be used to react with hydroxyl groups and crosslink.

[0128] Example 4 Evaluation of the antiviral activity of polymers and / or their coatings This study was conducted to evaluate the antiviral activity of the polymer coating of this technology. All samples and all accessories in the evaluation were first disinfected by either high temperature autoclaving, alcohol washing, or irradiation in a UV laminar flow chamber.

[0129] First, adenovirus (108 PFU / mL, plaque-forming units, MOI = 100) was inoculated into phosphate buffered saline (PBS) at 2 × 10 7 PFU / ml. Then, 0.1 mL of the diluted virus solution was deposited onto the disinfected sample.

[0130] The antiviral activity was determined by two different methods: (i) a human cell (HuH7) method, and (ii) a quantitative reverse transcription polymerase chain reaction (RT-qPCR) method.

[0131] (i) Human cell (HuH7) method HuH7 is a type of human liver cell line that can be grown in the laboratory for research purposes. According to the website huh7.com, it is "a cancer cell line derived from well-differentiated liver cells originally isolated from a liver tumor in a 57-year-old Japanese man in 1982."

[0132] For the evaluation of antiviral activity, 0.1 mL of virus (adenovirus) in Dulbecco's Modified Eagle Medium (DMEM) + 10% fetal bovine serum (FBS) medium was dropped onto the coating and onto the control substrate and left on the coating for 30 minutes. The virus / medium mixture was transferred to a Petri dish containing HuH7 cells (human hepatocytes) in medium. Residual virus on the coating was rinsed twice by combining 0.1 mL of medium and liquid with the virus solution in the Petri dish. The Petri dish was transferred to a CO2 incubator and incubated at 37°C with a relative humidity of about 95% and a CO2 concentration of about 5% for 48 hours to amplify the signal.

[0133] Once incubation was complete, visible and fluorescent micrographs of the virus / cell samples were taken to determine the virus and live / dead cell populations. For the positive control, 0.1 mL of virus in medium was transferred directly to a petri dish containing HuH7 cells in medium.

[0134] (ii) RT-qPCR method RT-qPCR is used in a variety of applications including pathogen detection, gene expression analysis, RNAi validation, microarray validation, genetic testing, and disease research.

[0135] Sample preparation Media (DMEM, high sucrose, pyruvate; ThermoFisher, Catalog Number: 11995040) was removed from the refrigerator and conditioned in a 37°C water bath for 30 minutes.

[0136] Preparation of virus fluid: Typical virus numbers for the stock are 5 lambda (5x10) per tube. 8 ) Add 1 mL of DMEM medium to the virus tube, mix the tube evenly with a vortex mixer for 5 to 10 seconds, and then mix 5 × 10 8 The virus fluid was prepared at a concentration of 5 × 10 / mL in DMEM medium for antiviral testing. 7 / mL.

[0137] RT-qPCR procedure for coating: The coated film was immersed in 99% alcohol for 1 second. Excess alcohol was removed from the surface. The film was then air-dried for 15-20 minutes in a new Petri dish. Then, 100 μL of diluted virus solution (5 × 10 6 A 50 μL drop of 1× PBD was dropped onto the dry film. The Petri dish was covered and the virus was allowed to contact the film for the desired contact time. In some of the experiments, the contact time was reduced to as little as 30 seconds. The virus fluid from the film was transferred to an Eppendorf tube. The film was then rinsed twice with 50 μL of 1× PBD and the rinse fluids were combined into the Eppendorf tube. The total test volume was 200 μL and ready for DNA extraction.

[0138] RT-qPCR procedure for aqueous solutions: Add 100 µL of test sample to 100 µL of diluted virus fluid (5 × 10) in an Eppendorf tube. 7 / mL) and the mixture (5 × 10 6 The virus count was measured by shaking the tubes for 30 min on a shaker. DNA was extracted using the Novogene DNA kit according to the specified extraction procedure.

[0139] RT-qPCR testing: Each sample was tested in quadruplicate. The components listed in Table 1 were mixed thoroughly in an Eppendorf tube. [Table 1] [Table 2]

[0140] As illustrated in Figure 6A, 10 μL of premix was added to each cavity of the test plate, and three samples were taken for each coating, with each sample run in quadruplicate, resulting in a total of 12 tests for each coating.

