Antimicrobial microfibers from electrospinning

Abstract

Microfibers and nanofibers containing quaternary ammonium polymers and / or interpenetrating polymer networks are provided. For example, a microfiber or nanofiber including a blend, composite, or interpenetrating polymer network is provided. The blend, composite or interpenetrating polymer network can include (i) a polyethyleneimine intermediate, in which the polyethyleneimine intermediate includes a reaction product of reagents including a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate that are partially or completely quaternized by the one or more alkylating agents; and (ii) a hydroxy-functionalized oligomer, polymer, or copolymer including pendant and / or terminal hydroxy group(s).

Description

[0001] Atty. Dkt. No. 136938-0902

[0002] ANTIMICROBIAL MICROFIBERS FROM ELECTROSPINNING

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] [1] The present application claims priority to U. S. Patent Application No. 63 / 720511 filed November 14, 2024, the entire contents of which are incorporated herein by reference.

[0005] FIELD

[0006] [2] The embodiments of the present disclosure relate to antimicrobial microfibers comprising quaternary ammonium polymer structures with broad spectrum antimicrobial properties, and methods of their production.

[0007] BACKGROUND

[0008] [3] Melt-spinning processes are typically conducted at high temperature (160-210 °C) and therefore are not suitable for antibacterial fibers with a low degradation temperature. Moreover, the specific surface area or the surface area / volume ratio of a melt-spun fiber tends to be quite low and a significant part of the antimicrobial functional group may be trapped inside the fiber, thereby resulting in a lower antimicrobial efficiency. To avoid degradation during the high temperature melt-spinning process, an antibacterial agent may be applied (e.g., by coating, spraying, dipping, or impregnation techniques) after fiber formation; however, degradation of the antimicrobial efficiency may still occur due to loss or leaching of the antimicrobial agent from the treated fibers.

[0009] [4] Some of the disadvantages such as high processing temperature and low specific surface area of melt-spun antimicrobial fibers may be resolved by wet-spinning and / or electro-spinning processes. However, the processing window, particularly the green-time of the crosslinking reactions of the antimicrobial compositions, and / or the physico-mechanical properties of the resultant fibers may still be insufficient for many applications.

[0010] [5] There is a need in the art for improved antimicrobial fibers (e.g., microfibers or nanofibers). The present disclosure satisfies this need by addressing the problems described above.

[0011] SUMMARY

[0012] [6] Described herein are antimicrobial microfibers and nanofibers prepared using electrospinning processes of a wide processing window and a long crosslinking green-time Atty. Dkt. No. 136938-0902

[0013] window which effectively increases the specific surface area of the microfibers / nanofibers and reduces processing temperature.

[0014] [7] In one aspect, described herein is a microfiber or nanofiber comprising a blend, composite, or interpenetrating polymer network comprising:

[0015] (1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents; and

[0016] (2) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

[0017] [8] In some embodiments, the polyethyleneimine intermediate and the hydroxyfunctionalized oligomer, polymer, or copolymer are non-covalently blended together.

[0018] [9] In another aspect, described herein is a microfiber or nanofiber comprising a polymer or interpenetrating polymer network comprising a polymerization / crosslinking product of reagents comprising:

[0019] (1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents;

[0020] (2) a multifunctional crosslinker; and

[0021] (3) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

[0022]

[0010] In another aspect, described herein is a microfiber or nanofiber comprising a polymer or interpenetrating polymer network comprising a polymerization / crosslinking product of reagents comprising:

[0023] (1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one Atty. Dkt. No. 136938-0902

[0024] or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents;

[0025] (2) an adduct of a quaternary ammonium salt and a multifunctional crosslinker; and (3) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

[0026]

[0011] In some embodiments, the polymer or interpenetrating polymer network are comprised in a blend or composite within the microfiber or nanofiber. In some embodiments, the polymer is comprised in an interpenetrating polymer network within the microfiber or nanofiber.

[0027]

[0012] In some embodiments, the polyethyleneimine intermediate is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 50 wt.%. In some embodiments, the polyethyleneimine intermediate is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 10 wt.%.

[0028]

[0013] In some embodiments, the polyethyleneimine intermediate comprises hydroxyalkylene functionality. In some embodiments, the hydroxyalkylene functionality is optionally substituted with Ci-Ce alkyl optionally substituted with a substituent selected from -N+(R20)3X-, -(C6-C10aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH, -(Ci-Ce alkoxy), -(C6-C10aryl) optionally substituted with -(Ci-Ce alkyl), and carboxy; each R20is independently selected from a group consisting of C1-C18 alkyl; C1-C18 heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10aryl optionally substituted with -(C1-C6alkyl), -(Ci-Ce alkoxy), -C(O)O-(Ci-Ce alkyl), -C(O)NH(CI-C6alkyl), -C(O)N(CI-C6alkyl)2, or -OC(O)-(Ci-C6alkyl); and each X- is independently selected from a group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives. In some embodiments, the hydroxyalkylene functionality is hydroxyethylene, hydroxypropylene, hydroxybutylene, or an oligomer thereof.

[0029]

[0014] In some embodiments, the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and two alkylating agents. In some embodiments, the one or more alkylating agents, which introduce hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate, comprise a hydroxyl group. In some embodiments, the one or more alkylating agents, which introduce hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate, comprise a primary hydroxyl group. In some embodiments, the one or more Atty. Dkt. No. 136938-0902

[0030] alkylating agents, which introduce hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate, comprise a spacer of at least three carbon atoms between a leaving group and the hydroxyl group.

[0031]

[0015] In some embodiments, at least one of the one or more alkylating agents is selected from a group consisting of a mono-epoxide, lactone, and R21-LG, wherein:

[0032] the mono-epoxide is optionally substituted with:

[0033] (i) Ci-Ce alkyl optionally substituted with a substituent selected from -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with hydroxy, Ci-Ce alkoxy, C6-C10aryl optionally substituted with Ci-Ce alkyl, and carboxy; or

[0034] (ii) -(Ci-Ce alkyl)-N+(R20)3X-; each R20is independently selected from a group consisting of Ci-Cw alkyl; Ci-Cw heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and Ce-Cw aryl optionally substituted with -(Ci-Ce alkyl), -(Ci-Ce alkoxy), -C(O)O-(Ci-C6alkyl), -C(O)NH(Ci-Ce alkyl), -C(O)N(Ci-Ce alkyl)2, or-OC(O)-(Ci-Ce alkyl); and each X' is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives; and

[0035] each R21is independently selected from Ci-Ce alkyl optionally substituted with a substituent selected from -OH, -(Ci-Ce alkoxy), carboxy, -(Ce-Cw aryl), -C(O)O(Ci-Ce alkyl), -C(O)-(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH; and each LG is a leaving group. In some embodiments, the leaving group is selected from a group consisting of iodide, bromide, chloride, mesylate, tosylate, nonaflate, and triflate. In some embodiments, at least one of the one or more alkylating agents is selected from R21-LG. In some embodiments, the one or more alkylating agents comprise a C1-C6 alkyl halide and a haloalkanol, wherein the haloalkanol is X30-(C2-C6 alkylene)-OH, wherein X30is Cl, Br, or I. In some embodiments, the one or more alkylating agents comprise 1-bromohexane and 3-bromopropanol. In some embodiments, the lactone is caprolactone or butyrolactone.

[0036]

[0016] In some embodiments, the polyethyleneimine intermediate is selected from

[0037]

[0038] Atty. Dkt. No. 136938-0902

[0039]

[0040] copolymer of any two or more thereof, wherein:

[0041] each Y3is independently H or -OH, wherein every Y3cannot be H;

[0042] each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000;

[0043] Z is -(C2-C6 alkylene)-;

[0044] each R10is independently selected from hydrogen; Ci-Ce alkyl optionally substituted with a substituent selected from -N(R20)3, -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH, -(Ci-Ce alkoxy), -(C6-C10aryl) optionally substituted with -(Ci-Ce alkyl), and carboxy; and each R20is independently selected from a group consisting of C1-C18 alkyl; C1-C18 heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and Ce-Cw aryl optionally substituted with -(Ci-Ce alkyl), -(Ci-Ce alkoxy), -C(O)O-(Ci-C6alkyl), -C(O)NH(Ci-Cealkyl), -C(O)N(Ci-Cealkyl)2, or -OC(O)-(Ci-C6alkyl);

[0045] each R21is independently selected from C1-C6alkyl optionally substituted with a substituent selected from -OH, -(C1-C6alkoxy), carboxy, -(C6-C10aryl), -C(O)O(C1-C6alkyl), -C(O)-(C6-C10aryl), and -(C1-C6alkoxy) optionally substituted with -OH;

[0046] each R30is independently selected from (1) C6-C20 alkyl optionally substituted with 1-3 substituents independently selected from halogen, -SiRa(ORb)(ORc), and -(C6-C10 aryl); and (2) C6-C10 aryl optionally substituted with 1-3 substituents independently selected from halogen, -(C1-C6 alkyl), and -SiRa(ORb)(ORc); wherein each Rais independently - (Ci-Ce alkyl); and each Rband each Rcare independently selected from -(Ci-Ce alkyl) and -Si(Ci-Ce alkyl)3; and

[0047] each X’ is independently selected from a group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives. Atty. Dkt. No. 136938-0902

[0048]

[0017] In some embodiments, the polyethyleneimine has a molecular weight of about 300 to about 270,000 daltons. In some embodiments, the polyethyleneimine has a molecular weight of about 10,000 to about 200,000 daltons. In some embodiments, the polyethyleneimine has a molecular weight of about 25,000 to about 120,000 daltons.

[0049]

[0018] In some embodiments, the polyethyleneimine is branched. In some embodiments, the polyethyleneimine is hyperbranched. 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 polyethyleneimine is QPEI-C3OHC6.

[0050]

[0019] In another aspect, described herein is a microfiber or nanofiber comprising polymer or interpenetrating polymer network comprising a polymerization / crosslinking product of reagents comprising:

[0051] (1) an adduct of a quaternary ammonium salt and a multifunctional crosslinker; and (2) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

[0052] In some embodiments, the polymer or interpenetrating polymer network are comprised in a blend or composite within the microfiber or nanofiber. In some embodiments, the polymer is comprised in an interpenetrating polymer network within the microfiber or nanofiber.

[0053]

[0020] In some embodiments, the quaternary ammonium salt has a chemical structure of R1v- R2U +X

[0054]

[0055] RA, wherein:

[0056] R1is selected from a group consisting of -(Cs-Cso alkyl), -(Cs-Cso heteroalkyl), -(Cs-Cso heteroalkyl)-(Ce-Cio aryl), -(Ce-Cw aryl), -(Ce-Cw aryl)-(Cs-C3o alkyl), -(Ce-Cw aryl)-(Cs- C3o heteroalkyl), -(CRmRn)xw-W10-(CRPRc’)yw-H, and -(CRmRn)xn-W11-(CRPRc’)yiiH-; wherein -(Cs-Cso heteroalkyl), -(Cs-Cso heteroalkyl)-(Cs-Cio aryl), and -(Ce-Cw aryl)-(Cs- C30 heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;

[0057] R2is selected from a group consisting of -(C1-C4 alkyl), -(C1-C4 heteroalkyl), -(C1-C4 heteroalkyl)-(Ce-Cw aryl), -(Ce-Cw aryl), -(Ce-Cw aryl)-(Ci-C4 alkyl), -(Ce-Cw aryl)-(Ci-C4 heteroalkyl); -(CRmRn)X2o-W2O-(CRPRc’)y2o-H, and -(CRmRn)X2i-21-(CRPRc’)y2i-H; wherein -(C1-C4 heteroalkyl), -(Ci-C4heteroalkyl)-(Ce-Cw aryl), and -(Ce-Cw aryl)-(Ci-C4 heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;

[0058] R3is selected from a group consisting of -(C1-C30 alkyl), -(C1-C30 heteroalkyl), -(C1-C30 heteroalkyl)-(Ce-Cw aryl), -(Ce-Cw aryl), -(Ce-Cw aryl)-(Ci-Cso alkyl), -(Ce-Cw aryl)-(Cr Atty. Dkt. No. 136938-0902

[0059] C30heteroalkyl), -(CRmRn)x30-W30-(CRpRq)y30-H, and -(CRmRn)x31-W31-(CRpRq)y31-H; wherein -(C1-C30 heteroalkyl), -(C1-C30 heteroalkyl)-(Ce-Cw aryl), and -(Ce-Cw aryl)-(Ci- C30 heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;

[0060] A is a linking group selected from a group consisting of -(C3-C20 alkylene)-, -(C3-C20 heteroalkylene)-, -(C6-C10arylene)-(Cs-C2o alkylene)-, -(CRmRn)X4o-W4O-(CRPRc’)y4o-, and -(CRmRn)x4i-W41-(CRPRq)y4i-, wherein -(C3-C20 heteroalkylene)- has 1 to 4 heteroatoms independently selected from O, S, and Si; and -(C3-C20 alkylene)- and -(C3-C20 heteroalkylene)- are optionally substituted with 1 to 6 substituents independently selected from -(C6-Cw aryl)-(Ci-C3alkyl), -(C6-C aryl)-(Ci-C3 heteroalkyl), -(C1-C3 alkyl)-(C6-C aryl), -(C1-C3 heteroalkyl)-(C6-C aryl), and -(C6-C aryl);

[0061] each Rm, Rn, RP, and Rqis independently selected from H and C1-C4 alkyl;

[0062] W10, W20, W30, and W40are independently selected from -C(O)-; -C(O)O-; -OC(O)-; -C(O)NH-; and -NHC(O)-;

[0063] W11, W21, W31, and W41are independently selected from 5- to 6-membered cycloalkyl, Ce-Cw aryl, 5- to 6-membered heterocycloalkyl, and 5- to 6-membered heteroaryl, wherein the heterocycloalkyl contains 1-2 ring heteroatoms selected from O, N, S, and Si; and the heteroaryl contains 1-3 ring heteroatoms selected from O, N, S, and Si;

[0064] x10 is an integer from 1 to 30 and y10 is an integer from 0 to 29, wherein 8 ≤ (x10 + y10) ≤ 30;

[0065] x11 is an integer from 1 to 30 and y11 is an integer from 0 to 29, wherein 8 ≤ (x11 + y11) ≤ 30;

[0066] x20 is an integer from 1 to 4 and y20 is an integer from 0 to 3, wherein x20 + y20 ≤ 4;

[0067] x21 is an integer from 1 to 4 and y21 is an integer from 0 to 3, wherein x21 + y21 ≤ 4;

[0068] x30 is an integer from 1 to 30 and y30 is an integer from 0 to 29, wherein x30 + y30 ≤ 30;

[0069] x31 is an integer from 1 to 30 and y31 is an integer from 0 to 29, wherein x31 + y31 ≤ 30;

[0070] x40 is an integer from 1 to 19 and y40 is an integer from 1 to 19, wherein 3 ≤ (x40 + y40) ≤ 20;

[0071] x41 is an integer from 1 to 20, and y41 is an integer from 0 to 19, wherein 3 ≤ (x41 + y41) ≤ 20; Atty. Dkt. No. 136938-0902

[0072] Y is selected from a group consisting of -OH, -NHR4, -SH, -CO2H, -C(O)NHR4, -C(S)NHR4,

[0073] R4

[0074]

[0075] R4R4, and Rc ' R4;

[0076] each R4is independently selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-Cs alkyl), - (Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(Ci-C3alkyl)-(Ce-Cwaryl), -(Ci-C3heteroalkyl)-(Ce-Cw aryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroalkyl)-(Ce-Cw aryl) have 1 to 4 heteroatoms independently selected from O, S, and Si; and

[0077] X’ is independently acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, borate, or an organo- substituted derivative of any of the foregoing.

[0078]

[0021] In some embodiments, R1is selected from a group consisting of -(C12-C30 alkyl), -(C12-C30 heteroalkyl), -(Ci2-C3oalkyl)-(Ce-Cw aryl), -(C12-C30 heteroalkyl)-(Ce-Cw aryl), -(Ce-Cw aryl)-(Ci2-Cso alkyl), and -(Ce-Cw aryl)-(Ci2-Cso heteroalkyl); wherein -(C12-C30 heteroalkyl), -(C12-C30 heteroalkyl)-(Ce-Cw aryl), and -(Ce-Cw aryl)-(Ci2-Cso heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si.

[0079]

[0022] In some embodiments, R3is selected from a group consisting of -(C1-C4 alkyl), -(C1-C4heteroalkyl), -(Ci-C4alkyl)-(Ce-Cw aryl), -(C1-C4 heteroalkyl)-(C6-Cw aryl), -(C6-Cw aryl)-(C1-C4 alkyl), and -(Ce-Cw aryl)-(Ci-C4 heteroalkyl); wherein -(C1-C4 heteroalkyl), -(C1-C4 heteroal kyl)-(Ce-Cw aryl), and -(Ce-Cw aryl)-(Ci-C4 heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si.

[0080]

[0023] In some embodiments, R2and R3are methyl.

[0081]

[0024] In some embodiments, A is -(CH2)m- or -(CH2CHR5-O-)nCH2CHR5-, wherein m is an integer from 2 to 20; n is 0, 1, 2, 3, 4, or 5; and each R5is independently selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-Cs alkyl), -(Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(C1-C3 alkyl)-(Ce-Cwaryl), -(Ci-C3heteroalkyl)-(Ce-Cwaryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroal kyl)-(Ce-Cw aryl) have 1 to 4 heteroatoms independently selected from O, S, and Si.

[0082]

[0025] In some embodiments, R5is H or methyl. Atty. Dkt. No. 136938-0902

[0083] ^18^37^ ' + Bl"

[0084]

[0026] In some embodiments, the quaternary ammonium salt is

[0085]

[0086] C18H37X C16H33

[0087] C16H33 | Br"

[0088] C14H29 I+Br" C14H29- CI2H25 I+Br"

[0089]

[0090] O

[0091] C12H25J+Br

[0092] / \ X)H

[0093]

[0094] O, or a combination of two or more thereof.

[0095]

[0027] In some embodiments, the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of about 5 wt.% to about 50 wt.%. In some embodiments, the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of about 1.0 x10-4to about 1.2 x10-3mole of the quaternary ammonium group per gram of the dried microfiber or the dried nanofiber.

[0096]

[0028] In some embodiments, the multifunctional crosslinker is present in the dried microfiber or dried nanofiber in an amount of about 3 wt.% to about 20 wt.%. In some embodiments, the multifunctional crosslinker is a multifunctional isocyanate, isothiocyanate, epoxide, or a precursor thereof. In some embodiments, the multifunctional crosslinker is a polyisocyanate.

[0097]

[0029] In some embodiments, the polyisocyanate has an average isocyanate functionality of 2 to 5 or 3 to 4. In some embodiments, the polyisocyanate is prepared from a diisocyanate independently selected from a group consisting of hexamethylene diisocyanate (H DI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylenediisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), metatetramethylxylene diisocyanate (TMXDI ), and trimethylhexamethylene diisocyanate (TMDI). In some embodiments, the polyisocyanate is selected from a group consisting of DESMODUR® N-3300, DESMODUR® N-100, DESMODUR® Z4470SN, WANNATE® T series polyisocyanates, and LUPRANATE® M series polyisocyanates.

[0098]

[0030] In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is a polymer, copolymer or oligomer of a hydroxy-functionalized monomer or a precursor thereof selected from a group consisting of ethylene oxide, propylene oxide, tetrahydrofuran (THF), caprolactone, butyrolactone, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N- methylol acrylamide, N-methylol methacryamide, allyl alcohol, triethanol amine, diethanol alkylamine, and N, N, N’N’-tetrakis(2-hydroxyalkyl) ethylenediamine. In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is a copolymer of 2-hydroxyethyl methacrylate. Atty. Dkt. No. 136938-0902

[0099]

[0031] In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 300 to about 100,000. In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 400 to about 10,000. In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 600 to about 3,000. In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 20 wt.%.

[0100]

[0032] In some embodiments, (1) the polyethyleneimine intermediate and the quaternary ammonium salt are present in the dried microfiber or dried nanofiber in a combined amount of less than 35 wt.%; or (2) in the absence of any polyethyleneimine intermediate, the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of less than 35 wt.%.

[0101]

[0033] In some embodiments, (1) the polyethyleneimine intermediate and the quaternary ammonium salt are present in a combined amount of less than 1.2 x10-3mole of the quaternary ammonium group per gram of the dried polymer or interpenetration network, or (2) in the absence of any polyethyleneimine intermediate, the quaternary ammonium salt is present in an amount of less than 1.2 x10-3mole of the quaternary ammonium group per gram of the dried microfiber or dried nanofiber.

[0102]

[0034] In some embodiments, the adduct further comprises a chain extender (i.e., the adduct is a reaction product of the quaternary ammonium salt, the multifunctional crosslinker, and the chain extender). In some embodiments, the chain extender comprises, consists essentially of, or consists of polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), or a combination of two or more thereof, or a copolymer of one or more thereof with polyester, polycaprolactone, polybutadiene, poly(acrylonitrile-butadiene), polysiloxane, or polyacrylate. In some embodiments, the chain extender is selected from a group consisting of poly(tetramethylene glycol), polyethylene glycol, polypropylene glycol, poly(ethylene glycol-b-propylene glycol-b-ethylene glycol), and polypropylene glycol-b-polyethylene glycol-b-propylene glycol). In some embodiments, the chain extender is PTMG.

[0103]

[0035] In some embodiments, the microfiber or nanofiber further comprises covalent attachment of a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof. Atty. Dkt. No. 136938-0902

[0104]

[0036] In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is present in the microfiber or the nanofiber in an amount of about 25 wt.% to about 50 wt.%.

[0105]

[0037] In some embodiments, the microfiber or the nanofiber has a total quaternary ammonium salt density of at least 3.0 x10-4mole, preferably at least 5.0 x10-4mole, of total quaternary ammonium salt functionality per gram of dried microfiber or dried nanofiber.

[0106]

[0038] In some embodiments, the microfiber or the nanofiber is a core-shell microfiber or nanofiber.

[0107]

[0039] In some embodiments, quaternary ammonium salt density of the shell is different from quaternary ammonium salt density of the core. In some embodiments, quaternary ammonium salt density of the shell is higher than quaternary ammonium salt density of the core.

[0108]

[0040] In another aspect, described herein is a nonwoven fabric comprising the microfiber or nanofiber disclosed herein. In some embodiments, the nonwoven fabric has a coverage of microfibers or nanofibers of at least 3 g / m2, preferably at least 5 g / m2. In some embodiments, the nonwoven fabric is deposited on a support to form a composite nonwoven fabric. In some embodiments, the support is a non-antimicrobial nonwoven fabric having a coverage of microfibers or nanofibers of at least 3 g / m2, preferably at least 5 g / m2. In some embodiments, the support is a second nonwoven fabric with the same coverage of microfibers or nanofibers as the nonwoven fabric. In some embodiments, the support is a second nonwoven fabric with different coverage of microfibers or nanofibers compared to the nonwoven fabric. In some embodiments, the support is a second nonwoven fabric with the same quaternary ammonium salt density as the nonwoven fabric. In some embodiments, the support is a second nonwoven fabric with different quaternary ammonium salt density compared to the nonwoven fabric.

[0109]

[0041] In another aspect, described herein is an apparatus or accessory comprising the nonwoven fabric disclosed herein. In some embodiments, the apparatus or accessory is selected from a group consisting of a filter, a mask, a membrane, a diaper, a wound care dressing, a super absorbent, a humectant, a synthetic skin, a synthetic organ, a skincare product, and a scaffold for controlled release of a fertilizer, a nutritional supplement, a pesticide, or a pharmaceutically active agent. In some embodiments, the wound care dressing comprises a film, a gel, a matrix product, a wound therapy system, a placental membrane, a non-silver wound dressing product, a negative-pressure wound therapy system, a surgical dressing, an adhesive antimicrobial dressing, a barrier dressing, an adhesive or non-adhesive hydrocellular foam dressing, a gelling fiber wound dressing, or a low adherent absorbent dressing.

[0110]

[0042] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a solution comprising (1) the Atty. Dkt. No. 136938-0902

[0111] polyethyleneimine intermediate, and (2) the hydroxy-functionalized oligomer, polymer, or copolymer; and electrospinning the solution to form the microfiber or nanofiber.

[0112]

[0043] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the multifunctional crosslinker; and (3) the hydroxyfunctionalized oligomer, polymer, or copolymer; and electrospinning the solution to form the microfiber or nanofiber.

[0113]

[0044] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the adduct of the quaternary ammonium salt, the multifunctional crosslinker, and optionally the chain extender; and (3) the hydroxyfunctionalized oligomer, polymer, or copolymer; and electrospinning the solution to form the microfiber or nanofiber. In some embodiments, the solution further comprises a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof; and optionally a catalyst selected from a group consisting of citric acid, oxalic acid, and XK-651 (bismuth carboxylate catalyst).

[0114]

[0045] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the adduct of the quaternary ammonium salt and the multifunctional crosslinker; and (3) the hydroxy-functionalized oligomer, polymer, or copolymer; and electrospinning the solution to form the microfiber or nanofiber. In some embodiments, the adduct further comprises a chain extender (e.g., PTMG such as PTMG-1000). In some embodiments, the solution further comprises a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof; and optionally a catalyst selected from a group consisting of citric acid, oxalic acid, and XK-651 (bismuth carboxylate catalyst).

[0115]

[0046] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the adduct of the quaternary ammonium salt, the multifunctional crosslinker, and the chain extender; and (3) the hydroxy-functionalized oligomer, polymer, or copolymer; and electrospinning the solution to form the microfiber or Atty. Dkt. No. 136938-0902

[0116] nanofiber. In some embodiments, the solution further comprises a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof; and optionally a catalyst selected from a group consisting of citric acid, oxalic acid, and XK-651 (bismuth carboxylate catalyst).

[0117]

[0047] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a first solution comprising (1) the polyethyleneimine intermediate; and (2) the adduct of the quaternary ammonium salt, the multifunctional crosslinker, and optionally the chain extender; preparing a second solution comprising the hydroxy-functionalized oligomer, polymer, or copolymer; and combining the first solution and the second solution via in-line mixing to form a third solution; and electrospinning the third solution to form the microfiber or nanofiber.

[0118]

[0048] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a first solution comprising (1) the polyethyleneimine intermediate; and (2) the adduct of the quaternary ammonium salt and the multifunctional crosslinker; preparing a second solution comprising the hydroxyfunctionalized oligomer, polymer, or copolymer; and combining the first solution and the second solution via in-line mixing to form a third solution; and electrospinning the third solution to form the microfiber or nanofiber. In some embodiments, the adduct further comprises a chain extender (e.g., PTMG such as PTMG-1000).

[0119]

[0049] In another aspect, described herein is a method to prepare the microfiber or nanofiber disclosed herein, the method comprising: preparing a first solution comprising (1) the polyethyleneimine intermediate; and (2) the adduct of the quaternary ammonium salt, the multifunctional crosslinker, and the chain extender; preparing a second solution comprising the hydroxy-functionalized oligomer, polymer, or copolymer; and combining the first solution and the second solution via in-line mixing to form a third solution; and electrospinning the third solution to form the microfiber or nanofiber.

[0120]

[0050] In some embodiments, the microfiber or nanofiber has a total quaternary ammonium salt density of at least 3.0 x10-4mole of total quaternary ammonium salt functionality per gram of dried microfiber or dried nanofiber. In some embodiments, the hydroxyfunctionalized oligomer, polymer, or copolymer is present in the dried microfiber or dried nanofiber in an amount of about 20 wt.% to about 50 wt.%.

[0121]

[0051] In some embodiments, the method further comprises curing the microfiber or nanofiber. In some embodiments, the method further comprises washing the microfiber or nanofiber. Atty. Dkt. No. 136938-0902

[0122]

[0052] In some embodiments, the microfiber or nanofiber is electrospun onto a temporary substrate and released as a free-standing nonwoven fabric. In some embodiments, the microfiber or nanofiber is electrospun onto an inert nonwoven support to form a composite nonwoven fabric. In some embodiments, the microfiber or nanofiber is electrospun onto a surface of a nonwoven fabric support to create a nonwoven surface layer to form a composite nonwoven fabric. In some embodiments, the nonwoven surface layer has the same quaternary ammonium salt density as the nonwoven fabric support. In some embodiments, the nonwoven surface layer has different quaternary ammonium salt density compared to the nonwoven fabric support.

[0123] BRIEF DESCRIPTION OF THE DRAWINGS

[0124]

[0053] FIG. 1 depicts scanning electron microscopy (SEM) micrographs of electrospun microfibers of Example II.

[0125]

[0054] FIG. 2 depicts SEM micrographs of electrospun microfibers of Example III.

[0126]

[0055] FIG. 3 depicts SEM micrographs of electrospun microfibers of Example VI.

[0127]

[0056] FIG. 4 depicts SEM micrographs of electron microfibers of Example VI on nonwoven substrates.

[0128]

[0057] FIG. 5 depicts a non-limiting example of a facemask containing an antiviral composite nonwoven fabric with electrospun microfibers of Example VI.

[0129]

[0058] FIG. 6 depicts a non-limiting example of a baby diaper containing an antiviral composite nonwoven fabric with electrospun microfibers of Example VI.

[0130] DETAILED DESCRIPTION

[0131]

[0059] 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. It may be evident, however, that the present technology may be practiced without these specific details. It is to be appreciated that certain aspects, modes, embodiments, variations and features of the technology are described below in various levels of detail in order to provide a substantial understanding of the present technology.

[0132] DEFINITIONS

[0133]

[0060] For convenience, the meaning of some terms and phrases used in the specification, examples, and appended claims, are provided below. Unless stated otherwise, or implicit from context, the following terms and phrases include the meanings provided below. The definitions are provided to aid in describing particular embodiments, and are not intended to limit the claimed subject-matter. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the Atty. Dkt. No. 136938-0902

[0134] art to which this present technology belongs. If there is an apparent discrepancy between the usage of a term in the art and its definition provided herein, the definition provided within the specification shall prevail.

[0135]

[0061] As used in this specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the content clearly dictates otherwise. For example, reference to “a cell” includes a combination of two or more cells, and the like.

[0136]

[0062] As used herein, the term “approximately” or “about” in reference to a value or parameter are generally taken to include numbers that fall within a range of 5%, 10%, 15%, or 20% in either direction (greater than or less than) of the number unless otherwise stated or otherwise evident from the context (except where such number would be less than 0% or exceed 100% of a possible value). As used herein, reference to “approximately” or “about” a value or parameter includes (and describes) embodiments that are directed to that value or parameter. For example, description referring to “about X” includes description of “X”.

[0137]

[0063] As used herein, the term “or” means “and / or.” The term “and / or” as used in a phrase such as “A and / or B” herein is intended to include both A and B; A or B; A (alone); and B (alone). Likewise, the term “and / or” as used in a phrase 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).

[0138]

[0064] As used herein, the term “comprising” means that other elements can also be present in addition to the defined elements presented. The use of “comprising” indicates inclusion rather than limitation.

[0139]

[0065] The term “consisting of” refers to compositions, methods, and respective components thereof as described herein, which are exclusive of any element not recited in that description of the embodiment.

[0140]

[0066] As used herein the term “consisting essentially of” refers to those 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 characteristic(s) of that embodiment of the present technology.

[0141]

[0067] As used herein, “aryl” refers to a carbocyclic (all carbon) ring that is fully aromatized. An “aryl” group can be made up of two or more fused rings (rings that share two adjacent carbon atoms). When an aryl group is a fused ring system, then the ring that is connected to the rest of the molecule is fully aromatized. The other ring(s) in the fused ring system may or may not be fully aromatized. Examples of aryl groups include, without limitation, the radicals of benzene, naphthalene and azulene.

[0142]

[0068] As used herein, “alkyl” refers to a straight or branched chain fully saturated (no double or triple bonds) hydrocarbon group. An alkyl group of the presently disclosed compounds may comprise from 1 to 15 carbon atoms. An alkyl group herein may have 1 to 4 Atty. Dkt. No. 136938-0902

[0143] carbon atoms, 1 to 5 carbon atoms, 1 to 6 carbon atoms, 1 to 7 carbon atoms, 1 to 8 carbon atoms, 1 to 9 carbon atoms, 1 to 10 carbon atoms, 1 to 11 carbon atoms, 1 to 12 carbon atoms, 1 to 13 carbon atoms, 1 to 14 carbon atoms, or 1 to 15 carbon atoms. As used herein, a C₁-C₆ alkyl represents an alkyl group having 1 to 6 carbon atoms, a C₁-C₄ alkyl represents an alkyl group having 1 to 4 carbon atoms and a C₁-C₃ alkyl represents an alkyl group having 1 to 3 carbon atoms, etc. Examples of alkyl groups include, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, / -butyl, sec-butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

[0144]

[0069] 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, a C₁-C₆ alkoxy represents an alkoxy group containing 1 to 6 carbon atoms and a 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 etc.

[0145]

[0070] As used herein, “cycloalkyl” refers to a monocyclic, bicyclic or polycyclic hydrocarbon ring system having, in some embodiments, 3 to 14 carbon atoms (e.g., C3-C14 cycloalkyl), or 3 to 10 carbon atoms (e.g., C3-C10 cycloalkyl), or 3 to 8 carbon atoms (e.g., C₃-C₈ cycloalkyl), or 3 to 6 carbon atoms (e.g., C₃-C₆ cycloalkyl) or 5 to 6 carbon atoms (e.g., C₅-C₆ cycloalkyl). Cycloalkyl groups can be saturated or characterized by one or more points of unsaturation (i.e., carbon-carbon double and / or triple bonds), provided that the points of unsaturation do not result in an aromatic system. Examples of monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexeneyl, cyclohexynyl, cycloheptyl, cyclohepteneyl, cycloheptadieneyl, cyclooctyl, cycloocteneyl, cyclooctadieneyl and the like. The rings of bicyclic and polycyclic cycloalkyl groups can be fused, bridged, or spirocyclic.

[0146]

[0071] As used herein, unless otherwise stated, “heteroalkyl” refers to an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by nitrogen, oxygen, sulfur, or silicon. A representative example of a heteroalkyl group is an alkoxy. A heteroalkylene is a divalent heteroalkyl group.

[0147]

[0072] As used herein, unless otherwise stated, term “heteroaryl” refers to monocyclic or fused bicyclic aromatic groups (or rings) having, in some embodiments, from 5 to 14 (i.e., 5-to 14-membered heteroaryl), or from 5 to 10 (i.e., 5- to 10-membered heteroaryl), or from 5 to 6 (i.e., 5- to 6-membered heteroaryl) members (i.e., ring vertices), and containing from one to five, one to four, one to three, one to two or one heteroatom selected from nitrogen (N), oxygen (O), and sulfur (S). A heteroaryl group can be attached to the remainder of the molecule through a carbon atom or a heteroatom of the heteroaryl group, when chemically permissible. Non-limiting examples of heteroaryl groups include pyridyl, pyridazinyl, Atty. Dkt. No. 136938-0902

[0148] pyrazinyl, pyrimindinyl, triazinyl, purinyl, thienopyridinyl, thienopyrimidinyl, pyrazolopyrimidinyl, pyrazolopyridinyl, imidazopyridines, isothiazolyl, pyrazolyl, indazolyl, pteridinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, pyrrolyl, thiazolyl, furyl, thienyl and the like.

[0149]

[0073] The term “heterocycloalkyl” refers to a non-aromatic monocyclic, bicyclic or polycyclic cycloalkyl ring having, in some embodiments, 3 to 14 members (e.g., 3- to 14-membered heterocycle), or 3 to 10 members (e.g., 3- to 10-membered heterocycle), or 3 to 8 members (e.g., 3- to 8-membered heterocycle), or 3 to 6 members (e.g., 3- to 6-membered heterocycle), or 5 to 6 members (e.g., 5- to 6-membered heterocycle), and having from one to five, one to four, one to three, one to two or one heteroatom selected from nitrogen (N), oxygen (O), sulfur (S) and silicon (Si). Heterocycloalkyl groups are saturated or characterized by one or more points of unsaturation (e.g., one or more carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and / or nitrogennitrogen double bonds), provided that the points of unsaturation do not result in an aromatic system. The rings of bicyclic and polycyclic heterocycloalkyl groups can be fused, bridged, or spirocyclic. Non-limiting examples of heterocycloalkyl groups include aziridine, oxirane, thiirane, pyrrolidine, imidazolidine, pyrazolidine, dioxolane, phthalimide, piperidine, 1,4-dioxane, morpholine, thiomorpholine, thiomorpholine-S-oxide, thiomorpholine-S, S-oxide, piperazine, 3,4,5,6-tetrahydropyridazine, tetrahydropyran, pyran, decahydroisoquinoline, 3-pyrroline, thiopyran, tetrahydrofuran, tetrahydrothiophene, quinuclidine, and the like. A heterocycloalkyl group can be attached to the remainder of the molecule through a ring carbon atom, or a ring heteroatom, when chemically permissible.

[0150]

[0074] As used herein, unless otherwise stated, “independently selected” indicates that each one of a designated group is selected independently from a subsequent list of species.

[0151]

[0075] The term “statistically significant” or “significantly” refers to statistical significance and generally means a two standard deviation (2SD) or greater difference.