[0141] The plate was centrifuged to ensure that all premix fluid flowed to the bottom of the cavity. As illustrated in FIG. 6B, the plate was inserted into Applied Biosystems QuantStudio3 (ThermoFisher) to determine the cycle threshold (CT) number for the calculation of antiviral efficiency. Quantitative RT-PCR method may be performed. Antiviral efficiency is quantitatively calculated from the CT number. For the use of QuantStudio3 PCR procedure, see https: / / www.youtube.com / watch?v=udy7iskkZwE and https: / / www.youtube.com / watch?v=PjgwDhN63Zc.

[0142] test Qualitative cell viability test of the coating: The coating was placed in a Petri dish and 100 μL of DMEM medium was dropped onto the coating. The Petri dish was then covered for 30 minutes. The medium on the film was then dropped into 8 × 10 cells in 500 μL of medium in each fraction, as shown in Figure 7. 4 The film was then transferred to a cell plate containing 100 μL of cells. The film was rinsed twice with 50 μL of DMEM medium and the rising fluid was combined with the previous test fluid in the same position in the plate. A total of 200 μL of test fluid was added to the 500 μL of cells / medium. The cell plate was incubated in a 37°C / 95% RH CO2 incubator for 48-96 hours, after which cell growth and morphology were observed under a visible microscope. Dead cells floated or suspended in the medium, while live cells remained fixed to the bottom of the plate. This test was for the evaluation of contact cytotoxicity of the polymer film. If this test shows some degree of cytotoxicity, the actual mechanism of cell death is not given, although cell death due to extraction of chemicals from the coating is one possibility.

[0143] Qualitative cell viability testing of polymer solutions or dispersions: 100 μL of polymer solution or dispersion and 100 μL of DMEM medium were added to an Eppendorf and mixed thoroughly on a shaker for 30 min. For polymer films, fixed areas of the film were cut and dispersed in the medium for testing. The test fluids were transferred to cell plates and cells were grown for 48-96 h in a 37°C / 95% RH CO2 incubator. Cell growth and morphology were recorded under a visible microscope.

[0144] Qualitative antiviral efficiency test of polymer films: 100 μL of virus solution (5 × 10 7 Virus solution was added at 8 × 10 / mL in 500 μL of medium in each fraction onto a polymer film in a Petri dish. The Petri dish was covered for 30 min. Virus solution was added at 8 × 10 / mL in 500 μL of medium in each fraction. 4 The film was then rinsed twice with 50 μL of DMEM medium and the rising fluid was combined with the previous test fluid in the same position in the plate. The total volume of the test fluid was 200 μL. The cell plate was then incubated in a 37 °C / 95% RH CO2 incubator for 48-96 h. Finally, the cell morphology and fluorescence were recorded under a UV microscope.

[0145] Qualitative antiviral efficiency test of polymer solutions or dispersions: 100 μL of virus solution (5 × 10 7 100 μL of polymer solution or dispersion was added to the Eppendorf and thoroughly shaken on a shaker for 30 min. The test mixture was diluted with 8 × 10 4 The cells were then added to the cell plates containing 100 μg / mL of 10 ...

[0146] Experimental Results - Antiviral Activity and Toxicity of Crosslinked Polymer Compound (III) Coating Coatings of crosslinked polymer compound (III), prepared and tested as described above, killed >99.9% of adenoviruses with a contact time of only 30 seconds. Furthermore, compound (III) was non-toxic to HuH7 cells. Coatings of compound (III) were essentially colorless, transparent, durable in contact with water and alcohol, and showed excellent adhesion to various substrates such as PET and metal plates. Similar highly efficient antiviral activity and non-toxicity were observed with coatings of compound (II) polymer, which have slightly inferior durability to water and alcohol relative to coatings of compound (III), but are also essentially colorless and transparent.

[0147] The following examples further illustrate the advantage and versatility of this technology.

[0148] Example 5 Aqueous antiviral efficiency against adenovirus of HA-Q-PEI polymers with various PEI molecular weights, nitrogen quaternized groups, and anionic counterions The following formula: [ka] A variety of HA-Q-PEIs (hydroxyalkyl quaternary PEIs) were prepared using procedures similar to those described in Example 1 and analyzed for their antiviral (AV) efficiency against adenovirus as described in Example 4. Selected data are shown in Table 2 (R1 = methyl for each polymer). These results demonstrate high antiviral efficiency across a range of PEI molecular weights, using a variety of nitrogen quaternization groups (R2) and anionic counterions (X-). [Table 3]

[0149] Example 6 Aqueous antiviral efficiency of HA-Q-PEI polymers with various PEI molecular weights against adenovirus The following formulas with various molecular weights: [ka] Additional HA-Q-PEI polymers (R1=methyl, R2=hexyl, X=bromide) were prepared using procedures similar to those described in Example 1 and analyzed for their antiviral (AV) efficiency against adenovirus as described in Example 4. Selected data are shown in Table 3. [Table 4]

[0150] These results demonstrate that for this series of HA-Q-PEI polymers, solution antiviral efficiency against adenovirus increases as PEI molecular weight increases, leveling off at a maximum of >99% within the range of 25,000-270,000.