[0152]

[0076] The terms “decrease”, “reduced”, “reduction”, or “inhibit” are all used herein to mean a decrease by a statistically significant amount. In some embodiments, “reduce,” “reduction” or “decrease” or “inhibit” typically means a decrease by at least 10% as compared to a reference level {e.g., the absence of a given treatment or agent) and can include, for example, a decrease by 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, “reduction” or “inhibition” does not encompass a complete inhibition or reduction as compared to a reference level. Atty. Dkt. No. 136938-0902

[0153] “Complete inhibition” is a 100% inhibition as compared to a reference level. A decrease can be preferably down to a level accepted as within the range of normal in a given context.

[0154]

[0077] The terms “increased”, “increase”, “enhance”, or “activate” are all used herein to mean an increase by a statically significant amount. In some embodiments, the terms “increased”, “increase”, “enhance”, or “activate” can mean an increase of at least 10% as compared to a reference level, for example an increase of 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 and including a 100% increase or any increase between 10-100% as compared to a reference level, or at least about a 2-fold, or at least about a 3-fold, or at least about a 4-fold, or at least about a 5-fold or at least about a 10-fold increase, or any increase between 2-fold and 10-fold or greater as compared to a reference level. In the context of a marker or symptom, an “increase” is a statistically significant increase in such level.

[0155]

[0078] As used herein, the term “polyisocyanates” generally represents the family of polyisocyanates containing more than one isocyanate reactive group such as, but not limited to, DESMODUR® N3300 and N100 (made by Covestro Deutschland AG of Leverkusen, Germany) which are aliphatic polyisocyanates based on HDI (hexamethylene diisocyanate) trimer, DESMODUR® Z4470SN (made by Covestro Deutschland AG of Leverkusen, Germany) which is a multifunctional polyisocyanate based on IPDI (isophorone

[0156] di isocyanate), WANNATE® T series polyisocyanates which are toluene diisocyanate (TDI)-based aromatic polyisocyanates, and LUPRANATE® M series polyisocyanates which are 4,4- diphenylmethane diisocyanate (MDI)-based aromatic polyisocyanates.

[0157]

[0079] As used herein, the term “antimicrobial” is used generally to indicate at least some level of microbe kill by a composition or a coating on a portion of a surface (e.g., on a wound). For example, antimicrobial may be used to indicate a biostatic efficacy, sanitizing 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). Microbes, or microorganisms, may include any species of bacteria, virus, fungus including mold and yeast, or spore. Thus, antimicrobial herein encompasses antiviral, antibacterial and antifungal.

[0158]

[0080] The term “polymer” herein includes random polymer, alternating polymer, block polymer, and graft polymer. The term “copolymer” herein includes random copolymer, block copolymer, graft copolymer, interpolymer complex, interpenetration network, etc., and their blends.

[0159]

[0081] As used herein, the term “blend” refers to a mixture in which components are optionally bonded to one another via a covalent bond, hydrogen bond, hydrophobic interaction, charge-transfer interaction, coulombic interaction, acid-base interaction, or a Atty. Dkt. No. 136938-0902

[0160] combination of two or more thereof. In some embodiments, components within the blend are not bonded to each other via covalent bonding. As used herein, the term “composite” refers to a mixture of two or more materials, one of which serves as a support or reinforcement for one or more of the others. In some embodiments, the term “composite” refers to a mixture containing at least one polymer and one or more inorganic and / or organic additives.

[0161] Typically, the polymer-containing composite has a continuous phase (e.g., polymer phase) and a discontinuous phase, which serves as reinforcement or additive. In some embodiments, the composite or blend comprises more than one continuous phase in various forms or morphologies such as, but not limited to, bi-continuous or co-continuous phase lamellar, rod, and / or column morphologies.

[0162]

[0082] As used herein, and unless otherwise indicated, the term “wt.%” takes on the ordinary meaning of percent (%) by weight of an ingredient in a chemical composition, based on the total weight of the composition “as made.” For example, an aqueous composition comprising 1 wt. % amine “based on the total weight of the composition” equates to a composition containing 99.0 grams water and 1.0 gram amine. Wt. % in a composition indicates the wt. % of active material, unless indicated otherwise. “As made” means that a written composition shows what was added to a mixing vessel, and not what might end up in the mixture after certain ingredients react, such as if an ingredient hydrolyzes or polymerizes.

[0163]

[0083] Unless otherwise defined herein, scientific and technical terms used in connection with the present application shall have the meanings that are commonly understood by those of ordinary skill in the art to which this disclosure belongs. It should be understood that this present technology is not limited to the particular methodology, protocols, and reagents, etc., described herein and as such can 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 can be found in The Merck Manual of Diagnosis and Therapy (2011), 19thEdition, published by Merck Sharp & Dohme Corp. (ISBN 978-0-911910-19-3); The Encyclopedia of Molecular Cell Biology and Molecular Medicine, Robert S. Porter et al. (eds.), published by Blackwell Science Ltd., 1999-2012 (ISBN 9783527600908); Molecular Biology and Biotechnology: a Comprehensive Desk Reference (1995). Robert A. Meyers (ed.), published by VCH Publishers, Inc. (ISBN 1-56081-569-8); Immunology (2006). Werner Luttmann, published by Elsevier; Janeway’s Immunobiology (2014). Kenneth Murphy, Allan Mowat, Casey Weaver (eds.), Taylor & Francis Limited, (ISBN 0815345305, 9780815345305); Lewin’s Genes XI, (2014). Published by Jones & Bartlett Publishers (ISBN-1449659055); Molecular Cloning: A Laboratory Manual., 4thed., 2012, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N. Y., USA (ISBN Atty. Dkt. No. 136938-0902

[0164] 1936113414); Basic Methods in Molecular Biology, 2012, Elsevier Science Publishing, Inc., New York, USA (ISBN 044460149X); Laboratory Methods in Enzymology: DNA, (2013). Jon Lorsch (ed.) Elsevier (ISBN 0124199542); Current Protocols in Molecular Biology (CPMB) (2014). Frederick M. Ausubel (ed.), John Wiley and Sons (ISBN 047150338X, 9780471503385); Current Protocols in Protein Science (CPPS) (2005). John E. Coligan (ed.), John Wiley and Sons, Inc.; and Current Protocols in Immunology (CPI) (2003).

[0165] Coligan, J. E., et al., (eds.) John Wiley and Sons, Inc. (ISBN 0471142735, 9780471142737).

[0166]

[0084] Other terms are defined herein within the description of the various aspects of the present technology.

[0167] MICROFIBERS AND NANOFIBERS

[0168]

[0085] The microfibers and nanofibers described herein are anti-infective. In some embodiments, the microfibers and nanofibers are antibacterial against one of or both gram negative strain bacteria and gram positive strain bacteria.

[0169]

[0086] In one aspect, provided herein is a microfiber or nanofiber comprising, consisting essentially of, or consisting of a blend, composite, or interpenetrating polymer network comprising, consisting essentially of, or consisting of:

[0170] (1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents; and

[0171] (2) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

[0172]

[0087] In some embodiments, the polyethyleneimine intermediate and the hydroxyfunctionalized oligomer, polymer, or copolymer are non-covalently blended together.

[0173]

[0088] In another aspect, provided herein is microfiber or nanofiber comprising, consisting essentially of, or consisting of a polymer or interpenetrating polymer network comprising, consisting essentially of, or consisting of a polymerization / crosslinking product of reagents comprising, consisting essentially of, or consisting of:

[0174] (1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the Atty. Dkt. No. 136938-0902

[0175] polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents;

[0176] (2) a multifunctional crosslinker; and

[0177] (3) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

[0178]

[0089] In another aspect, provided herein is microfiber or nanofiber comprising, consisting essentially of, or consisting of a polymer or interpenetrating polymer network comprising, consisting essentially of, or consisting of a polymerization / crosslinking product of reagents comprising, consisting essentially of, or consisting of:

[0179] (1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents;

[0180] (2) an adduct of a quaternary ammonium salt and a multifunctional crosslinker; and (3) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s)

[0181]

[0090] In another aspect, provided herein is microfiber or nanofiber comprising, consisting essentially of, or consisting of a polymer or interpenetrating polymer network comprising, consisting essentially of, or consisting of a polymerization / crosslinking product of reagents comprising, consisting essentially of, or consisting of:

[0182] (1) an adduct of a quaternary ammonium salt and a multifunctional crosslinker; and (2) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

[0183]

[0091] In some embodiments, the polymerization / crosslinking product is a random polymerization / crosslinking product. In some embodiments, the polymerization / crosslinking product is a block polymerization / crosslinking product. In some embodiments, the polymerization / crosslinking product is a graft polymerization / crosslinking product.

[0184]

[0092] In some embodiments, the polymer or interpenetrating polymer network are comprised in a blend or composite within the microfiber or nanofiber. In some embodiments, the polymer is comprised in an interpenetrating polymer network within the microfiber or nanofiber.

[0185]

[0093] As described herein, the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol Atty. Dkt. No. 136938-0902

[0186] group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents. In some embodiment, the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and two or more alkylating agents; at least one of the two or more alkylating agents introduces hydroxyl group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the two or more alkylating agents. In some embodiment, the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and two alkylating agents; at least one of the two alkylating agents introduces hydroxyl group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the two alkylating agents. In some embodiment, the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and two alkylating agents; one of the two alkylating agents introduces hydroxyl group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the two alkylating agents. In some embodiments, the hydroxyl group functionality is hydroxyalkylene functionality. In some embodiments, the one or more alkylating agents comprise a hydroxyl group. In some embodiments, the one or more alkylating agents, which introduce hydroxyl group functionality on the polyethyleneimine intermediate, comprise a hydroxyl group. In some embodiments, the one or more alkylating agents comprise a primary hydroxyl group. In some embodiments, the one or more alkylating agents, which introduce hydroxyl group functionality on the polyethyleneimine intermediate, comprise a primary hydroxyl group. In some embodiments, the one or more alkylating agents comprise a spacer of at least three carbon atoms between a leaving group and the hydroxyl group. In some embodiments, the one or more alkylating agents, which introduce hydroxyl group functionality on the polyethyleneimine intermediate, comprise a spacer of at least three carbon atoms between a leaving group and the hydroxyl group. In some embodiments, the leaving group is selected from a group consisting of iodide, bromide, chloride, mesylate, tosylate, nonaflate, and triflate.

[0187]

[0094] In some embodiments, the polyethyleneimine intermediate comprises optionally substituted hydroxyalkylene functionality. In some embodiments, the polyethyleneimine intermediate comprises optionally substituted hydroxyalkylene functionality that reacts with the adduct of a quaternary ammonium salt and a multifunctional crosslinker. In some embodiments, the polyethyleneimine intermediate comprises optionally substituted hydroxyalkylene functionality that reacts with the multifunctional crosslinker. Atty. Dkt. No. 136938-0902

[0188]

[0095] In some embodiments, the hydroxyalkylene functionality is optionally substituted with Ci-Ce alkyl optionally substituted with a substituent selected from -N+(R20)3X-, -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH, -(Ci-Ce alkoxy), -(Ce-Cw aryl) optionally substituted with -(Ci-Ce alkyl), and carboxy; each R20is independently selected from a group consisting of Ci-C alkyl; Ci-Cw heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and Ce-Cw aryl optionally substituted with -(CrC6alkyl), -(C C6alkoxy), -C(O)O-(Ci-C6alkyl), -C(O)NH(CrC6alkyl), -C(O)N(CrC6al kyl)2, or -OC(O)-(Ci-Ce alkyl); and each X-is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives. In some embodiments, the hydroxyalkylene functionality is substituted with Ci-Ce alkyl substituted with -N+(R20)3X-, each R20is independently selected from a group consisting of C1-C18alkyl; C1-C18heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10aryl optionally substituted with -(C1-C6alkyl), -(C1-C6alkoxy), -C(O)O-(C1-C6alkyl), -C(O)NH(C1-C6alkyl), -C(O)N(C1-C6alkyl)2, or -OC(O)-(C1-C6alkyl); and each X-is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives. In some embodiments, the hydroxyalkylene functionality is substituted with -(CH2)-N+(Me)3Cl-. In some embodiments, the hydroxyalkylene functionality is hydroxyethylene, hydroxypropylene, hydroxybutylene, or an oligomer thereof.

[0189]

[0096] In some embodiments, the polyethyleneimine intermediate comprises optionally substituted HS-(alkylene) functionality. In some embodiments, the polyethyleneimine intermediate comprises optionally substituted HS-(alkylene) functionality that reacts with the adduct of a quaternary ammonium salt and a multifunctional crosslinker. In some embodiments, the polyethyleneimine intermediate comprises optionally substituted HS-(alkylene) functionality that reacts with the multifunctional crosslinker.

[0190]

[0097] In some embodiments, at least one of the one or more alkylating agents is selected from a group consisting of a mono-epoxide, lactone, and R21-LG; wherein each R21is independently selected from Ci-Ce alkyl optionally substituted with a substituent selected from -OH, -(Ci-Ce alkoxy), carboxy, -(Ce-Cw aryl), -C(O)O(Ci-Ce alkyl), -C(O)-(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH; and each LG is a leaving group. As used herein, and unless otherwise indicated, the leaving group may be a halide, a sulfonate, or the like. In some embodiments, the leaving group is selected from a group consisting of iodide, bromide, chloride, mesylate, tosylate, nonaflate, and triflate.

[0191]

[0098] In some embodiments, the mono-epoxide or the lactone is optionally substituted with Ci-Ce alkyl optionally substituted with a substituent selected from -(Ce-Cw aryl), and -(Ci-Ce Atty. Dkt. No. 136938-0902

[0192] alkoxy) optionally substituted with hydroxy, Ci-Ce alkoxy, Ce-Cw aryl optionally substituted with Ci-Ce alkyl, and carboxy.

[0193]

[0099] In some embodiments, the mono-epoxide is optionally substituted with Ci-Ce alkyl optionally substituted with a substituent selected from -(C6-C10aryl), and -(Ci-Ce alkoxy) optionally substituted with hydroxy, Ci-Ce alkoxy, Ce-Cw aryl optionally substituted with Ci-Ce alkyl, and carboxy.

[0194]

[0100] In some embodiments, the mono-epoxide is a Ci-Ce alkyl oxirane. In some embodiments, the Ci-Ce alkyl oxirane is selected from the group consisting of methyl oxirane (propylene oxide), ethyl oxirane (1-butylene oxide or 1,2-epoxy butane), propyl oxirane (1-pentene oxide), butyl oxirane (1-hexene oxide), and hexyl oxirane (1-octene oxide). In some embodiments, the Ci-Ce alkyl oxirane is methyl oxirane or propylene oxide. In some embodiments, the Ci-Ce alkyl oxirane is butyl oxirane or 1-hexene oxide. In some embodiments, the Ci-Ce alkyl oxirane is hexyl oxirane or octene oxide.

[0195]

[0101] In some embodiments, the mono-epoxide is substituted with -(Ci-Ce alkylene)-N+(R20)3X'; each R20is independently selected from a group consisting of C1-C18alkyl; C1-C18heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10aryl optionally substituted with -(C1-C6alkyl), -(C1-C6alkoxy), -C(O)O-(C1-C6alkyl), -C(O)NH(C1-C6alkyl), -C(O)N(C1-C6alkyl)2, or -OC(O)-(C1-C6alkyl); and each X-is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

[0196]

[0102] In some embodiments, R21-LG is independently selected from phenacyl halide, benzyl halide, or hexyl halide.

[0197]

[0103] In some embodiments, the lactone is caprolactone or butyrolactone.

[0198]

[0104] In some embodiments, at least one of the one or more alkylating agents is selected from a group consisting of a mono-epoxide, lactone, and R21-LG, wherein:

[0199] the mono-epoxide is optionally substituted with:

[0200] (i) Ci-Ce alkyl optionally substituted with a substituent selected from -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with hydroxy, Ci-Ce alkoxy, Ce-Cw aryl optionally substituted with Ci-Ce alkyl, and carboxy; or

[0201] (ii) -(C1-C6alkyl)-N+(R20)3X-; each R20is independently selected from a group consisting of C1-C18alkyl; C1-C18heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10aryl optionally substituted with -(C1-C6alkyl), -(C1-C6alkoxy), -C(O)O-(C1-C6alkyl), -C(O)NH(C1-C6alkyl), -C(O)N(C1-C6alkyl)2, or -OC(O)-(C1-C6alkyl); and each X-is independently selected from the group consisting of acetate, halide, sulfate, Atty. Dkt. No. 136938-0902

[0202] sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives; and

[0203] each R21is independently selected from C1-C6alkyl optionally substituted with a substituent selected from -OH, -(C1-C6alkoxy), carboxy, -(C6-C10aryl), -C(O)O(C1-C6alkyl), -C(O)-(C6-C10aryl), and -(C1-C6alkoxy) optionally substituted with -OH; and each LG is a leaving group.

[0204]

[0105] In some embodiments, at least one of the one or more alkylating agents is selected from R21-LG.

[0205]

[0106] In some embodiments, the one or more alkylating agents comprise a C1-C6 alkyl halide and a haloalkanol, wherein the haloalkanol is X30-(C2-C6 alkylene)-OH, wherein X30is Cl, Br, or I. In some embodiments, the one or more alkylating agents comprise 1-bromohexane and 3-bromopropanol.

[0206]

[0107] The polyethyleneimine intermediate may be present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 50 wt.%. This includes 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 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, or 50 wt.%, or any value therebetween. In some embodiments, the polyethyleneimine intermediate is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 10 wt.%. As described herein, the polyethyleneimine intermediate is not in the form of nanoparticles or particulates prior to further use in the preparation of electrospun fibers.

[0207]

[0108] In some embodiments, at least 20% of the nitrogen atoms of the polyethyleneimine intermediate are quaternized. In some embodiments, at least 30% of the nitrogen atoms of the polyethyleneimine intermediate are quaternized.

[0208]

[0109] The polyethyleneimine may have a molecular weight of about 300 to about 270,000 daltons. This includes about 300; 400; 500; 600; 700; 800; 900; 1000; 2500; 5000; 10,000; 25,000; 50,000; 75,000; 100,000; 125,000; 150,000; 175,000; 200,000; 225,000; 250,000; or 270,000 daltons, or any value therebetween. In some embodiments, the polyethyleneimine has a molecular weight of about 10,000 to about 200,000 daltons, or about 25,000 to about 120,000 daltons.

[0209]

[0110] In some embodiments, the polyethyleneimine is branched. In some embodiments, the polyethyleneimine is hyperbranched. Atty. Dkt. No. 136938-0902

[0210]

[0111] 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.