[0151] Although these HA-Q-PEI polymers show high solution antiviral efficiency, their high water solubility makes them not directly suitable for the creation of durable, water-resistant surface coatings. Coating durability to solvents such as water and ethanol is highly desirable, as it maintains antibacterial efficiency and greatly reduces the need for frequent resterilization of surfaces even after they have been cleaned by washing.

[0152] Example 7 Adenovirus Antiviral Efficiency of PUA-Q-PEI-C Coatings as a Function of the Weight Percentage of N100 Crosslinker Used The following formula: [ka] Coating of the PUA-Q-PEI-C polymer was performed using a procedure similar to that described in Example 2, replacing the octadecyl / octyl urethane quaternary ammonium PEI with HA-Q-PEI (prepared from PEI: molecular weight = 70,000 (branched), R1 = methyl, R2 = hexyl, X = bromide) with crosslinker Z (DESMODUR® N100): [ka] The amount of each was varied.

[0153] The antiviral efficacy of these PUA-Q-PEI-C polymers against adenovirus (as described in Example 4) was investigated. Selected data are shown in Table 4. [Table 5]

[0154] Cross-linking the HA-Q-PEI coating to form a polyurethane PUA-Q-PEI-C polymer coating improved the water and ethanol durability of the coating (data not shown), but as can be seen by this example, this was associated with a significant decrease in antiviral efficiency with increasing amounts of cross-linking.

[0155] Example 8 Antiviral Efficiency of Aqueous Solutions of HA-Q-PEI Polymer as Non-Crosslinked Coating and MUA-Q-PEI-A and MUA-Q-PEI-A100 Polymers Against Adenovirus The following formula: [ka] MUA-Q-PEI-A polymer (R3=C 18 HA-Q-PEI (prepared from PEI: molecular weight = 70,000 (branched), R1 = methyl, R2 = benzyl) and a monoisocyanate mixture (mixture of octadecyl isocyanate and octyl isocyanate in a 7:3 ratio), with approximately 90% of the HA-Q-PEI hydroxyl groups reacting with the monoisocyanate mixture (see similar protocol in Example 2). MUA-Q-PEI-A100 polymer was similarly prepared, with approximately 100% of the HA-Q-PEI hydroxyl groups reacting with the monoisocyanate mixture. Films of these MUA-Q-PEI-A and MUA-Q-PEI-A100 polymers were examined for their antiviral efficiency against adenovirus as described in Example 4. The results are shown in Table 5. [Table 6]

[0156] These results indicate that the high solution antiviral efficiency of the HA-Q-PEI polymer was maintained and / or increased after reaction with a mixture of monoisocyanates to form coatings of the MUA-Q-PEI-A and MUA-Q-PEI-A100 polymers. These results also demonstrate that the coatings exhibited >99% antiviral efficiency even at contact times as short as 30 seconds.

[0157] Example 9 PUA-Q-PEI-B Coating Antiviral Efficiency Against Adenovirus and Coating Durability as a Function of the Amount (Weight Percent) of N3300 Polyisocyanate Crosslinker Used The following formula: [ka] PUA-Q-PEI-B polymer (R3=C 18 Alkyl or C8 alkyl) were prepared using a procedure similar to that described in Example 3. In particular, HA-Q-PEI (prepared from PEI: molecular weight = 25,000 (hyperbranched), R1 = methyl, R2 = hexyl, X = bromide) was reacted with a monoisocyanate mixture (7:3 mixture of octadecyl isocyanate and octyl isocyanate) and the remaining hydroxyl groups were cross-linked with various amounts of cross-linker Z (DESMODUR® N3300): [ka] Approximately 90% of the HA-Q-PEI hydroxyl groups were reacted with the monoisocyanate mixture prior to reaction with .

[0158] These PUA-Q-PEI-B polymer coatings were evaluated for their antiviral efficiency against adenovirus (as described in Example 4), water durability, and ethanol durability. The general procedure for measuring water and ethanol durability was to immerse the center cross-cut coating samples in water or ethanol for 10 minutes, followed by gently wiping the samples with a cotton swab. Intact coatings passed the test. Selected data are shown in Table 6. [Table 7]

[0159] This data suggests that crosslinker is necessary to achieve good durability and that for these samples there was an optimal range of crosslinker levels where the antiviral efficiency was >99% and above which the antiviral efficiency decreased significantly.