[0211]

[0112] In some embodiments, the polyethyleneimine intermediate is selected from

[0212]

[0213] copolymer or blend of any two or more thereof, wherein:

[0214] each Y3is independently H or -OH, wherein every Y3cannot be H;

[0215] each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000;

[0216] Z is -(C2-C6 alkylene)-;

[0217] each R10is independently selected from hydrogen; C1-C6alkyl optionally substituted with a substituent selected from -N(R20)3, -(C6-C10aryl), and -(C1-C6alkoxy) optionally substituted with -OH, -(C1-C6alkoxy), -(C6-C10aryl) optionally substituted with -(C1-C6alkyl), and carboxy; and each R20is independently selected from a group consisting of C1-C18alkyl; C1-C18heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10aryl optionally substituted with -(C1-C6alkyl), -(C1-C6alkoxy), -C(O)O-(C1-C6alkyl), -C(O)NH(C1-C6alkyl), -C(O)N(C1-C6alkyl)2, or -OC(O)-(C1-C6alkyl);

[0218] each R21is independently selected from C1-C6alkyl optionally substituted with a substituent selected from -OH, -(C1-C6alkoxy), carboxy, -(C6-C10aryl), -C(O)O(C1-C6alkyl), -C(O)-(C6-C10aryl), and -(C1-C6alkoxy) optionally substituted with -OH; Atty. Dkt. No. 136938-0902

[0219] each R30is independently selected from (1) C6-C20 alkyl optionally substituted with 1-3 substituents independently selected from halogen, -SiRa(ORb)(ORc), and -(C6-C10 aryl); and (2) C6-C10 aryl optionally substituted with 1-3 substituents independently selected from halogen, -(C1-C6 alkyl), and -SiRa(ORb)(ORc); wherein each Rais independently - (Ci-Ce alkyl); and each Rband each Rcare independently selected from -(Ci-Ce alkyl) and -Si(Ci-Ce alkyl)3; and

[0220] each X’ is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

[0221]

[0113] In some embodiments, the polyethyleneimine intermediate is:

[0222]

[0223] wherein each R60is independently selected from -Y4-(C1-C18alkyl) optionally substituted with 1-3 substituents selected from -OH, -N+(R20)3X-, -(C1-C6alkoxy), carboxy, -(C6-C10aryl), -C(O)O(C1-C6alkyl), -C(O)-(C6-C10aryl), and -(C1-C6alkoxy) optionally substituted with -OH; and at least one R60is substituted with -OH but less than 50% of all R60are substituted with -OH;

[0224] Y4is absent or -C(O)-;

[0225] and each R20is independently selected from a group consisting of C1-C18alkyl; C1-C18heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10aryl optionally substituted with -(C1-C6alkyl), -(C1-C6alkoxy), -C(O)O-(C1-C6alkyl), -C(O)NH(C1-C6alkyl), -C(O)N(C1-C6alkyl)2, or -OC(O)-(C1-C6alkyl);

[0226] each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000; and

[0227] each X’ is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

[0228]

[0114] In some embodiments, the polyethyleneimine intermediate is: Atty. Dkt. No. 136938-0902

[0229]

[0230] wherein

[0231] each R60is independently selected from -Y4-(C1-C18alkyl) optionally substituted with 1-3 substituents selected from -OH, -N+(R20)3X-, -(C6-C10aryl), -C(O)O(C1-C8alkyl), and -C(O)-(C6-C10aryl); and at least one R60is substituted with -OH but less than 50% of all R60are substituted with -OH;

[0232] Y4is absent or -C(O)-;

[0233] and each R20is independently selected from a group consisting of C1-C8alkyl;

[0234] each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000; and

[0235] each X' is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

[0236]

[0115] In some embodiments, each R60is independently selected from -(C1-C18alkyl) optionally substituted with -OH; and at least one R60is substituted with -OH but less than 50% of all R60are substituted with -OH.

[0237]

[0116] In some embodiments, each R60is independently selected from the group consisting of -CH3, -C4H9, -C6H13, -C8H17, -C18H37, -CH2Ph, -CH2C(O)OCH2CH3, -CH2C(O)Ph, -(CH2)3OH, -CH2CH(CH3)OH, -CH2CH(OH)CH2N+(CH3)3, and -C(O)(CH2)5OH. In some embodiments, each R60is independently selected from the group consisting of -CH3, -C4H9, -C6H13, -C8H17, -C18H37, -CH2Ph, -CH2C(O)OCH2CH3, -CH2C(O)Ph, -(CH2)3OH, -CH2CH(CH3)OH, -CH2CH(OH)CH2N+(CH3)3, and -C(O)(CH2)5OH; and at least one R60is substituted with -OH but less than 50% of all R60are substituted with -OH.

[0238]

[0117] In some embodiments, at least one R60is substituted with -OH but less than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 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, or 49% of all R60are substituted with -OH. In some embodiments, about 1% to about 49% of all R60are substituted with -OH. This includes about 1% to about 40%, about 1% to about 30%, about 1% to about 20%, about 1% to about 18%, about 1% to about 15%, about 1% to about 10%, Atty. Dkt. No. 136938-0902

[0239] about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, about 5% to about 18%, about 5% to about 15%, about 5% to about 10%, and any range therebetween.

[0240]

[0118] In some embodiments, the polyethyleneimine intermediate has a ratio of total quaternary amines to total hydroxyl groups of at least 1:1. This includes a ratio of 1: 1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9:1, 9.2:1, 9.4:1, 9.6:1, 9.8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 99:1, or higher, or any value therebetween.

[0241]

[0119] In some embodiments, the polyethyleneimine intermediate is selected from a group consisting of:

[0242] Compound General PEI MW* R60(mole %)“

[0243] Structure

[0244] 20-1 B 270 kDa -CH2CH(CH3)OH (<50%) (batch 105159) (branched) -C6Hi3 (>50%)

[0245] 20-1 B 270 kDa -CH2CH(CH3)OH (50%) (batch 99367) (branched) -C6H13(50%)

[0246] 21-1 A 25 kDa -CH2CH(CH3)OH (50%)

[0247] (hyperbranched) -C6H13(50%)

[0248] 22-1 B 70 kDa -CH2CH(CH3)OH (50%)

[0249] (branched) -C6H13(50%)

[0250] 23-1 B 70 kDa -CH2CH(CH3)OH (50%)

[0251] (branched) -CH2C(O)Ph (50%) 24-1 B 70 kDa -CH2CH(CH3)OH (50%)

[0252] (branched) -CH2Ph (50%)

[0253] 26-1 B 70 kDa -CH2CH(OH)CH2N+(CH3)3CI- (branched) (100%)

[0254] 29-1 B 70 kDa -(CH2)3OH (1%)

[0255] (branched) -C6Hi3 (99%)

[0256] 30-1 A 25 kDa -(CH2)3OH (10%)

[0257] (hyperbranched) 75:25 -Ci8H37:-C8H17(90%) 31-1 B 70 kDa -C(O)(CH2)5OH (7%)

[0258] (branched) -C6H13(93%)

[0259] 32-1 B 70 kDa -(CH2)3OH (10%)

[0260] (branched) -C6H13(90%)

[0261] 32-2 B 70 kDa -(CH2)3OH (5%)

[0262] (branched) -C6H13(95%)

[0263] 32-3 B 70 kDa -CH2CH(CH3)OH (5%)

[0264] (branched) -C6H13(95%)

[0265] 32-4 B 70 kDa -C(O)(CH2)5OH (7.5%)

[0266] (branched) -C6H13(92.5%)

[0267] 32-5 A 25 kDa -CH2CH(CH3)OH (50%)

[0268] (hyperbranched) 50:50 -Ci8H37:-C8H17(50%) 32-6 B 72 kDa -(CH2)3OH (13%)

[0269] (branched) 75:25 -Ci8H37:-C8H17(87%) 32-7 B 72 kDa -C(O)(CH2)5OH (6.5%)

[0270]

[0271] (branched) 75:25 -Ci8H37:-C8H17(93.5%) Atty. Dkt. No. 136938-0902

[0272] 32-8 A 25 kDa -C(O)(CH2)5OH (7%)

[0273] (hyperbranched) 75:25 -Ci8H37:-C8H17(93%) 32-9 A 25 kDa -CH2CH(CH3)OH (50%)

[0274]

[0275] (hyperbranched) 25:75 -C18H37:-C8H17(50%) indicates molecular weight of polyethyleneimine precursor

[0276] ** theoretical stoichiometric ratio (based on amount of reactants used in the synthetic protocol)

[0277] R60R60R60R60| R60R60| R60

[0278] wherein A is

[0279]

[0280] is p60

[0281] ; B is ; and each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 100. In some embodiments, one or more bromide anions is replaced with X' independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

[0282]

[0120] In some embodiments, the polyethyleneimine intermediate is selected from a group consisting of

[0283] Compound General Structure PEI MW* R60(mole %)**

[0284] 32-10 A 25 kDa -C(O)(CH2)5OH (11%)

[0285] (hyperbranched) -C6H13(89%)

[0286] 32-11 B 70 kDa -C(O)(CH2)5OH (9%)

[0287] (branched) -C6H13(91%)

[0288] 32-13 B 70 kDa -(CH2)3OH (7%)

[0289] (branched) 75:25 -Ci8H37:-C8H17(93%) 32-14 A 25 kDa -(CH2)3OH (7%)

[0290] (hyperbranched) 75:25 -Ci8H37:-C8H17(93%) 32-15 B 70 kDa -C(O)(CH2)5OH (9%)

[0291] (branched) 75:25 -Ci8H37:-C8H17(91%) 32-16 A 25 kDa -C(O)(CH2)5OH (11%)

[0292] (hyperbranched) 75:25 -Ci8H37:-C8H17(89%) 32-17 B 70 kDa -C6H13(100%)

[0293] (branched)

[0294] 32-18 A 25 kDa -C6H13(100%)

[0295] (hyperbranched)

[0296] 32-1 A B 70 kDa -(CH2)3OH (10%)

[0297] (branched) -C6H13(90%)

[0298] 32-1 B B 70 kDa -(CH2)3OH (10%)

[0299] (branched) -C6H13(90%)

[0300] 32-2A B 70 kDa -(CH2)3OH (5%)

[0301]

[0302] (branched) -C6H13(95%) Atty. Dkt. No. 136938-0902

[0303] 32-2B B 70 kDa -(CH2)3OH (5%)

[0304] (branched) -C6H13(95%)

[0305] 32-2C B 70 kDa -(CH2)3OH (15%)***

[0306] (branched) -C6H13(85%)

[0307] 32-2D B 70 kDa -(CH2)3OH (5%)

[0308] (branched) -C6H13(95%)

[0309] 32-2E B 70 kDa -(CH2)3OH (12%)***

[0310] (branched) -C6H13(88%)

[0311] 32-2 F B 70 kDa -(CH2)3OH (5%)

[0312] (branched) -C6H13(95%)

[0313] 32-2G B 70 kDa -(CH2)3OH (5%)

[0314] (branched) -C6H13(95%)

[0315] 32-2H B 70 kDa -(CH2)3OH (5%)

[0316] (branched) -C6H13(95%)

[0317] 32-2I B 70 kDa -(CH2)3OH (5%)

[0318]

[0319] (branched) -C6H13(95%) indicates molecular weight of polyethyleneimine precursor

[0320] ** theoretical stoichiometric ratio (based on amount of reactants used in the synthetic protocol) unless otherwise indicated

[0321] ***actual stoichiometric ratio as determined by NMR analysis

[0322] R60R60R60

[0323] R60+ I i

[0324] R60 | R60r6< | >60

[0325] .. ■ p60 r> ■ p60 -.. wherein A

[0326]

[0327] is K B isK; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 100; and each X' is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivative.

[0328]

[0121] In some embodiments, the reagents for the reaction product comprised in the polyethyleneimine intermediate further comprise a monoisocyanate. In some embodiments, the monoisocyanate comprises one or more R30-NCO, wherein each R30is independently selected from (1) C6-C20 alkyl optionally substituted with 1-3 substituents independently selected from halogen, -SiRa(ORb)(ORc), and -(C6-C10aryl); and (2) C6-C10aryl optionally substituted with 1-3 substituents independently selected from halogen, -(C1-C6alkyl), and -SiRa(ORb)(ORc); wherein each Rais independently C1-C6alkyl; and each Rband each Rcare independently selected from -(C1-C6alkyl) and -Si(C1-C6alkyl)3. In some embodiments, the monoisocyanate comprises octylisocyanate, octadecylisocyanate, or a combination thereof.

[0329]

[0122] Accordingly, in some embodiments, the polyethyleneimine intermediate is selected from: Atty. Dkt. No. 136938-0902

[0330]

[0331] copolymer or blend of any two or more thereof, wherein:

[0332] each Y3is independently H or -O-Y2, wherein every Y3cannot be H;

[0333] each Y2is independently H or -C(O)-NHR30, wherein every Y2cannot be -C(O)-NHR30; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000;

[0334] Z is -(C2-C6 alkylene)-;

[0335] each R10is Ci-Ce alkyl substituted with -N+(R20)3X’, and each R20is independently selected from a group consisting of C1-C18 alkyl; C1-C18 heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and Ce-Cw aryl optionally substituted with -(Ci-Ce alkyl), -(Ci-Ce alkoxy), -C(O)O-(Ci-Ce alkyl), - C(O)NH(CI-C6alkyl), -C(O)N(CI-C6alkyl)2, or -OC(O)-(Ci-C6alkyl);

[0336] each R21is independently selected from Ci-Ce alkyl optionally substituted with a substituent selected from -OH, -(Ci-Ce alkoxy), carboxy, -(C6-C10aryl), -C(O)O(Ci-Ce alkyl), - C(O)-(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH;

[0337] each R30is independently selected from (1) C6-C20 alkyl optionally substituted with 1-3 substituents independently selected from halogen, -SiRa(ORb)(ORc), and -(C6-C10 aryl); and (2) C6-C10 aryl optionally substituted with 1-3 substituents independently selected from halogen, -(C1-C6 alkyl), and -SiRa(ORb)(ORc); wherein each Rais independently -(Ci-Ce alkyl); and each Rband each Rcare independently selected from -(Ci-Ce alkyl) and -Si(Ci-Ce alkyl)3; and Atty. Dkt. No. 136938-0902

[0338] each X’ is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives

[0123] The multifunctional crosslinker may be a bisfunctional crosslinker. In some embodiments, the bisfunctional crosslinker is a diisocyanate. In some embodiments, the diisocyanate is selected from the group consisting of: hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylenediisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), metatetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI).

[0339]

[0124] The multifunctional crosslinker may be a multifunctional isocyanate, isothiocyanate, epoxide, or a precursor thereof.

[0340]

[0125] In some embodiments, the multifunctional crosslinker is 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 to 4.

[0341]

[0126] The polyisocyanate may be prepared from a diisocyanate independently selected from the group consisting of: hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylenediisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), metatetramethylxylene diisocyanate (TMXDI), and trimethylhexamethylene diisocyanate (TMDI).

[0342]

[0127] In some embodiments, the polyisocyanate is independently selected from the group consisting of DESMODUR® N-3300, DESMODUR® N-100, DESMODUR® Z4470SN, WANNATE® T series polyisocyanates, and LUPRANATE® M series polyisocyanates.

[0343] 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 toluene diisocyanate (TDI)-based aromatic polyisocyanates.

[0344] LUPRANATE® M series polyisocyanates are 4,4- diphenylmethane diisocyanate (MDI)-based aromatic polyisocyanates.

[0345]

[0128] The multifunctional crosslinker may be present in the dried microfiber or in the dried nanofiber in an amount of about 3 wt.% to about 20 wt.%. This includes 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt.%, or any value therebetween. In some embodiments, the multifunctional crosslinker is present in the dried microfiber or in the dried nanofiber in an amount of about 3 wt.% to about 10 wt.%, about 5 wt.% to about 20 wt.%, or about 5 wt.% to about 15 wt.%. Atty. Dkt. No. 136938-0902

[0346]

[0129] In some embodiments, the polyethyleneimine intermediate reacts with the multifunctional crosslinker (e.g., polyisocyanate) to form a compound of formula (I):

[0347]

[0348] formula (I)

[0349] wherein:

[0350] each A is independently selected from

[0351]

[0352]

[0353] more

[0354] thereof; and attachment of each A forms a carbamate linkage;

[0355] each Y3is independently H or -O-Y2, wherein every Y3cannot be H; Atty. Dkt. No. 136938-0902

[0356] each Y2is independently H or-C(O)-NHR30, wherein every Y2cannot be -C(O)-NHR30; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000;

[0357] Z is -(C2-C6 alkylene)-;

[0358] each R10is independently selected from hydrogen; Ci-Ce alkyl optionally substituted with a substituent selected from -N(R20)3, -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH, -(Ci-Ce alkoxy), -(Ce-Cw aryl) optionally substituted with -(Ci-Ce alkyl), and carboxy; and each R20is independently selected from a group consisting of C1-C18 alkyl; Ci-Cw heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and Ce-Cw aryl optionally substituted with -(Ci-Ce alkyl), -(C1-C6alkoxy), -C(O)O-(C1-C6alkyl), -C(O)NH(C1-C6alkyl), -C(O)N(C1-C6alkyl)2, or -OC(O)-(C1-C6alkyl);

[0359] each R21is independently selected from C1-C6alkyl optionally substituted with a substituent selected from -OH, -(C1-C6alkoxy), carboxy, -(C6-C10aryl), -C(O)O(C1-C6alkyl), -C(O)-(C6-C10aryl), and -(C1-C6alkoxy) optionally substituted with -OH;

[0360] each R30is independently selected from (1) C6-C20 alkyl optionally substituted with 1-3 substituents independently selected from halogen, -SiRa(ORb)(ORc), and -(Ce-Cw aryl); (2) Ce-Cw aryl optionally substituted with 1-3 substituents independently selected from O

[0361] o HN^YX

[0362] Rt? ^R40

[0363] N N

[0364] O^N^O

[0365] p40

[0366] HN-Rhalogen, -(Ci-Ce alkyl), a

[0367]

[0368] nd -SiRa(ORb)(ORc); and (3); wherein each Rais independently -(Ci-Ce alkyl); and each Rband each Rcare independently selected from -(Ci-Ce alkyl) and -Si(C1-C6alkyl)3;

[0369] each R40is independently -(Ci-Cw alkylene)- optionally substituted with phenyl or a 3- to 8- member cycloalkyl ring; and

[0370] each X’ is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

[0371]

[0130] In some embodiments, the polyethyleneimine intermediate reacts with the multifunctional crosslinker (e.g., polyisocyanate) to form a compound of formula (II): Atty. Dkt. No. 136938-0902

[0372]

[0373] formula (II)

[0374] wherein:

[0375] each A is independently selected from

[0376]

[0377]

[0378] more thereof; and attachment of each A forms a carbamate linkage;

[0379] each Y3is independently H or -O-Y2, wherein every Y3cannot be H;

[0380] each Y2is independently H or-C(O)-NHR30, wherein every Y2cannot be -C(O)-NHR30; each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000; Atty. Dkt. No. 136938-0902

[0381] Z is -(C2-C6 alkylene)-;

[0382] each R10is independently selected from hydrogen; Ci-Ce alkyl optionally substituted with a substituent selected from -N(R20)3, -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH, -(Ci-Ce alkoxy), -(Ce-Cw aryl) optionally substituted with -(Ci-Ce alkyl), and carboxy; and each R20is independently selected from a group consisting of Ci-Cw alkyl; Ci-Cw heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and Ce-Cw aryl optionally substituted with -(Ci-Ce alkyl), -(C1-C6alkoxy), -C(O)O-(C1-C6alkyl), -C(O)NH(C1-C6alkyl), -C(O)N(C1-C6alkyl)2, or -OC(O)-(C1-C6alkyl);

[0383] each R21is independently selected from Ci-Ce alkyl optionally substituted with a substituent selected from -OH, -(Ci-Ce alkoxy), carboxy, -(Ce-Cw aryl), -C(O)O(Ci-Ce alkyl), -C(O)- (C6-C10aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH;

[0384] each R30is independently selected from (1) C6-C20 alkyl optionally substituted with 1-3 substituents independently selected from halogen, -SiRa(ORb)(ORc), and -(Ce-Cw aryl); (2) Ce-Cw aryl optionally substituted with 1-3 substituents independently selected from O

[0385] •~ywHN^^A

[0386] p^40 R40

[0387] '"'''NH HN^ O^N^O

[0388] p40

[0389] HN-Rhalogen, -(Ci-Ce alkyl), a

[0390]

[0391] nd -SiRa(ORb)(ORc); and (3) CX^A; wherein each Rais independently -(Ci-Ce alkyl); and each Rband each Rcare independently selected from -(Ci-Ce alkyl) and -Si(C1-C6alkyl)3;

[0392] each R40is independently -(Ci-Cw alkylene)- optionally substituted with phenyl or a 3- to 8- member cycloalkyl ring; and

[0393] each X’ is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

[0394]

[0131] The quaternary ammonium salt may have a chemical structure of:

[0395]

[0396] wherein: Atty. Dkt. No. 136938-0902

[0397] R1is selected from a group consisting of -(C8-C30alkyl), -(C8-C30heteroalkyl), -(C8-C30heteroalkyl)-(C6-C10aryl), -(C6-C10aryl), -(C6-C10aryl)-(C8-C30alkyl), -(C6-C10aryl)-(C8-C30heteroalkyl), -(CRmRn)x10-W10-(CRpRq)y10-H, and -(CRmRn)x11-W11-(CRpRq)y11H-; wherein -(C8-C30heteroalkyl), -(C8-C30heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl)-(C8-C30heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;

[0398] R2is selected from a group consisting of -(Ci-C4 alkyl), -(C1-C4 heteroalkyl), -(C1-C4 heteroalkyl)-(C6-Cio aryl), -(C6-Cw aryl), -(C6-Cw aryl)-(Ci-C4alkyl), -(C6-Cw aryl)-(Ci-C4heteroalkyl); -(CRmRn)x2o-W2O-(CRPRq)y2o-H, and -(CRmRn)x2i-W21-(CRPRq)y2i-H; wherein - (C1-C4 heteroalkyl), -(Ci-C4 heteroalkyl)-(C8-Cio aryl), and -(C6-C10aryl)-(Ci-C4 heteroalkyl) have 1 to 2 heteroatoms independently selected from O, S, and Si;

[0399] R3is selected from a group consisting of -(Ci-C8o alkyl), -(C1-C30 heteroalkyl), -(C1-C30 heteroalkyl)-(C6-Cio aryl), -(C6-Cw aryl), -(C6-Cw aryl)-(Ci-C3o alkyl), -(C6-Cw aryl)-(Ci-C3o heteroalkyl), -(CRmRn)x3o-W3O-(CRPRq)y3o-H, and -(CRmRn)x3i-W31-(CRPRq)y3i-H; wherein - (C1-C30 heteroalkyl), -(C1-C30heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl)-(C1-C30heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;

[0400] A is a linking group selected from a group consisting of -(C3-C20 alkylene)-, -(C3-C20 heteroalkylene)-, -(C6-C10arylene)-(C3-C20alkylene), -(CRmRn)x40-W40-(CRpRq)y40-, and -(CRmRn)x41-W41-(CRpRq)y41-, wherein -(C3-C20heteroalkylene)- has 1 to 4 heteroatoms independently selected from O, S, and Si; and -(C3-C20alkylene)- and -(C3-C20heteroalkylene)- are optionally substituted with 1 to 6 substituents independently selected from -(C6-C10aryl)-(C1-C3alkyl), -(C6-C10aryl)-(C1-C3heteroalkyl), -(C1-C3alkyl)-(C6-C10aryl), -(C1-C3heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl);

[0401] each Rm, Rn, Rp, and Rqis independently selected from H and C1-C4 alkyl;

[0402] W10, W20, W30, and W40are independently selected from -C(O)-; -C(O)O-; -OC(O)-; -C(O)NH-; and -NHC(O)-;

[0403] W11, W21, W31, and W41are independently selected from 5- to 6-membered cycloalkyl, C6-C10aryl, 5- to 6-membered heterocycloalkyl, and 5- to 6-membered heteroaryl, wherein the heterocycloalkyl contains 1-2 ring heteroatoms selected from O, N, S, and Si; and the heteroaryl contains 1-3 ring heteroatoms selected from O, N, S, and Si;

[0404] x10 is an integer from 1 to 30 and y10 is an integer from 0 to 29, wherein 8 ≤ (x10 + y10) ≤ 30;

[0405] x11 is an integer from 1 to 30 and y11 is an integer from 0 to 29, wherein 8 ≤ (x11 + y11) ≤ 30;

[0406] x20 is an integer from 1 to 4 and y20 is an integer from 0 to 3, wherein x20 + y20 ≤ 4; x21 is an integer from 1 to 4 and y21 is an integer from 0 to 3, wherein x21 + y21 ≤ 4; x30 is an integer from 1 to 30 and y30 is an integer from 0 to 29, wherein x30 + y30 ≤ 30; x31 is an integer from 1 to 30 and y31 is an integer from 0 to 29, wherein x31 + y31 ≤ 30; Atty. Dkt. No. 136938-0902

[0407] x40 is an integer from 1 to 19 and y40 is an integer from 1 to 19, wherein 3 ≤ (x40 + y40) ≤ 20;

[0408] x41 is an integer from 1 to 20, and y41 is an integer from 0 to 19, wherein 3 ≤ (x41 + y41) ≤ 20;

[0409] Y is selected from a group consisting of -OH, -NHR4, -SH, -CO2H, -C(O)NHR4, -C(S)NHR4,

[0410] R4

[0411] I

[0412]

[0413] each R4is independently selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-Cs alkyl), - (Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(Ci-C3alkyl)-(Ce-Cwaryl), -(C1-C3 heteroal kyl)-(Ce-Cw aryl), and -(C6-C10aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroal kyl)-(Ce-Cw aryl) have 1 to 4 heteroatoms independently selected from O, S, and Si; and

[0414] X’ is independently acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, borate, or an organo- substituted derivative of any of the foregoing.

[0415]

[0132] In some embodiments, R1is selected from a group consisting of -(Ci2-Cso alkyl), -(C12-C30 heteroalkyl), -(C12-C30 alkyl)-(C6-Cw aryl), -(C12-C30 heteroalkyl)-(C6-Cw aryl), -(Ce-Cw aryl)-(Ci2-C3o alkyl), and -(C6-Cw aryl)-(Ci2-C3o heteroalkyl); wherein -(C12-C30 heteroalkyl), -(C12-C30 heteroalkyl)-(Ce-Cw aryl), and -(Ce-Cw aryl)-(Ci2-Cso heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R1is -(C12-C30 alkyl). In some embodiments, R1is -(Cs-Cso heteroalkyl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R1is -(Ce-Cw aryl)-(Cw-C30 alkyl). In some embodiments, R1is -(Ci2-C3oalkyl)-(Ce-Cw aryl). In some embodiments, R1is -(Ce-Cw aryl)-(Ci2-Cso heteroalkyl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R1is -(C12-C30 heteroalkyl)-(Ce-Cw aryl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R1is -(CRmRn)xw-W10-(CRpRq)yw-H. In some embodiments, R1is -(CRmRn)xii-W11-(CRpRq)yii-H.

[0416]

[0133] In some embodiments, R2is -(C1-C4 alkyl). In some embodiments, R2is -(C1-C4 heteroalkyl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R2is -(Ce-Cw aryl)-(Ci-C4 alkyl). In some embodiments, R2is -(C1-C4 alkyl)-(Ce-Cw aryl). In some embodiments, R2is -(Ce-Cw aryl). In some embodiments, R2is -(Ce-Cw aryl)-(Ci-C4 heteroalkyl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R2is -(C1-C4 heteroalkyl)-(Ce-Cw aryl) with 1 to 4 heteroatoms Atty. Dkt. No. 136938-0902

[0417] independently selected from O, S, and Si. In some embodiments, R2is -(CRmRn)x20-W20-(CRpRq)y20-H. In some embodiments, R2is -(CRmRn)x21-W21-(CRpRq)y21-H.

[0418]

[0134] In some embodiments, R3is selected from a group consisting of -(Ci-C4 alkyl), -(C1-C4heteroalkyl), -(C1-C4alkyl)-(C6-C10aryl), -(C1-C4heteroalkyl)-(C6-C10aryl), -(C6-C10aryl)-(C1-C4alkyl), and -(C6-C10aryl)-(C1-C4heteroalkyl); wherein -(Ci-C4heteroalkyl), -(Ci-C4heteroal kyl)-(Ce-Cw aryl), and -(Ce-Cw aryl)-(Ci-C4heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R3is -(Ci-C4alkyl). In some embodiments, R3is -(Ci-C4heteroalkyl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R3is -(Ce-Cw aryl)-(Ci-C4alkyl). In some embodiments, R3is -(Ci-C4alkyl)-(Ce-Cw aryl). In some embodiments, R3is -(Ce-Cw aryl)-(Ci-C4heteroalkyl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R3is -(Ci-C4heteroalkyl)-(Ce-Cw aryl) with 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R3is -(CRmRn)X3o-W30-(CRpRq)y3o-H. In some embodiments, R3is -(CRmRn)X3i-W31-(CRpRq)y3i-H.

[0419]

[0135] In some embodiments, at least one of R2and R3is -(Ci-C4alkyl). In some embodiments, R2and R3are methyl. In some embodiments, R1is C12-C30 alkyl, and R2and R3are methyl.

[0420]

[0136] In some embodiments, A is -(C3-C20 alkylene)- optionally substituted with 1 to 6 substituents independently selected from -(Ce-Cw aryl)-(Ci-Cs alkyl), -(Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(Ci-C3alkyl)-(Ce-Cwaryl), -(C1-C3 heteroalkyl)-(Ce-Cwaryl), and -(Ce-Cw aryl). In some embodiments, A is -(C3-C20 heteroalkylene)- with 1 to 4 heteroatoms independently selected from O, S, and Si, and optionally substituted with 1 to 6 substituents independently selected from -(C6-C10aryl)-(C1-C3alkyl), -(C6-C10aryl)-(C1-C3heteroalkyl), -(C1-C3alkyl)-(C6-C10aryl), -(C1-C3heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl). In some embodiments, A is -(Ce-Cw arylene)-(Cs-C2o alkylene)-. In some embodiments, A is -(C3-C2oalkylene)-(Ce-Cw arylene)-.

[0421]

[0137] In some embodiments, A is -(CRmRn)x4o-W4O-(CRpRq)y4o-. In some embodiments, A is -(CRmRn)x4i-W41-(CRpRq)y4i-.

[0422]

[0138] In some embodiments, A is -(CH2)m- or-(CH2CHR5-O-)nCH2CHR5-, wherein m is an integer from 2 to 20; n is 0, 1, 2, 3, 4, or 5; and each R5is independently selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-Cs alkyl), -(Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(C1-C3 alkyl)-(Ce-Cwaryl), -(Ci-C3heteroalkyl)-(Ce-Cwaryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroalkyl)-(Ce-Cw aryl) have 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, R5is H or methyl.

[0423]

[0139] In some embodiments, Y is -OH. In some embodiments, Y is -NHR4. In some embodiments, Y is -SH. In some embodiments, Y is -CO2H. In some embodiments, Y is -C(O)NHR4, wherein R4is selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-Cs alkyl), - Atty. Dkt. No. 136938-0902

[0424] (Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(Ci-C3alkyl)-(Ce-Cwaryl), -(C1-C3 heteroal kyl)-(Ce-Cw aryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroalkyl)-(C6-C10aryl) have 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, Y is -C(S)NHR4, wherein R4is selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-C3alkyl), -(C6-Cw aryl)-(Ci-C3heteroalkyl), -(Ci-C3alkyl)-(Ce-Cwaryl), -(C1-C3 heteroal kyl)-(Ce-Cw aryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroalkyl)-(Ce-Cw aryl) have 1 to 4 heteroatoms independently selected from O, S,

[0425] R4

[0426] and Si. In some embodiments, Y is

[0427]

[0428] R4R4, wherein each R4is independently selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-Cs alkyl), -(Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(Ci-C3alkyl)-(Ce-Cwaryl), -(C1-C3 heteroalkyl)-(Ce-Cwaryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroalkyl)-(Ce-Cwaryl) have 1 to 4 heteroatoms independently selected from O, S, and Si. In some embodiments, Y is

[0429] R4

[0430] R4

[0431]

[0432] R4R4, wherein each R4is independently selected from a group consisting of H, -(Ce-Cw aryl)-(Ci-Cs alkyl), -(Ce-Cw aryl)-(Ci-Cs heteroalkyl), -(Ci-C3alkyl)-(Ce-Cwaryl), -(C1-C3heteroalkyl)-(Ce-Cwaryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-Cs heteroalkyl) and -(C1-C3 heteroalkyl)-(Ce-Cwaryl) have 1 to 4 heteroatoms independently selected from O, S, and Si.

[0433]

[0140] X' may be independently selected from the group consisting of acetate, halide (e.g., chloride, bromide, or iodide), sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives. As used herein, and unless stated otherwise, “organo-substituted derivatives” refers to anions wherein a sulfur atom, a phosphorous atom, a boron atom, a silicon atom or carbonyl group is substituted with either an alkyl or an aryl group. Nonlimiting examples include methylsulfate, methanesulfonate, p-toluene sulfonate, trifluoromethylsulfonate, and trifluoroacetate.

[0434] C-18H37X I + Br

[0141] In some embodiments, the quaternary ammonium salt is

[0435]

[0436] C18H37J|+Br’ p |_i I Br" C16H33X I +Br

[0437] OHCl6 33^N^^OH / N'^O-. OH

[0438]

[0439] Atty. Dkt. No. 136938-0902

[0440] C-I4H29 X I

[0441] C14H29X I Ci 122^2255 x'NI

[0442]

[0443] T-N^ / x / X / OH

[0444]

[0445] O, or a combination of two or more thereof.

[0446]

[0142] The quaternary ammonium salt may be present in the dried microfiber or dried nanofiber in an amount of about 5 wt.% to about 50 wt.%. This includes about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 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, or 50 wt.%, or any value therebetween. In some embodiments, the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of about 5 wt.% to about 25 wt.%.

[0447]

[0143] The quaternary ammonium salt may be present in the dried microfiber or dried nanofiber in an amount of about 1.0 x10'4to about 1.2 x10-3mole of the quaternary ammonium group per gram of the dried microfiber or dried nanofiber. This includes about 1.0 x10’4, 1.2 x10’4, 1.4 x10’4, 1.6 x10’4, 1.8 x10’4, 2.0 x10’4, 2.2 x10’4, 2.4 x10’4, 2.6 x10’4, 2.8 x10’4, 3.0 x10’4, 3.2 x10’4, 3.4 x10’4, 3.6 x10’4, 3.8 x10’4, 4.0 x10’4, 4.2 x10’4, 4.4 x10’4, 4.6 x10’4, 4.8 x10’4, 5.0 x10’4, 5.2 x10’4, 5.4 x10’4, 5.6 x10’4, 5.8 x10’4, 6.0 x10’4, 6.2 x10’4, 6.4 x10’4, 6.6 x10’4, 6.8 x10’4, 7.0 x10’4, 7.2 x10’4, 7.4 x10’4, 7.6 x10’4, 7.8 x10’4, 8.0 x10’4, 8.2 x10’4, 8.4 x10’4, 8.6 x10’4, 8.8 x1 O’4, 9.0 x1 O’4, 9.2 x1 O’4, 9.4 x10’4, 9.6 x1 O’4, 9.8 x1 O’4, 1.0 x10'3, or 1.2 x10-3mole, including any value therebetween.

[0448]

[0144] The hydroxy-functionalized oligomer, polymer, or copolymer may be a polymer, copolymer or oligomer of a hydroxy-functionalized monomer, or a precursor thereof selected from a group consisting of ethylene oxide, propylene oxide, tetrahydrofuran (THF), caprolactone, butyrolactone, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N-methylol acrylamide, N-methylol methacryamide, allyl alcohol, triethanol amine, diethanol alkylamine, and N, N, N’N’-tetrakis(2-hydroxyalkyl) ethylenediamine. In some embodiments, the hydroxyfunctionalized oligomer, polymer, or copolymer is a copolymer of 2-hydroxyethyl methacrylate. In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is a copolymer of methyl methacrylate (MMA), ethylhexyl acrylate (2-EHA), and 2-hydroxyethyl methacrylate (HEMA). In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is a copolymer of methyl methacrylate (MMA), 2-ethylhexyl acrylate (2-EHA), and 2-hydroxyethyl methacrylate (HEMA) in a molar ratio of 64.8:34.2:1.

[0449]

[0145] In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 300 to about 100,000 daltons. This includes a weight average molecular weight of about 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, 2000, 2050, 2100, Atty. Dkt. No. 136938-0902

[0450] 2150, 2200, 2250, 2300, 2350, 2400, 2450, 2500, 2550, 2600, 2650, 2700, 2750, 2800, 2850, 2900, 2950, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, 8000, 8100, 8200, 8300, 8400, 8500, 8600, 8700, 8800, 8900, 9000, 9100, 9200, 9300, 9400, 9500, 9600, 9700, 9800, 9900, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, 70000, 75000, 80000, 85000, 90000, 95000, or 100,000daltons, or any value therebetween. In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 400 to about 10,000 daltons, or from about 600 to about 3000 daltons.

[0451]

[0146] In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 20 wt.%. This includes about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt.%, or any value therebetween.

[0452]

[0147] In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is present in the microfiber or nanofiber in an amount of about 25 wt.% to about 50 wt.%. This includes about 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, or 50 wt.%, or any value therebetween.

[0453]

[0148] In some embodiments, the polyethyleneimine intermediate and the quaternary ammonium salt are present in the dried microfiber or dried nanofiber in a combined amount of less than 35 wt.%. In some embodiments, in the absence of any polyethyleneimine intermediate, the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of less than 35 wt.%. In some embodiments, (1) the polyethyleneimine intermediate and the quaternary ammonium salt are present in the dried microfiber or dried nanofiber in a combined amount of less than 35 wt.%; or (2) in the absence of any polyethyleneimine intermediate, the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of less than 35 wt.%.