[0160] Example 10. Retention of high coating antiviral efficiency after extended time and under more extreme environmental conditions The following formula: [ka] PUA-Q-PEI-B polymer (R3=C 18 X=X=X-alkyl) was prepared using a procedure similar to that described in Example 3. In particular, HA-Q-PEI (prepared from PEI: molecular weight=70,000 (branched), R1=methyl, R2=benzyl, X=chloride) was reacted with octadecyl isocyanate such that approximately 85% of the HA-Q-PEI hydroxyl groups were reacted with octadecyl isocyanate before the remaining hydroxyl groups were reacted with crosslinker Z (DESMODUR® N3300).

[0161] After coating and drying, the coating was optically clear, passed water and ethanol durability tests (protocol described in Example 9), was non-toxic to human hepatocytes, and showed 99.9% antiviral efficiency against adenovirus after a contact time of 30 seconds (protocol described in Example 4).

[0162] After storing the coatings at ambient conditions for 105 days, the coatings still exhibited an antiviral efficiency of >98%, and after storing at 40°C / 85% RH for 72 hours, the coatings exhibited an antiviral efficiency of >99.73%. Furthermore, these results were shown to be independent of the level of crosslinker used, which ranged from 1.62 to 7.61 weight percent.

[0163] In contrast, the commercially available LIVINGUARD® face mask showed an antiviral efficiency against adenovirus of only 44% after 1 minute of contact time, and only 72% after 20 minutes of contact time. When subjected to the same long-term and harsh conditioning test, the LIVINGUARD® face mask efficiency dropped to 0% after 105 days of storage at ambient conditions at 20 minutes of contact time, and decreased from 72% to only 16% after 72 hours of storage at 40°C / 85% RH.

[0164] Using the antiviral and toxicity test procedures described above, as well as the durability test procedures, several commercially available products were tested for comparison.

[0165] In contrast to the coatings of the present technology, the quaternary PEI polymer shown below did not form a colorless, transparent, durable water- and alcohol-resistant coating and had only moderate antiviral activity.Two latex quaternary polymers shown below showed antiviral activity but were toxic to HuH7 cells. [ka]

[0166] Mundex-W and Mundex-LK (from Munditech, Germany) are two "self-disinfecting polymer emulsions" for treating surfaces. Both were found to be very weakly antiviral against adenovirus. Not unexpectedly, the water-based Mundex-W did not provide a durable, water- or alcohol-resistant surface coating. The solvent-based Mundex-LK provided a more hydrophobic coating, but one that was only slightly water- or alcohol-resistant. Furthermore, both of them were found to be toxic to HuH7 cells.

[0167] Example 11 Evaluation of the Antibacterial and Antifungal Activity of Additional Coatings of the Present Technology The following formula: [ka] PUA-Q-PEI-B polymer (R3=C 18 A series of HA-Q-PEI (C8 alkyl or C8 alkyl) was prepared using a procedure similar to that described in Example 3. In particular, HA-Q-PEI (prepared from PEI: molecular weight = 25,000 (hyperbranched) or 600 (branched), R1 = methyl, R2 = hexyl, X = bromide) was reacted with a mixture of monoisocyanates (7:3 mixture of octadecyl isocyanate and octyl isocyanate) to react approximately 75% of the HA-Q-PEI hydroxyl groups with octadecyl isocyanate before reacting the remaining hydroxyl groups with various amounts of crosslinker Z (DESMODUR® N100).

[0168] These PUA-Q-PEI-B polymer coatings were evaluated for their antibacterial and antifungal efficiency, and selected data are shown in Table 7. [Table 8] † Antibacterial efficiency evaluated using the PN-EN ISO22196:2011 standard at 35°C. ‡Antibacterial efficiency evaluated using the PN-EN ISO21702:2019 standard at 25°C. * PEI molecular weight = 25,000 Daltons (multiple branched), ** PEI molecular weight = 600 daltons (branched), A = Staphylococcus aureus (MRSA), B = Pseudomonas aeruginosa, C = Candida albicans, D = Clostridium difficile, E = Influenza A virus H3N2, F = Influenza A virus H1N1, G = Human coronavirus 220E