[0454]

[0149] In some embodiments, the polyethyleneimine intermediate and the quaternary ammonium salt are present in a combined amount of less than 1.2 x10-3mole of the quaternary ammonium group per gram of the dried polymer or interpenetration network. In some embodiments, in the absence of any polyethyleneimine intermediate, the quaternary ammonium salt is present in an amount of less than 1.2 x10'3mole of the quaternary ammonium group per gram of the dried microfiber or dried nanofiber. In some embodiments, (1) the polyethyleneimine intermediate and the quaternary ammonium salt are present in a combined amount of less than 1.0 x10'3mole of the quaternary ammonium group per gram of the dried polymer or interpenetration network, or (2) in the absence of any Atty. Dkt. No. 136938-0902

[0455] polyethyleneimine intermediate, the quaternary ammonium salt is present in an amount of less than 1.0 x10'3mole of the quaternary ammonium group per gram of the dried microfiber or dried nanofiber.

[0456]

[0150] In some embodiments, the microfiber or nanofiber further comprises covalent attachment of a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof. In some embodiments, the trialkoxysilane is 3-aminopropyl triethoxysilane.

[0457]

[0151] In some embodiments, the microfiber or nanofiber has a total quaternary ammonium salt density of at least 3.0 x10-4mole, preferably at least 5.0 x10-4mole, of total quaternary ammonium salt functionality per gram of dried microfiber or dried nanofiber.

[0458]

[0152] In some embodiments, the microfiber or nanofiber comprises, consists essentially of, or consists of a blend, composite, or interpenetrating polymer network comprising, consisting essentially of, or consisting of:

[0459] (1) QPEI-C3OHC6; and

[0460] (2) a HEMA polyol (e.g., pHEMA-2).

[0461]

[0153] In some embodiments, the microfiber or nanofiber comprises, consists essentially of, or consists of a polymer or interpenetrating polymer network comprising, consisting essentially of, or consisting of a polymerization product of reagents and / or a crosslinking product of reagents comprising, consisting essentially of, or consisting of:

[0462] (1) QPEI-C3OHC6;

[0463] (2) DESMODUR® N100; and

[0464] (3) a HEMA polyol (e.g., pHEMA-2).

[0465]

[0154] In some embodiments, the microfiber or nanofiber comprises, consists essentially of, or consists of a polymer or interpenetrating polymer network comprising, consisting essentially of, or consisting of a polymerization product and / or a crosslinking product of reagents comprising, consisting essentially of, or consisting of:

[0466] (1) QPEI-C3OHC6;

[0467] (2) an adduct of C18DMDEG, DESMODUR® N100, and PTMG-1000; and

[0468] (3) a HEMA polyol (e.g., pHEMA-2).

[0469]

[0155] In some embodiments, the microfiber or nanofiber comprises, consists essentially of, or consists of a polymer or interpenetrating polymer network comprising, consisting essentially of, or consisting of a polymerization product and / or a crosslinking product of reagents comprising, consisting essentially of, or consisting of:

[0470] (1) QPEI-C3OHC6; Atty. Dkt. No. 136938-0902

[0471] (2) an adduct of C18DMDEG, DESMODUR® N100, and PTMG-1000;

[0472] (3) a HEMA polyol (e.g., pHEMA-2); and

[0473] (4) 3-aminopropyltriethoxysilane.

[0474]

[0156] In some embodiments, the microfiber or nanofiber comprises, consists essentially of, or consists of a polymer or interpenetrating polymer network comprising, consisting essentially of, or consisting of a polymerization product and / or a crosslinking product of reagents comprising, consisting essentially of, or consisting of:

[0475] (1) an adduct of C18DMDEG, DESMODUR® N100, and PTMG-1000; and

[0476] (2) a HEMA polyol (e.g., pHEMA-2).

[0477]

[0157] In some embodiments, the microfiber or nanofiber is a core-shell microfiber or nanofiber. In some embodiments, quaternary ammonium salt density of the shell is different from quaternary ammonium salt density of the core. In some embodiments, quaternary ammonium salt density of the shell is higher than quaternary ammonium salt density of the core.

[0478]

[0158] The electrospun fibers described herein may have a diameter of 0.1 to 10 microns. Typically, microfibers have a thickness of >100 nm, whereas nanofibers have a diameter of < 100 nm. In some embodiments, the microfibers have a diameter of about 1 to 4 microns, or 1 to 10 microns. In some embodiments, the nanofibers have a diameter of about 100 nm.

[0479]

[0159] In another aspect, provided herein is a nonwoven fabric comprising the microfiber and / or nanofiber described herein. In some embodiments, the nonwoven fabric has a coverage of microfibers or nanofibers of at least 3 g / m2, preferably at least 5 g / m2. This includes a coverage of 3, 4, 5, 6, 7, 8, 9, or 10 g / m2, or more, or any value therebetween. In some embodiments, the nonwoven fabric has a coverage of microfibers or nanofibers of about 3 g / m2to about 10 g / m2.

[0480]

[0160] In some embodiments, the nonwoven fabric is deposited on a support to form a composite nonwoven fabric. In some embodiments, the support is a non-antimicrobial nonwoven fabric having a coverage of microfibers or nanofibers of at least 3 g / m2, preferably at least 5 g / m2. In some embodiments, the support is a second nonwoven fabric with the same coverage of microfibers or nanofibers as the nonwoven fabric. In some embodiments, the support is a second nonwoven fabric with different coverage of microfibers or nanofibers compared to the nonwoven fabric. In some embodiments, the support is a second nonwoven fabric with the same quaternary ammonium salt density as the nonwoven fabric. In some embodiments, the support is a second nonwoven fabric with different quaternary ammonium salt density compared to the nonwoven fabric.

[0481]

[0161] In another aspect, provided herein is an apparatus or accessory comprising the nonwoven fabric described herein. In some embodiments, the apparatus or accessory is selected from a group consisting of a filter, mask, membrane, diaper, wound care dressing, Atty. Dkt. No. 136938-0902

[0482] super absorbent, humectant, synthetic skin, synthetic organ, skincare product, and scaffold for controlled release of compounds such as fertilizers, nutritional supplements, pesticides, or pharmaceutically active agents. In some embodiments, the wound care dressing includes a film, a gel, a matrix product, a wound therapy system, placental membrane, a non-silver wound dressing product, a negative-pressure wound therapy system, a surgical dressing, an adhesive antimicrobial dressing, a barrier dressing, an adhesive or non-adhesive hydrocellular foam dressing, a gelling fiber wound dressing, or a low adherent absorbent dressing.

[0483] METHODS OF PREPARATION

[0484]

[0162] Methods are provided herein for the preparation of the microfibers and nanofibers described herein.

[0485]

[0163] In another aspect, provided herein is a method to prepare a microfiber or nanofiber described herein, the method comprising:

[0486] preparing a solution comprising (1) the polyethyleneimine intermediate, and (2) the hydroxyfunctionalized oligomer, polymer, or copolymer; and

[0487] electrospinning the solution to form the microfiber or nanofiber.

[0488]

[0164] In another aspect, provided herein is a method to prepare a microfiber or nanofiber described herein, the method comprising:

[0489] preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the multifunctional crosslinker; and (3) the hydroxy-functionalized oligomer, polymer, or copolymer; and

[0490] electrospinning the solution to form the microfiber or nanofiber.

[0491]

[0165] In another aspect, provided herein is a method to prepare a microfiber or nanofiber described herein, the method comprising:

[0492] preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the adduct of the quaternary ammonium salt and the multifunctional crosslinker; and (3) the hydroxyfunctionalized oligomer, polymer, or copolymer; and

[0493] electrospinning the solution to form the microfiber or nanofiber.

[0494]

[0166] In some embodiments, the adduct further comprises a chain extender as described herein. In some embodiments, the chain extender is PTMG (e.g., PTMG-1000).

[0495]

[0167] In some embodiments, the solution further comprises a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof; and optionally a catalyst selected from a group consisting of citric acid, oxalic acid, and XK-651 (bismuth carboxylate catalyst). Atty. Dkt. No. 136938-0902

[0496]

[0168] In another aspect, provided herein is a method to prepare a microfiber or nanofiber described herein, the method comprising:

[0497] preparing a first solution comprising (1) the polyethyleneimine intermediate; and (2) the adduct of the quaternary ammonium salt and the multifunctional crosslinker; preparing a second solution comprising the hydroxy-functionalized oligomer, polymer, or copolymer;

[0498] combining the first solution and the second solution via in-line mixing to form a third solution;

[0499] and

[0500] electrospinning the third solution to form the microfiber or nanofiber.

[0501] In some embodiments, the third solution is formed in situ by for example, a static mixer or other in-line mixer, immediately before the third solution enters a spinneret or a nozzle of an electrospinning machine. In some embodiments, the adduct further comprises a chain extender as described herein. In some embodiments, the chain extender is PTMG (e.g., PTMG-1000).

[0502]

[0169] In some embodiments, the method further comprises curing the microfiber or nanofiber. In some embodiments, the method further comprises washing the microfiber or nanofiber.

[0503]

[0170] In some embodiments, the microfiber or nanofiber has a total quaternary ammonium salt density of at least 3.0 x10-4mole of total quaternary ammonium salt functionality per gram of dried microfiber or dried nanofiber.

[0504]

[0171] In some embodiments, the hydroxy-functionalized oligomer, polymer, or copolymer is present in the dried microfiber or dried nanofiber in an amount of about 20 wt.% to about 50 wt.%.

[0505]

[0172] In some embodiments, the microfiber or nanofiber is electrospun onto a temporary substrate and released as a free-standing nonwoven fabric. In some embodiments, the microfiber or nanofiber is electrospun onto an inert nonwoven support to form a composite nonwoven fabric.

[0506]

[0173] In some embodiments, the microfiber or nanofiber is electrospun onto a surface of a nonwoven fabric support to create a nonwoven surface layer to form a composite nonwoven fabric. In some embodiments, the nonwoven surface layer has the same quaternary ammonium salt density as the nonwoven fabric support. In some embodiments, the nonwoven surface layer has different quaternary ammonium salt density compared to the nonwoven fabric support.

[0507]

[0174] The description of embodiments of the disclosure is not intended to be exhaustive or to limit the disclosure to the precise form disclosed. While specific embodiments of, and examples for, the disclosure are described herein for illustrative purposes, various equivalent modifications are possible within the scope of the disclosure, as those skilled in the relevant Atty. Dkt. No. 136938-0902

[0508] art will recognize. For example, while method steps or functions are presented in a given order, alternative embodiments may perform functions in a different order, or functions may be performed substantially concurrently. The teachings of the disclosure provided herein can be applied to other procedures or methods as appropriate. The various embodiments described herein can be combined to provide further embodiments. Aspects of the disclosure can be modified, if necessary, to employ the compositions, functions and concepts of the above references and application to provide yet further embodiments of the disclosure. Moreover, due to biological functional equivalency considerations, some changes can be made in protein structure without affecting the biological or chemical action in kind or amount. These and other changes can be made to the disclosure in light of the detailed description. All such modifications are intended to be included within the scope of the appended claims.

[0509]

[0175] Specific elements of any of the foregoing embodiments can be combined or substituted for elements in other embodiments. Furthermore, while advantages associated with certain embodiments of the disclosure have been described in the context of these embodiments, other embodiments may also exhibit such advantages, and not all embodiments need necessarily exhibit such advantages to fall within the scope of the disclosure.

[0510]

[0176] The technology described herein is further illustrated by the following examples which in no way should be construed as being further limiting. 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.

[0511] EXAMPLES

[0512]

[0177] The present technology now being generally described, it will be more readily understood by reference to the following examples. These are included merely for purposes of illustration of certain aspects and embodiments of the present technology and are not intended to limit the present technology.

[0513] ASSESSMENT OF THE ANTIVIRAL ACTIVITY OF THE POLYMERS AND / OR COATINGS THEREOF

[0178] Assessment of the antiviral activity of microfibers of the present technology was conducted as follows. All samples and all accessories in the assessment were first disinfected by either high temperature autoclave treatment, alcohol cleaning or irradiation in a UV laminar flow chamber.

[0514]

[0179] First, adenovirus (108 PFU / mL, plaque forming unit, MOI=100 multiplicity of infection) was diluted to 2x107PFU / ml in a phosphate buffer solution (PBS). Then, 0.1 mL of the diluted virus solution was deposited on the disinfected samples. Atty. Dkt. No. 136938-0902

[0515]

[0180] The antiviral activity was determined by the quantitative reverse transcription polymerase chain reaction (RT-qPCR) method.

[0516] SAMPLE PREPARATION

[0517]

[0181] The medium (DMEM, high sucrose, pyruvate; ThermoFisher, Catalog number:

[0518] 11995040) was removed from the refrigerator and conditioned in a water bath at 37 °C for 30 min.

[0519]

[0182] Preparation of Virus Fluid: The typical virus count of the stock is 5 Lambda (5x108) per tube. To the virus tube, 1 mL of DMEM medium was added and the tube was mixed homogeneously with a vortex mixer for 5-10 sec to make a virus fluid of 5x108 / mL concentration. The virus fluid was further diluted to 5x107 / mL with DMEM medium for the antivirus tests.

[0520]

[0183] RT-qPCR Procedure for Coatings: The coated film was immersed in 99% alcohol for 1 sec. Any excess alcohol was removed from the surface. The film was then air-dried in a new petri dish for 15-20 min. Then 100 pL of the diluted virus fluid (5x106 / mL) was dropped onto the dried film. The petri dish was covered, and the virus allowed to contact the film for desired contact time period. In some of the experiments, the contact time was reduced to as short as 30 sec. The virus fluid from the film was transferred to an Eppendorf tube. The film was then rinsed twice with 50 pL of 1X PBD and the rinsing fluid was combined into the Eppendorf tube. The total test fluid volume was 200 pL and ready for the DNA extraction.

[0521]

[0184] RT-qPCR Procedure for Aqueous Solutions: 100 pL of the test sample was added to 100 pL of the diluted virus fluid (5x107 / mL) in an Eppendorf tube and the mixture (5x106virus count) was shaken on a shaker for 30 min. DNA was extracted using the Novogene DNA kit following the specified extraction procedure.

[0522]

[0185] RT-qPCR Tests: Each sample was tested in quadruplicates. The ingredients listed in the table below were mixed thoroughly in an Eppendorf tube.

[0523] Formulation of the premix for q-RT-PCR Test

[0524] Items Volume (pL)

[0525] DI Water 15.4

[0526] Forward-primer 2.2

[0527] Reverse-primer 2.2

[0528] Master mix buffer 22.0

[0529] (Kapa BioSystems

[0530] PCR reagent)

[0531] Sample DNA 4.4 (Added as the last ingredient)

[0532]

[0533] TOTAL VOLUME 46.2 pL Atty. Dkt. No. 136938-0902

[0534] EGFP primer sequence:

[0535] Forward-primer FLenti-GFP 5’AJkCCACTACCTgAgCACCCA3:(2Q) SEQ ID NO:1 2 OPC Reverse-primer RLenti-GFP 5’gTCCATgCCgAgAgTgATCC3'(20) SEQ ID NO:2 2 OPC

[0536]

[0537]

[0186] Ten pL of the premix was added to each cavity of a test plate, with three samples taken for each coating and each sample was done in quadruplicate. Accordingly, a total of 12 tests were done for each coating.

[0538]

[0187] The plate was centrifuged to assure all the premix fluid flowed to the bottom of the cavities. The plate was then inserted into an Applied Biosystems QuantStudio 3 (ThermoFisher) to determine the Cycle Threshold (CT) number for the calculation of the antiviral efficiency. The antiviral efficiency was calculated quantitatively from the CT number.

[0539] TESTING

[0540]

[0188] Qualitative Cell Viability Test for Coatings: The microfiber was placed in a petri dish and 100 pL of DMEM medium was dropped on the coating. The petri dish was then covered for 30 min. The medium on the film was then transferred to a cell plate containing 8x104cells in 500 pL of medium in each partition. The film was rinsed twice with 50 pL of DMEM medium and the rising fluid was combined with previous test fluid in the same location in the plate. A total of 200 pL of the test fluid was added to the 500 pL cell / medium. The cell plate was incubated at a 37°C / 95%RH CO2 incubator for 48-96 hours, after which the cell growth and morphology were observed under visible microscope. Dead cells floated or were suspended in the medium, while live cells remained fixed to the bottom of the plate. This test was for the assessment of the contact cytotoxicity of the polymer film. In cases where this test indicates some degree of cytotoxicity, the actual mechanism for the cell death is not given although cell death due to chemicals extracting from the coating are one possibility.

[0541]

[0189] Qualitative Cell Viability Test for Polymer Solution or Dispersion: 100 pL of the polymer solution or dispersion and 100 pL of DMEM medium were added to an Eppendorf and mixed thoroughly with a shaker for 30 min. For polymer film, a fixed area of the film was cut and dispersed in the medium for the test. The test fluid was transferred to the cell plate and the cells were grown in a 37°C / 95%RH CO2 incubator for 48-96 hours. The cell growth and morphology were recorded under visible microscope.

[0542]

[0190] Qualitative Antiviral Efficiency Test of Polymer film: 100 pL of the virus fluid (5x107 / mL) was dropped on the polymer film in a petri dish. The petri dish was covered for Atty. Dkt. No. 136938-0902

[0543] 30 min. The virus fluid was transferred to a cell plate containing 8x104cells in 500 pL of medium in each partition. The film was then rinsed twice with 50 pL of DMEM medium and the rising fluid was combined with previous test fluid in the same location in the plate. The total volume of the test fluid was 200 pL. The cell plate was then incubated at a 37°C / 95%RH CO2 incubator for 48-96 hours. Finally, the cell morphology and the fluorescence were recorded under UV microscope.

[0544]

[0191] Qualitative Antiviral Efficiency Test of Polymer Solution or Dispersion: 100 pL of the virus fluid (5x107 / mL) and 100 pL of the polymer solution or dispersion were added to an Eppendorf and shaken thoroughly with a shaker for 30 min. The test mixture was added in a cell plate containing 8x104cells in 500 pL of medium in each partition. The cell plate was then incubated at a 37°C / 95%RH CO2 incubator for 48-96 hours. Finally, the cell morphology and the fluorescence were recorded under UV microscope.

[0545]

[0192] Example I. Synthesis of polyethyleneimine intermediate QPEI-C3OHC6

[0546] 4C6PEI QPEI-C3OHC6

[0547]

[0548] (R = hexanyl) (R=" CeHnor-CaH6OH)

[0549]

[0193] EPOMIN P-1000 (polyethyleneimine, Mw = about 70,000, 30% solid in water, from Nippon Shokubai) (800 g), 2,5-di-t-butyl-4-methyl-phenol (BHT, from Aldrich) (1.403 g), 1-bromohexane (99% purity, from Aldrich) (977.22 g), and isopropanol (I PA) (2900 g) were mixed in a flask at room temperature under nitrogen at about 300 rpm for 30 minutes to obtain a clear solution. The mixture was then refluxed under nitrogen for an hour. A solution of K2CO3 (404.996 g) in distilled water (367.177 g) was added into the mixture by a metering pump in 6 hours at an addition rate of about 2.145 g / min. The reaction mixture was allowed to continue to reflux under nitrogen for another 18 hours. The IPA and water in the reaction mixture were then stripped off by a rotavap at 50°C to obtain a slurry. Distilled water (3700 g) was added and mixed thoroughly at 300 rpm for 30 minutes. The resultant mixture was transferred to a separation funnel and the aqueous phase was removed. The oil phase was diluted with methyl ethyl ketone (MEK) (1345 g) and filtered to obtain 2017.6 g of a 33.33% solution with about 672.6 g (dried) of the intermediate 4C6-PEI in MEK (a yield rate of about 95%).

[0550]

[0194] To the 33.33% solution of intermediate 4C6-PEI (2017.6 g) in MEK, BHT (0.861 g), 1-bromohexane (99% purity) (678.613 g) and 3-bromo-1 -propanol (95% purity, from Aldrich) (174.11 g) were mixed thoroughly under nitrogen. The mixture was stirred at 300 rpm, refluxed in nitrogen for 24 hours, and filtered to obtain 2871 g of a pale-yellow solution in Atty. Dkt. No. 136938-0902

[0551] MEK containing about 957 g (dried) of quaternary poly-ethyleneimine salt QPEI-C3OHC6, (a yield rate of about 90%).

[0552]

[0195] Example II. Microfibers of QPEI-C3OHC6 and HEMA polyol blend

[0553]

[0196] QPEI-C3OHC6 (1.5 g, dried) as prepared in Example I and HEMA polyol (pHEMA-2, the weight ratio of methyl methacrylate (MMA) / 2-ethyl hexyl acrylate (2-EHA) / 2-hydroxyethyl methacrylate (HEMA) = 64.8 / 34.2 / 1, Mw=175,460, Tg= 20°C, obtained from Gelie Chemicals, Taiwan) (1.5 g, dried), were dissolved in MEK (7 g) and transferred to a 3-ml plastic syringe equipped with a 21G stainless steel flat head needle. The mixture was electro-spun onto a corona-treated PET wrapped on the metal roller collector of an electrospinning equipment FES-COS obtained from Falco Tech Enterprise Co., Ltd, Taiwan, at 20kV, with a flow rate of 0.01 ml / min and a distance of 20 cm between needle and collector.

[0554]

[0197] Nonwoven fabrics of the QPEI-C3OHC6 / HEMA polyol blend with various coverages were collected as shown in Table 1. They were post-heated in an oven at 40 °C for about 2 hours and their antiviral efficiency and cytotoxicity were tested by the procedures described above. Microfibers (1-2 mm) were obtained for the 1:1 blend of QPEI-C3OHC6 and HEMA Polyol (FIG. 1), gsm = g / m2. The fiber coverage increased with increasing collecting time (Table 1). Antiviral efficiency against adenovirus reached 99.41% at a coverage of about 5.18 g / m2. In contrast, QPEI-C3OHC6 itself (Example II-0) failed to form any stable microfiber under the same electrospinning conditions.

[0555] Table 1.

[0556] HEMA Collecting Microfiber Antiviral QPEI-C3OHC6

[0557] Example polyol time coverage efficiency against (wt.%)

[0558] (wt.%) (min) (g / m2) adenovirus Failed to

[0559] ll-O 100 0 — form stable N / A

[0560] fiber

[0561] 11-1 50 50 30 2.01 ± 0.13 89.35 ± 0.56% II-2 50 50 60 3.04 ± 0.14 79.74 ± 2.41% II-3 50 50 90 4.01 ± 0.16 89.35 ± 2.80%

[0562]

[0563]

[0198] Example III. Microfibers of crosslinked polymer networks comprising

[0564] C18H37S I + Br / covalently-bonded quaternary ammonium saltN

[0565]

[0566] O (C18DMDEG)

[0567]

[0199] Polyisocyanate (DESMODUR® N100) (281.9 g) and C18DMDEG (281.1 g) were dissolved completely in anhydrous MEK (269.2 g) under nitrogen at 70 °C with magnetic stirring. 10 wt.% catalyst (XK-651, from King Industries) in MEK solution (5.0 g) was added, Atty. Dkt. No. 136938-0902

[0568] and the resultant mixture stirred at 70 °C for 1.5 hours. The reaction mixture was concentrated to 75 wt.% solid by rotary evaporation at 45 °C, 90 torr for about 10 min.

[0569] Poly(tetra-methylene ether) glycol (PTMG-1000, Mw = 1000, obtained from Aldrich) (100.0 g) was added, and the resultant mixture stirred at 70 °C under nitrogen for 1 hour and divided evenly to obtain 5 containers of equal-weight of C18DMDEG-N100-PTMG adduct solutions. To each container was added an additional 0.0 g, 24.00 g, 36.00 g, 48.02 g, 114.02 g of C18DMDEG and 0.0 g, 0.72 g, 0.78 g, 0.84 g, 1.17 g of a 10 wt.% XK-651 solution in MEK, respectively, and the mixtures allowed to react at 70 °C under nitrogen for 1.5 hours. A 35 wt.% solution of a HEMA polyol (as described in Example II) in MEK (257.37 g) was then added, and the mixture allowed to react at 70 °C for an additional 30 min. The reaction mixtures were diluted with anhydrous MEK to 30 wt.% solid for electrospinning with the same electrospinning process as described in Example II. The microfibers were collected for 90 min with a target fiber coverage of about 4 g / m2and post-cured at 40 °C for 16 hours followed by 4 hours at 60 °C.

[0570]

[0200] Antiviral efficiencies against Adenovirus and MTT assay results of the C18DMDEG-containing microfibers are shown in Table 2. Antiviral efficacy against Adenovirus increased from 96.96 ± 1.45% to 99.90 ± 0.01% as the total concentration of C18DMDEG in the fiber increased from 20.77 wt.% to 48.65 wt.%. However, as the total concentration of C18DMDEG exceeded about 32.36 wt.% (Example HI-3), microfiber integrity and cell survival percentage (as measured by MTT assay) appeared to deteriorate rapidly (FIG. 2 and Table 2). The diameter of the fibers also increased from 1-2 pm to about 4 pm. Without being bound by theory, it is believed that too high a concentration of C18DMDEG in the microfiber composition resulted in a poor incorporation of the quaternary ammonium salt into the polymer network as well as an insufficient degree of crosslinking, thereby adversely impacting physico-mechanical properties of the fibers as well as the cell survival rate, potentially due to leaching out of some of the insufficiently bonded excess quaternary ammonium salts during the tests.

[0571] Table 2

[0572] C18DMDEG MTT Assay PTMG- HEMA Antiviral

[0573] In pre Total efficiency

[0574] E Polyiso. In postx. Total 1000 polyol

[0575] (dry wt.%) reaction reaction (dry against Cell survival (dry (dry (dry

[0576] (dry (dry wt.%) adenovirus Cone.

[0577] w wt.%) wt.%) (%) wt.%) wt.%) t.%) (%)

[0578] 96.96 ± A(100%) 4.91 ± 0.4 111-1 26.83 20.77 0.00 20.77 9.52 42.88 100.00 A(50%) 16.71 ± 2.43

[0579] 1.45 A(25%) 62.67 ± 1.70 A(12.5%) 76.29 ± 5.03 98.61 ± A(100%) 7.09 ± 0.82 HI-2 24.08 18.64 10.25 28.89 8.54 38.49 100.00 A(50%) 82.58 ± 0.78

[0580] 2.01 A(25%) 81.27 ± 4.36 A(12.5%) 89.30 ± 3.17 HI-3 22.91 17.73 14.63 32.36 8.13 36.60 100.00 98.92 ± A(100%) 11.90 ± 1.51

[0581]

[0582] A(50%) 62.92 ± 3.37 Atty. Dkt. No. 136938-0902

[0583] 1.08 A(25%) 90.37 ± 2.51 A(12.5%) 93.99 ± 3.65 99.73 ± A(100%) 4.45 ± 0.13 III-4 21.84 16.91 18.60 35.51 7.75 34.90 100.00 A(50%) 4.18 ± 0.30

[0584] 0.24 A(25%) 9.03 ± 1.27 A(12.5%) 37.93 ± 0.60 99.90 ± A(100%) 7.89 ± 0.99 HI-5 17.40 13.46 35.19 48.65 6.17 27.78 100.00 A(50%) 7.57 ± 0.80

[0585] 0.01 A(25%) 7.97 ± 0.18

[0586]

[0587] A(12.5%) 16.69 ± 2.20

[0588]

[0201] Example IV. Microfibers of crosslinked polymer networks comprising covalently-bonded C18DMDEG and QPEI-C3OHC6

[0589]

[0202] Five equal-weight C18DMDEG-N100-PTMG adduct solutions were prepared as described in Example III. To each container was added 0.0 g, 12.00 g, 24.03 g, 36.01 g, or 48.02 g of a 30 wt.% solution of QPEI-C3OHC6 in anhydrous MEK and 0.0 g, 39.60 g, 43.21 g, 46.80 g, or 50.41 g, respectively, of a 10 wt.% XK-651 solution in anhydrous MEK, and the resultant mixtures were stirred at 70 °C under nitrogen for 2 hours. A 35 wt.% solution of HEMA polyol in anhydrous MEK (as described in Example III) (171.45 g) was then added and allowed to react at 70 °C for additional 5 min. The reaction mixtures were diluted to 30 wt.% solid with anhydrous MEK for electrospinning under the same electrospinning and post-curing conditions as described in Example III.

[0590]

[0203] Antiviral efficiencies against Adenovirus and MTT assay results are shown in Table 3. When the amount of C18DMDEG was maintained at about 22.44-24.23 wt.%, the electrospun microfibers comprising 0.00-7.41 wt.% of QPEI-C3OHC6 exhibited high antiviral efficiencies against Adenovirus and are essentially non-cytotoxic. The efficiency appeared to increase with increasing amount of QPEI-C3OHC6, reaching values of 99.80% and 99.97% for Example IV-3 (3.85 wt.% of QPEI-C3OHC6 and Example IV-4 (5.66 wt.% of QPEI-C3OHC6), respectively.

[0591] However, too high of an amount of QPEI-C3OHC6 (e.g., 7.41 wt.% in Example IV-5) resulted in a deterioration of the antiviral efficiency and a slight increase in cytotoxicity, potentially due to leaching out of some of the insufficiently bonded excess quaternary ammonium salts during the tests.

[0592] Table 3

[0593] quaternary ammonium MTT Assay salts PTMG- HEMA Antiviral

[0594] Ex. polyiso. C18 QPEI- 1000 polyol Total efficiency

[0595] (dry wt.%) DMDEG C3OHC6 Total (dry (dry (dry against Cell survival w

[0596] (dry (dry (dry

[0597] wt.%) w. ) wt.%) wt.%) wt.%) t.%) adenovirus Cone. (%) t % (%)

[0598]

[0599] Atty. Dkt. No. 136938-0902

[0600] A(100%) 11.90 ± 1.51 98.92 ±

[0601] IV-1 31.32 24.23 0.00 24.23 11.11 33.33 100.00 A(50%) 62.92 ± 3.37

[0602] 1.08 A(25%) 90.37 ± 2.51 A(12.5%) 93.99 ± 3.65 99.08 ± A(100%) 4.29 ± 0.29 I V-2 30.71 23.76 1.96 25.72 10.89 32.68 100.00 A(50%) 6.41 ± 0.47

[0603] 0.07 A(25%) 60.73 ± 1.95 A(12.5%) 93.11 ± 1.12 99.80 ± A(100%) 1.31 ± 0.41 IV-3 30.11 23.30 3.85 27.15 10.68 32.05 100.00 A(50%) 0.69 ± 0.13

[0604] 0.02 A(25%) 31.86 ± 2.90 A(12.5%) 92.96 ± 0.41 99.97 ± A(100%) 0.27 ± 0.07 IV-4 29.54 22.86 5.66 28.52 10.48 31.46 100.00 A(50%) 16.33 ± 0.67

[0605] 0.01 A(25%) 90.41 ± 2.09 A(12.5%) 98.65 ± 1.46 97.87 ± A(100%) 5.49 ± 1.19 IV-5 29.00 22.44 7.41 29.85 10.29 30.86 100.00 A(50%) 2.40 ± 1.00

[0606] 0.32 A(25%) 38.94 ± 1.39

[0607]

[0608] A(12.5%) 69.78 ± 0.99 polyiso. = polyisocyanate

[0609]

[0204] Example V. Microfibers of crosslinked polymer networks comprising covalently-bonded quaternary ammonium salts and 3-aminopropyltriethoxysilane (APTES)

[0610]

[0205] The procedures of Examples IV-4 and IV-5 were repeated except that 13.60 g (Example V-1) or 18.47 g (Example V-2) of 3-aminopropyltriethoxysilane (APTES, 98% purity from Thermo Scientific) were added to quench the respective reactions. The degree of the isocyanate conversions was monitored by assessing the characteristic NCO peak at 2270 cm-1by FTIR-ATR. After about 90% of the NCO moieties were reacted, the reaction mixtures were diluted to 30 wt% solid with anhydrous MEK, cooled quickly to room temperature, and stored in a refrigerator at 4 °C before electrospinning. The quenched solutions (Examples V-1 and V-2) demonstrated a gel time of about 16 hours at room temperature or 1.0-1.33 hours at 70 °C, respectively, as shown in Table 4. In contrast, nonquenched solutions of Examples IV-4 and IV-5 showed a gel time as short as 4 hours at room temperature or 0.25 hour at 70 °C, respectively. Use of the latent crosslinker, APTES, effectively extended the gel time or the process green time to a range that is practical for most typical production processes.

[0611]

[0206] The reaction mixtures were then reactivated by a 2 M citric acid solution to catalyze the siloxane condensation reaction immediately before electrospinning. In Examples V-1 and V-2, 0.32 and 0.33 dry phr (parts per hundred resin) of citric acid, respectively were added, and the mixtures were allowed to react at 70 °C for 30 minutes (about 3 / 8-1 / 2 of the gel time) before electrospinning at room temperature. The reaction mixtures were cooled down to room temperature and electrospun and post-cured as described in Example III.

[0612]

[0207] Gel time, antiviral efficiencies against Adenovirus, and MTT assay results of the microfibers comprising covalently-bonded C18DMDEG and QPEI-C3OHC6 quaternary ammonium salts and the latent crosslinker APTES are summarized in Table 4. In addition to Atty. Dkt. No. 136938-0902

[0613] the significantly longer process green time of the electrospinning fluid, electrospun microfibers (Examples V-1 and V-2) crosslinked with a latent crosslinker (APTES) demonstrated a similar or better antiviral efficacy and cell survival rate as compared to the comparative Examples IV-4 and I V-5, respectively.

[0614] Table 4

[0615] quaternary ammonium salts Gel time (h) MTT Assay polyiso. PTMG- HEMA APTES Citric

[0616] C18 QPEI- 1000 polyol added Total acid Antiviral Ex. (dry Cel DMDEG C3OHC6 Total

[0617] (dr (dry efficiency l wt.%) (dry y (dry (dry RT 70°C (dry Cone. survival (dry (dry wt.% wt.%) (%)

[0618] wt ) wt.%) wt.%) Phr) (%) wt.%) wt.%).%)

[0619] 9997 ± A(100%) 027 ± 007 IV-4 2954 2287 566 2853 1048 31 46 000 10000 40 025 0 A(50%) 1633 ± 067

[0620] 001 A(25%) 9041 ± 209 A(125%) 9865 ± 1 46 99 18 ± A(100%) 086 ± 0 16 V-1 2708 2096 5 19 26 15 961 2882 834 10000 160 1 0 032 A(50%) 608 ± 002

[0621] 007 A(25%) 6968 ± 225 A(125%) 9266 ± 243 9787 ± A(100%) 549 ± 1 19 IV-5 2900 2244 741 2985 1029 3086 000 10000 40 025 0 A(50%) 240 ± 1 00

[0622] 032 A(25%) 3894 ± 1 39 A(125%) 6978 ± 099 9997 ± A(100%) 071 ± 006 V-2 2648 2049 678 2727 939 28 18 868 10000 160 1 0 033 A(50%) 11 20 ± 032

[0623] 001 A(25%) 8252 ± 377

[0624]

[0625] A(125%) 9365 ± 3 16 polyiso. = polyisocyanate; antiviral efficiency: against adenovirus

[0626]

[0208] Example VI. Microfibers of crosslinked polymer networks comprising

[0627] covalently-bonded quaternary ammonium salts by electrospinning with in-line mixing

[0209] Preparation of Mixtures A: DESMODUR® N100 (225.52 g) and C18DMDEG

[0628] (174.48 g) were dissolved completely in anhydrous MEK (215.36 g) under nitrogen at 70 °C with stirring. A 10 wt.% XK-651 solution in anhydrous MEK (4.0 g) was added, and the mixture stirred at 70 °C for 1.5 hours. The reaction mixture was concentrated to 75 wt.%

[0629] solid by a rotary evaporation at 45 °C, 90 torr for about 10 min, and PTMG-1000 (20.0 g) was added and stirred under nitrogen at 70 °C for 1 hour. The resultant reaction mixture was divided into 4 solutions of equal weight. To each was added 43.22 g, 100.41 g, 118.06 g, or 172.90 g of a 25 wt.% QPEI-C3OHC6 solution in anhydrous MEK, and each mixture was stirred under nitrogen at 70 °C for 4 hours. The resultant reaction mixtures were then diluted with anhydrous MEK to 30 wt.% solid and ready for electrospinning.

[0630]

[0210] Preparation of Mixtures B: 435.73 g, 483.79 g, 498.26 g, or 543.77 g of a 30 wt.% HEMA polyol solution in anhydrous MEK (as described in Example III) were mixed with 3 phr (dry) of XK-651 as the catalyst (78.43 g, 87.08 g, 89.69 g, or 97.88 g, respectively of a 10 wt.% XK-651 solution in anhydrous MEK) to form the Mixture B for Examples VI-1, VI-2, VI-3 and VI-4, respectively.

[0631]

[0211] Electrospinning with in-line mixing: The same electrospinning process as described in Example III was used except that Mixtures A and B of equal weight were mixed in-line using a double channel syringe and two static mixers connected in series. Both Mixtures A and B showed a green time longer than 24 hours at room temperature before Atty. Dkt. No. 136938-0902

[0632] being in-line mixed in the static mixers. The microfibers were collected for 90 minutes on a 2 mm PET film (Milenex 339 from DuPont Teijin Film) and post-cured for 16 hours at 40 °C followed by 4 hours at 60 °C to obtain microfibers of about 4 g / m2coverage on a PET substrate.