[0169] Example 12. Evaluation of antibacterial and antifungal activity of coatings of the present technology Similar highly efficient antiviral activity and non-toxicity was observed for coating polymers of the general type of Compound (II) and Compound (III), with various substituents on PEI, as shown below: Polymer (2), fully reacted Polymer (2), and Polymer (3): [ka] Changed in TIFF2024510790000045.tif136159, where: R1=independently hydrogen, alkyl, alkylaryl, arylalkyl, aryl, alkyloxy, carboxy, hydroxyalkyloxyalkyl, and preferably methyl; R2=independently alkyl, arylalkyl, carboxyalkyl, hydroxyalkyl, alkoxyalkyl, hydroxyalkyloxyalkyl, and preferably benzyl, methyl, hexyl, ethyl acetate, ethyl butyrate, and acetophenone; R3=independently alkyl, alkylaryl, aryl, arylalkyl, fluoro or organosilicon substituted, and preferably CH 17 Or C 18 H 37 Long chain alkyl groups such as R4=independently, alkylene, including cyclic alkylene, CH 12 , C7H6, C10 H 17 , C 13 H 10 , or C 13 H 18 and preferably C6H 12 , X- = anionic counter ion to the quaternary ammonium ion such as chloride, bromide, iodide, sulfate, phosphate, borate, etc., and preferably chloride, bromide, and sulfate.

[0170] The percentage of hydroxyl groups converted to monoisocyanates in polymer (2) can range from 20% to 100%, preferably 50% to 95%. The mono-urethane functionalized polymers (2), fully reacted (2), and (3) can be derived from reaction with one or a blend of two or more monoisocyanates, and preferably a blend of octyl isocyanate and octadecyl isocyanate in a molar ratio range of 1 / 9 to 5 / 5, preferably 2 / 8 to 4 / 6. The crosslinking portion shown in polymer (3) is derived from a polyisocyanate alkyl diisocyanate trimer, such as hexamethylene diisocyanate trimer (HDI). Other possible crosslinkers include, but are not limited to, polyisocyanates with an average isocyanate functionality of 2 to 5, preferably from polyisocyanates derived from isophorone diisocyanate (IPDI), toluene isocyanate (TDI), methylene isocyanate (MDI), dicyclohexylmethane-4,4'-diisocyanate (DMDI), and other di-, tri-, and polyisocyanates. The weight percentage of polyisocyanate relative to the partially mono-urethane functionalized polymer (2) to form the crosslinked polymer (3) is preferably in the range of 1% to 30%, more preferably in the range of 3% to 10%. The PEI polymer backbone can be linear, branched, or hyperbranched, and is preferably of average molecular weight (average Mw) in the range of 0.6 to 1,000 kDa, more preferably in the range of 25 to 270 kDa.

[0171] Hydroxyalkyl quaternary ammonium PEI polymers of the type of compound (I) prepared as described above are typically water-soluble. In general, they have shown high antiviral efficiency in solution. Some of these polymers tested have shown a certain level of toxicity to HuH7 cells, and some are non-toxic, depending on the nature of the substituents and counterions.

[0172] Sample preparation and test methods To evaluate the antibacterial activity of the polymer coatings of the present disclosure, the polymer coatings were prepared as described above for the antiviral test. All samples and all accessories for the evaluation were first disinfected by either high temperature autoclaving, alcohol cleaning, or irradiation in a UV laminar flow chamber.

[0173] The test protocol used to determine the antibacterial and antifungal activity was the procedure described in ASTM-E2149-13a, a standard test method for determining the antibacterial activity of antimicrobial agents under dynamic contact conditions.

[0174] Test results When a coating of cross-linked polymeric compound (III) was prepared and tested as described above on the bacteria E. coli, at least 99.9% of the bacteria were killed after overnight incubation at 37° C. Furthermore, as previously described, compound (III) was non-toxic to HuH7 cells.

[0175] Similar highly efficient antibacterial activity and non-toxicity were observed upon coating of polymers of the general type of Compound (II) and Compound (III) with various substituents on PEI as described above.

[0176] Similar highly effective antibacterial activity was observed against other bacteria including Staphylococcus aureus, Pseudomonas aeruginosa, Klebsiella pneumoniae, Andida albicans, Salmonella enterica, and Streptococcus pneumoniae, as well as against the fungus Aspergillus niger.

[0177] In conclusion, the novel antimicrobial polymers of the present technology produce surface coatings that exhibit the following properties: (i) high antimicrobial activity against viruses, bacteria, and fungi, (ii) fast acting, (iii) long lasting, (iv) non-toxic and non-allergenic, (v) no materials leaching from the coating, (vi) colorless and transparent as a surface coating, (vii) easy application to a wide range of surfaces and materials, (viii) durable surface coatings that are resistant to water and common solvents, and (ix) easy and cost-effective to produce. Thus, these novel antimicrobial polymers represent an improved class of antimicrobial polymers.

[0178] References: 1 Ellingson, KD, et al. (2020). “Urban Hospital Study - Antimicrobial Surface Coating.” Clinical Infectious Diseases, 71(8):1807-1813. 2 Jarach, N., et al., (2020). “Polymers in the Medical Antiviral Front-Line”. Polymers, 12(8):1727. 3 THE MERCK MANUAL OF DIAGNOSIS AND THERAPY, (2011).19 th Edition, published by Merck Sharp & Dohme Corp., (ISBN 978-0-911910-19-3). 4 THE ENCYCLOPEDIA OF MOLECULAR CELL BIOLOGY AND MOLECULAR MEDICINE, Robert S. Porter et al.(eds.), published by Blackwell Science Ltd., 1999-2012 (ISBN 9783527600908). 5 MOLECULAR BIOLOGY AND BIOTECHNOLOGY: A COMPREHENSIVE DESK REFERENCE, (1995).Robert A. Meyers (ed.), published by VCH Publishers, Inc.(ISBN 1-56081-569-8). 6 IMMUNOLOGY, (2006).Werner Luttmann, published by Elsevier. 7 JANEWAY’S IMMUNOBIOLOGY, (2014).Kenneth Murphy, Allan Mowat, Casey Weaver (eds.), Taylor & Francis Limited, (ISBN 0815345305, 9780815345305). 8 LEWIN’S GENES XI, (2014). published by Jones & Bartlett Publishers (ISBN-1449659055). 9 Michael Richard Green and Joseph Sambrook, (2012).MOLECULAR CLONING: A LABORATORY MANUAL, 4th ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., USA (ISBN 1936113414). 10Davis et al., (2012).BASIC METHODS IN MOLECULAR BIOLOGY, Elsevier Science Publishing, Inc., New York, USA (ISBN044460149X). 11 LABORATORY METHODS IN ENZYMOLOGY: DNA, (2013).Jon Lorsch (ed.) Elsevier (ISBN 0124199542). 12 CURRENT PROTOCOLS IN MOLECULAR BIOLOGY (CPMB), (2014).Frederick M. Ausubel (ed.), John Wiley and Sons (ISBN 047150338X, 9780471503385). 13 CURRENT PROTOCOLS IN PROTEIN SCIENCE (CPPS), (2005).John E. Coligan (ed.), John Wiley and Sons, Inc. 14 CURRENT PROTOCOLS IN IMMUNOLOGY (CPI) (2003).Coligan, J.E., et al., (eds.)John Wiley and Sons, Inc.(ISBN 0471142735, 9780471142737). 15 Ikonen, N., et al., (2018).“Deposition of respiratory virus pathogens on frequently touched surfaces at airports.”BMC Infectious Diseases, 18(437):1-8. 16Geczi, Z., et al., (2018).“Antimicrobial Silver-Polyethyleneimine Polylactic Acid Polymer Composite Film for Coating Methacrylate-Based Denture Surfaces.”J.of Nanomaterials, 2018(6):1-9. 17 Park, D., et al., (2006).“One-Step, Painting-Like Coating Procedures To Make Surfaces Highly and Permanently Bactericidal.”Biotechnology Prog.22(2):584-589. 18 Xue, Y. and Xiao, H. (2015).“Antibacterial / Antiviral Property and Mechanism of Dual-Functional Quaternized Pyridinium-Type Copolymer.”Polymers, 7(11):2290-2303. 19 U.S.Patent No.5,783,502, “Virus Inactivating Coatings.”(Issued July 21, 1998). 20 Nurdin, N., et al., (1993).“Biocidal Polymers Active By Contact.II.Biological Evaluation of Polyurethane Coatings with Pendent Quaternary Ammonium Salts.”J.of Applied Polymer Science, 50:663-670. 21Chung, S., et al., (2016).“Antimicrobial Nanostructural Polyurethane Scaffolds.”Ch.17 in ADVANCES IN POLYURETHANE BIOMATERIALS, Cooper S.L. and Guan, J.(eds.), Elsevier Ltd. 22 Park, D., et al., (2013).“Antiviral and Antibacterial Polyurethanes of Various Modalities.”Appl.Biochem.Biotechnol., 169:1134-1146. 23 Gao, B., et al., (2007).“Studies on the Preparation and Antibacterial Properties of Quaternized Polyethyleneimine.”J.Biomaterials Science, Polymer Edition, 18(5):531-544. 24 Klibanov, A., et al., (2006).“One-Step Painting-Like Coating Procedures to make Surfaces Highly and Permanently Bactericidal.”Biotechnol.Prog., 22(2):584-589. 25 Gao, B., et al., (2007).“Studies on the Preparation and Antibacterial Properties of Quaternized Polyethyleneimine.”J.Biomaterials Science, Polymer Edition, 18(5):531-544. 26 Id.

[0179] All patents and other publications, including literature references, issued patents, published patent applications, and co-pending patent applications, are expressly incorporated herein by reference for the purpose of describing and disclosing, for example, the methodologies described in such publications that may be used in connection with the technology described herein. These publications are provided solely for their disclosure prior to the filing date of this application. Nothing in this regard should be construed as an admission that the present invention is not entitled to antedate such disclosure by virtue of prior invention or for any other reason. All statements as to the date or representation as to the contents of these documents are based on the information available to the applicant and do not constitute any admission as to the accuracy of the dates or contents of these documents.

[0180] The foregoing written specification is believed to be sufficient to enable one skilled in the art to practice the present aspects and embodiments. The present aspects and embodiments are not limited in scope by the examples provided, as the examples are intended to be merely illustrative of an embodiment, and other functionally equivalent embodiments are within the scope of the present disclosure. In addition to those shown and described herein, various modifications will be apparent to those skilled in the art from the foregoing description and are encompassed within the scope of the appended claims. The advantages and objectives described herein are not necessarily encompassed by each embodiment. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, many equivalents to the specific embodiments described herein. Such equivalents are intended to be encompassed by the following claims. [Sequence List Free Text]

[0181] SEQ ID NO:1 is a description of the artificial sequence: synthetic primer. SEQ ID NO:2 is a description of the artificial sequence: synthetic primer.

Claims

1. Compound (IV): 【Chemistry 1】 1. An antimicrobial composition comprising: Each A independently: 【Chemistry 2】 or a copolymer of any two or more thereof, wherein the bond at each A forms a carbamate bond; Each Y is independently H or —C(O)—NHR ３ and each n is an integer independently selected from 1 to 3000; each R 1 is independently hydrogen; C 1 -C 6 alkyl optionally substituted with a substituent selected from C 6 -C 10 aryl, and C 1 -C 6 alkoxy optionally substituted with hydroxy; C 1 -C 6 alkoxy; C 6 -C 10 aryl optionally substituted with C 1 -C 6 alkyl; and carboxy; Each R ２ are independently hydroxy, C １ -C ６ Alkoxy, carboxy, C ６ -C １０ Aryl, —C(O)O(C １ -C ６ alkyl), —C(O)—(C ６ -C １０ aryl), and C optionally substituted with hydroxy １ -C ６ C optionally substituted with a substituent selected from alkoxy １ -C ６ alkyl, Each R ３ are independently: (1) halogen, —SiR ａ (OR ｂ ) (OR ｃ ), and C ６ -C １０ C optionally substituted with 1 to 3 substituents independently selected from aryl ６ -C ２０ Alkyl, (2) halogen, C １ -C ６ Alkyl, and —SiR ａ (OR ｂ ) (OR ｃ C optionally substituted with 1 to 3 substituents independently selected from ６ -C １０ aryl, and (3) 【Transformation 3】 wherein each R ａ But independently, C １ -C ６ alkyl, and each R ｂ and each R ｃ But independently, C １ -C ６ Alkyl and -Si(C １ -C ６ alkyl) ３ is selected from Each R ４ is independently C optionally substituted with phenyl １ -C １０ alkylene or a 3- to 8-membered cycloalkyl ring; Each X － are independently selected from the group consisting of acetates, halides, sulfates, sulfonates, phosphoric acids, phosphonic acids, carbonates, silicic acids, hexafluorophosphates, hexafluoroantimonic acids, and borates, and organically substituted derivatives thereof.

2. Compound (V): 【Chemistry 4】 1. An antimicrobial composition comprising: Each A independently: 【Transformation 5】 or a copolymer of any two or more thereof, wherein the bond at each A forms a carbamate bond; Each Y is independently H or —C(O)—NHR ３ and each n is an integer independently selected from 1 to 3000; each R 1 is independently hydrogen; C 1 -C 6 alkyl optionally substituted with a substituent selected from C 6 -C 10 aryl, and C 1 -C 6 alkoxy optionally substituted with hydroxy; C 1 -C 6 alkoxy; C 6 -C 10 aryl optionally substituted with C 1 -C 6 alkyl; and carboxy; Each R ２ are independently hydroxy, C １ -C ６ Alkoxy, carboxy, C ６ -C １０ Aryl, —C(O)O(C １ -C ６ alkyl), —C(O)—(C ６ -C １０ aryl), and C optionally substituted with hydroxy １ -C ６ C optionally substituted with a substituent selected from alkoxy １ -C ６ alkyl, Each R ３ are independently: (1) halogen, —SiR ａ (OR ｂ ) (OR ｃ ), and C ６ -C １０ C optionally substituted with 1 to 3 substituents independently selected from aryl ６ -C ２０ Alkyl, (2) halogen, C １ -C ６ Alkyl, and —SiR ａ (OR ｂ ) (OR ｃ C optionally substituted with 1 to 3 substituents independently selected from ６ -C １０ aryl, and (3) 【Transformation 6】 wherein each R ａ But independently, C １ -C ６ alkyl, and each R ｂ and each R ｃ But independently, C １ -C ６ Alkyl and -Si(C １ -C ６ alkyl) ３ is selected from Each R ４ is independently C optionally substituted with phenyl １ -C １０ alkylene or a 3- to 8-membered cycloalkyl ring; Each X － are independently selected from the group consisting of acetates, halides, sulfates, sulfonates, phosphoric acids, phosphonic acids, carbonates, silicic acids, hexafluorophosphates, hexafluoroantimonic acids, and borates, and organically substituted derivatives thereof.

3. The R ３ at least 75% but not all of the ａ (OR ｂ ) (OR ｃ ), and C ６ -C １０ C optionally substituted with 1 to 3 substituents independently selected from aryl ６ -C ２０ Alkyl; and halogen, C １ -C ６ Alkyl, and —SiR ａ (OR ｂ ) (OR ｃ C optionally substituted with 1 to 3 substituents independently selected from ６ -C １０ aryl, wherein each R ａ But independently, C １ -C ６ alkyl, and each R ｂ and each R ｃ But independently, C １ -C ６ Alkyl and -Si(C １ -C ６ alkyl) ３ The antimicrobial composition according to claim 1 or 2, wherein the antimicrobial composition is selected from the group consisting of:

4. Each R ３ are independently halogen, —SiR ａ (OR ｂ ) (OR ｃ ), and C ６ -C １０ C optionally substituted with 1 to 3 substituents independently selected from aryl ６ -C ２０ alkyl, or each R ３ are independently halogen, C １ -C ６ Alkyl, and —SiR ａ (OR ｂ ) (OR ｃ C optionally substituted with 1 to 3 substituents independently selected from ６ -C １０ 3. The antimicrobial composition of claim 1, wherein the aryl is selected from the group consisting of aryl, aryl, aryls ...

5. R ３ but, 【Transformation 7】 2. The antimicrobial composition of claim 1, wherein:

6. R ３ but, 【Transformation 8】 3. The antimicrobial composition of claim 2, wherein

7. Each R １ But independently, C １ -C ６ The antimicrobial composition of claim 1 or 2, wherein the alkyl group is alkyl.

8. Each R ２ are independently methyl, butyl, hexyl, benzyl, -CH ２ C(O)Ph, and -CH ２ C(O)OCH ２ CH ３ The antimicrobial composition according to claim 1 or 2, wherein the antimicrobial composition is selected from the group consisting of:

9. R ４ But C １ -C １０ 3. The antimicrobial composition of claim 1, wherein the alkylene is alkylene.

10. An antimicrobial coating comprising the composition of claim 1 or 2.

11. A coating fluid comprising the composition of claim 1 or 2.

12. A device comprising the coating fluid of claim 11.

13. The device of claim 12 , wherein the device is selected from the group consisting of a keyboard, a keypad, a mouse, a remote control, a touch screen, a telephone, and a display.

14. 14. The device of claim 12 or 13, wherein the coating fluid is water-soluble, water-dispersible, alcohol-soluble, or alcohol-dispersible.

15. A device comprising the antimicrobial coating of claim 10.

16. 16. The device of claim 15, wherein the device is selected from the group consisting of a filter, an air purifier, and a mask.

17. 10. A method of disinfecting a surface, reducing antimicrobial growth on said surface, or preventing antimicrobial growth on said surface, comprising applying to said surface a composition according to claim 1 or 2.

18. 20. The method of claim 17, further comprising forming a coating solution containing the composition.

19. 20. The method of claim 18, further comprising directing the coating solution to the surface and providing a coating on the surface through the application of the coating solution to the surface.

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