[0633]

[0212] The antiviral efficiency and the MTT assay results of these microfibers are listed in Table 5. All microfibers in this example exhibited >99% antiviral efficiency against adenovirus and were nontoxic. The microfibers also exhibited good integrity with uniform fiber diameter (FIG. 3). Moreover, the morphology and fiber diameter of the microfibers prepared with in-line mixing remain essentially the same throughout the several hours of electrospinning.

[0634] Table 5

[0635] Mixture

[0636] Mixture A MTT Assay B

[0637] quaternary ammonium salts Total Cat. Antiviral

[0638] Ex. PTMG- HEMA

[0639] polyiso. C18 QPEI- (dry added efficiency

[0640] Total 1000 polyol

[0641] (dry DMDEG C3OHC6 wt.%) (phr) Cell survival (dry (dry (dry (%)

[0642] wt.%) Cone.

[0643] (dry (dry (%) wt.%) wt.%) wt.%)

[0644] wt.%) wt.%)

[0645] A(100%) 37.93 ± 2.34 99.65 ± A(50%) 99.78 ± 2.85 VI-1 21.55 16.67 4.14 20.81 7.64 50.00 100.00 3.00

[0646] 0.05 A(25%) 100.00 10.67 A(12.5%) 100.00 10.62 A(100%) 2.161 0.62 99.10 ± A(50%) 53.02 12.19 VI-2 19.43 15.03 8.65 23.68 6.89 50.00 100.00 3.00

[0647] 0.09 A(25%) 92.97 12.05 A(12.5%) 96.14 1 1.84 A(100%) 0.51 1 0.08 99.09 ±

[0648] A(50%) 1.301 0.13 VI-3 18.85 14.59 9.87 24.46 6.69 50.00 100.00 3.00

[0649] 0.10 A(25%) 72.77 12.13

[0650] 95.40 1 1.52 A(12.5%) A(100%) 0.71 1 0.06 99.96 ±

[0651] A(50%) 11.20 10.32 VI-4 17.27 13.36 13.24 26.60 6.13 50.00 100.00 3.00

[0652] 0.01 A(25%) 82.52 13.77 A(12.5%) 93.65 13.16

[0653]

[0654] polyiso. = polyisocyanate; antiviral efficiency: against adenovirus

[0655]

[0213] The microfibers of Example VI-4 were also electrospun with in-line mixing on two nonwoven substrates (15 g / m2hydrophobic nonwoven substrate from Filtrafine Co., Ltd., Taiwan and 20 g / m2hydrophilic nonwoven substrate, from Sanxion Co., Ltd., Taiwan ) to form antiviral composite nonwoven fabrics. In all cases, the nonwoven substrates were corona-treated immediately before the electrospinning.

[0656]

[0214] Bioassay results (Table 6) indicated that the two nonwoven substrates (Comparative Examples VI-4-1 and VI-4-3) did not show any antiviral efficiency. In contrast, the two composite nonwoven fabrics (Examples VI-4-2 and VI-4-4) with 5.73 ± 0.86 or 5.56 ± 1.19 g / m2coverages of the Example VI-4 microfibers electrospun onto the corona-treated hydrophobic and hydrophilic nonwoven substrates, respectively, demonstrated an antiviral efficiency of 99.75-99.82% without any detectable cytotoxicity. SEM micrographs (FIG. 4) indicated good integrity of the microfibers in the two composite nonwoven fabrics (Examples VI-4-2 and VI-4-4). Atty. Dkt. No. 136938-0902

[0657] Table 6

[0658] Quaternary qPCR MTT Assay ammonium

[0659] salt-containing

[0660] Examples Substrate Antiviral Cell survival microfiber efficiency Cone.

[0661] coverage (%)

[0662] (%)

[0663] (g / m2)

[0664] A(100%) 66.72 ± 1.86 Hydrophobic

[0665] A(50%) 89.67 ± 4.32 VI-4-1 nonwoven none 0.00 ± 7.27

[0666] A(25%) 95.44 ± 0.92 (15 g / m2)

[0667] A(12.5%) 100.00 ± 2.22 A(100%) 21.11 ± 1.47 Hydrophobic

[0668] A(50%) 22.59 ± 0.95 VI-4-2 nonwoven 5.73 ± 0.86 99.82 ± 0.07

[0669] A(25%) 80.07 ± 2.91 (15 g / m2)

[0670] A(12.5%) 93.04 ± 5.21 A(100%) 81.13 ± 8.24 Hydrophilic

[0671] A(50%) 87.70 ± 3.18 VI-4-3 nonwoven none 0.00 ± 3.26

[0672] A(25%) 95.83 ± 3.94 (20 g / m2)

[0673] A(12.5%) 91.76 ± 7.18 A(100%) 18.61 ± 1.60 Hydrophilic

[0674] A(50%) 23.75 ± 0.29 VI-4-4 nonwoven 5.56 ± 1.19 99.75 ± 0.01

[0675] A(25%) 71.25 ± 0.85 (20 g / m2)

[0676] A(12.5%) 84.15 ± 2.42

[0677]

[0678]

[0215] Example VI-4-2 composite nonwoven fabric (using the hydrophobic nonwoven substrate) was used as the interlayer for the preparation of N-95-like masks (FIG. 5).

[0679] Example VI-4-4 composite nonwoven fabric (using the hydrophilic nonwoven substrate) was used as the interlayer for the preparation of diapers (FIG. 6).

[0680] Additional examples of quaternary ammonium salts

[0681]

[0216] The following examples may be combined with a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s) to form microfibers of the present disclosure.

[0682]

[0217] Examples 1-4. Water-based compositions with or without a water-soluble polyethyleneimine intermediate

[0683] Examples (dry wt % in the dry film) 1 2 3 4

[0684] N100-C18DMDEG(Br-) 75 70 70 70 Oil

[0685] Phase PTMG (MW1000) 6 6 6 6

[0686]

[0687] N100 14 14 14 14 Atty. Dkt. No. 136938-0902

[0688] Polyethyleneimine Intermediate (QPEI) Used

[0689] None 37169 HB37169 HB37478 in the Aqueous Phase (wt.%)

[0690] Aqueous QPEI 0 5 5 5

[0691] Phase

[0692]

[0693] HEC (MW380K) 5 5 5 5

[0694]

[0218] Preparation of the aqueous phase:

[0695]

[0219] 3.1 parts of HEC 380K ((2-hydroxyethyl cellulose, average Mw= 380,000 from Aldrich) were dissolved thoroughly in 96.9 parts of DI water. The pH of the solution was adjusted to 4.5 by a 5% solution of H3PO4.

[0696]

[0220] Example 1: preparation of polymer without polyethyleneimine intermediate

[0221] Preparation of the Oil-phase:

[0697]

[0222] 5.0 g (10.7 mmol) of thoroughly dried C18DMDEG was added to a solution of 7.67 g (16.03 mmol, 48 mmol reactive NCO) of DESMODUR® N100 in 5 g dry toluene at 90 °C under nitrogen and allowed to react for 15 hours. A clear viscous liquid (first adduct) was obtained after the toluene was removed under reduced pressure.

[0698]

[0223] 4.144 parts of the first adduct (N100-C18DMDEG(Br-)), 0.356 parts of PTMG 1000 (Poly(tetramethylene glycol), Average Mn=1000 from Aldrich) and 1.5 parts of MEK (methyl ethyl ketone) were pre-reacted at 70 °C for 1 hour. The mixture was cooled to room temperature and dried under vacuum until the solid content reached about 90% by weight. To the solution, 0.828 parts of polyisocyanate N100 (DESMODUR N100 from Convestro) and 1.276 parts of dried acetone were added and mixed homogeneously.

[0699]

[0224] Preparation of Oil-in-Water Emulsion

[0700]

[0225] The aqueous phase solution as prepared above was added into the oil phase at room temperature and emulsified by ultrasonication (100 Watt) for 10 sec, 5 times with a 10 sec pulse between each ultrasonication. The total emulsification time was about 90-120 sec. Heating for 15 hours at 60 °C provided the polymer product.

[0701]

[0226] Examples 2-4

[0702]

[0227] Preparation of QPEI 37169

[0703]

[0704]

[0228] QPEI 37169 was prepared as shown in the reaction scheme above. Atty. Dkt. No. 136938-0902

[0705]

[0229] 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 has been reported in the literature. See, e.g., Klibanov, A., et al., (2006). “One-Step Painting-Like Coating Procedures to make Surfaces Highly and Permanently Bactericidal.” Biotechnol. Prog., 22(2): 584-589; and Gao, B., et al., (2007). “Studies on the Preparation and Antibacterial Properties of Quaternized Polyethyleneimine.” J. Biomaterials Science, Polymer Edition, 18(5): 531-544.

[0706]

[0230] The procedure used is essentially as described in Gao etal. (2007). The structure for QPEI 37169 is intended to be an approximation indicating that most of the primary and secondary amines have been reacted with the epoxide with most of the tertiary amines quaternized by alkylation with the benzyl chloride.

[0707]

[0231] To a 25 mL two-neck flask under nitrogen was added 3.33 g of 70 kDa PEI solution (30% in water / 1g PEI, assume mw = 43.1 g / mol, 23.2 mmol) and was cooled to 0°C. To this mixture, 5.4 g (92.8 mmol) propylene oxide was added dropwise at 0-3°C. After the addition was completed, the reaction mixture was stirred at 0-3°C for seven hours. Then the temperature of the reaction mixture was increased to 35°C and the unreacted propylene oxide was distilled out (-3.60 mL). Added to the resulting solution was 11.75 g (10.6 mL, 92.8 mmol) of benzylchloride and the reaction was heated to 50°C for 30 hours. The reaction was extracted with diethyl ether (3x20 mL) to remove unreacted benzylchloride, residual propylene oxide, and oleophilic side products or impurities, if there are any. The water phase was separated and vaporized under vacuum and dried by lyophilization leaving QPEI 37169 as a transparent solid (2.85 g). The product was characterized by proton NMR and Infrared (IR) spectroscopy. QPEI 37169 contains a ratio of about 1:1 of nitrogen functionalization by benzylchloride to nitrogen functionalization by propylene oxide (i.e., the number of benzyl groups is about equal to the number of 2-hydroxypropyl groups on the nitrogen atoms).

[0708]

[0232] Preparation of QPEI HB37169

[0709]

[0233] The same reaction as in the preparation of QPEI 37169 was used for the preparation QPEI HB37169 except that a hyperbranched polyethyleneimine of the same molecular weight was used.

[0710]

[0234] Preparation of QPEI HB37478

[0711]

[0235] The same reaction as in the preparation of QPEI 37169 was used for the preparation QPEI HB37478 except that the quaternization agent benzyl bromide was replaced by hexyl bromide, and a hyperbranched polyethyleneimine of the same molecular weight was used.

[0712]

[0236] Examples 5-9. QPEI 37169 as the Polyethyleneimine Intermediate in the Aqueous Phase Atty. Dkt. No. 136938-0902

[0713] Table 3.

[0714] Examples 2 5 6 7 8 9 Composition (wt% in the dry film)

[0715] First Adduct (N100-C18DMDEG(Br-)) 70 65 68 63 65 60 PTMG (MW1000) 6 6 8 8 11 11 N100 14 14 14 14 14 14 QPEI 37169 5 10 5 5 5 5 HEC (MW380K) 5 5 5 10 5 10

[0716]

[0237] The same procedures as those in Examples 1-4 were used to prepare the compositions of Examples 5-9, except that the composition was changed as shown in Table 3.

[0717]

[0238] Examples 10-20 describe additional examples of polyethyleneimine intermediates or further functionalized compounds that can be used in the present technology.

[0718]

[0239] Example 10. Synthesis of Polyethyleneimine Intermediate 40840

[0719]

[0720]

[0240] A 500 mL 3 neck round bottom flask was fitted with a thermometer, condenser and magnetic stirrer. The reaction flask was flushed with nitrogen gas and the reaction carried out under a nitrogen gas flow.

[0721]

[0241] 10 g of PEI (70 kDa branched, 30% by weight aqueous solution, amine content 18mmole / gram solid polymer, ratio of primary, secondary, tertiary amines = 1:2:1) and potassium carbonate (37.07g, 0.232 mol) and 150mL t-Amyl Alcohol were added to the

[0722] round bottom flask. This mixture was stirred under nitrogen for 30 minutes and then 3- bromo-1-propanol (64.5g, 0.464mol, 1.3 equivalents for complete quaternization) was added dropwise at room temperature. The resulting mixture was heated and stirred at 95 °C for 96 hours.

[0723]

[0242] After 96 hours, the mixture was allowed to cool to room temperature and filtered to remove insoluble solid. The filtered solid was washed with 150 mL methanol. The combined filtrates were treated with 250 mL diethyl ether and a white precipitate was formed. The organic phase was decanted and the white solid was dissolved in 200 mL methanol and precipitated with 200 mL diethyl ether. This dissolution / precipitation process was carried out Atty. Dkt. No. 136938-0902

[0724] two more times and the resulting white pasty solid was dried in a rotary evaporator and then further dried under high vacuum for 5 hours. Then yield of dry produce was 17.4g. The

[0725] product was characterized by1H NMR and the degree of quaternization analyzed using the Mohr argentometric titration method to measure the amount of bromide.

[0726]

[0243] Example 11. Synthesis of Polyethyleneimine Intermediate 40660

[0727] NH2

[0728] N+Me3o.

[0729] Cl- N N N H H

[0730] Triethylamine H2O 70 kDa Branched PEI (30% by weight in water) 18 mmole amine / gram solid Ratio of primary, secondary, tertiary amines = 1:2:1

[0731]

[0732]

[0244] A 2-L 3 neck round bottom flask was fitted with a dropping funnel, condenser and magnetic stirrer. The reaction flask was flushed with nitrogen gas and the reaction carried out under a nitrogen gas flow.

[0733]

[0245] 10 g of PEI (70 kDa branched, 30% by weight aqueous solution, amine content 18mmole / gram solid polymer, ratio of primary, secondary, tertiary amines = 1:2:1) was

[0734] added to the reaction flask and 835 mL water added to it. 114.3 g

[0735] glycidyltrimethylammonium chloride (0.754 mol, ~4 equivalents for theoretical full

[0736] conversion) was dissolved in 130 mL water and added dropwise to the reaction mixture. 153 g (210 mL, 1.5 mol) Triethylamine was added dropwise to the reaction mixture at room temperature. The resulting two-phased reaction mixture was vigorously stirred at room temperature for 4 days after which time the reaction mixture was one clear phase. All

[0737] solvents were removed in a rotary evaporator at 55 °C. The pasty liquid residue was

[0738] dissolved in 200 mL methanol and the polymer product precipitated with 400 mL diethyl

[0739] ether. This methanol / diethyl ether dissolution and precipitation was repeated six times. The final precipitate was dried in a rotary evaporator and then under high vacuum yielding 46.5 g of the final product. The product was characterized by1H NMR and the degree of quaternization analyzed using the Mohr argentometric titration method to measure the

[0740] amount of chloride.

[0741]

[0246] Example 12. Synthesis of Polyethyleneimine Intermediate 40818 Atty. Dkt. No. 136938-0902

[0742] N+Me3N+Me-,

[0743] 4 C1- OH OH

[0744] CSA13\ HO

[0745] 4Bt- J

[0746]

[0747] 'N+Me3Me3+Nx'

[0748]

[0247] A 100-mL 1 neck round bottom flask was fitted with a condenser, a heating cup and magnetic stirrer. The reaction flask was flushed with nitrogen gas and the reaction carried out under a nitrogen gas flow.

[0749]

[0248] 2 g of the glycidyl functionalized PEI (3.3 mmol 13.3 mmol reactive N), bromohexane (7 g, 40 mmol, 3 equivalents) and 4.4 mL t-amyl alcohol were added to the flask and the reaction mixture was heated at 96 °C for 96 hours. The reaction mixture turned from colorless to light orange in color. The reaction was cooled to room temperature and the resulting solution was poured into Tertiary Butyl Methyl Ether (TBME) with vigorous stirring causing a precipitate to form. The liquid was decanted away from the precipitated solid and the solid dissolved in methanol and reprecipitated with TBME. This process was repeated 3 times yielding 4.06 g of the product after drying with a rotary evaporator and then high vacuum. The product was characterized by1H NMR and the degree of quaternization analyzed using the Mohr argentometric titration method to measure the amount of halide.

[0750]

[0249] Example 13. Synthesis of a Polyethyleneimine Intermediate capped with monoisocyanate (approximately 85% of free OH groups)

[0751]

[0250] The structure for the polymer product, as shown below, is intended to be an approximation indicating that most of the hydroxyl groups (-85% molar equivalent) have been reacted with the blend of monoisocyanates to form urethanes with some hydroxyl groups remaining unreacted.

[0752] Cl8H37

[0753]

[0754] QPEI 37169-capped Atty. Dkt. No. 136938-0902

[0755]

[0251] The concentration of reactive hydroxyl groups (mmol / gram of dry polymer) was determined by titrating a known amount (grams) of the dried Hydroxyl Alkyl Quaternary Polyethyleneimine (HA-Q-PEI) with a known excess amount (grams, mmoles) of Octadecylisocyanate. The percentage of monoisocyanate which was consumed in the reaction was determined by monitoring the reaction progress using infrared (IR) spectroscopy to monitor the drop in the isocyanate peak at 2263 cm-1. From the percentage drop in this peak, the number of mmoles of isocyanate consumed was estimated. This value was equivalent to the number of mmoles of polymer hydroxyl groups which reacted with the isocyanate. In this way, a 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(s) required to functionalize specific percentages of the reactive hydroxyl groups in the polymer and by doing so, would fine-tune the hydrophilic / hydrophobic properties of the polymer.

[0756]

[0252] Using the procedure described in Example 2, 2.0 g (2.27 mmol assuming a molecular weight of 881 g / mole for the polymer unit cell) of the Hydroxypropyl Quaternary Ammonium PEI, QPEI 37169, was prepared and then dried under vacuum at 60°C for two hours followed by storing overnight in a desiccator at room temperature. To the dried polymer was added 13.8 g t-butyl alcohol and 9.2 g of dimethyl acetamide. The resulting mixture was stirred under nitrogen until the polymer completely dissolved. Both of these solvents were dried thoroughly with molecular sieve 4Å before use. A mixture of 1.6 g (5.41 mmol) of octadecylisocyanate 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 turned slightly cloudy. The resulting reaction mixture was stirred at room temperature under nitrogen for twelve hours. The resulting reaction mixture was filtered with a PTFE filter (1 µm pore size) affording the 20.83 grams of QPEI 37169-capped as a 12.19% solid solution. IR spectroscopy showed the expected new peak corresponding to the urethane carbonyls and no residual isocyanate peak.

[0757]

[0253] In some embodiments, after the reaction with monoisocyanate(s) is complete, the reaction mixture was added to water to precipitate the capped product. This product was isolated and washed with water to remove any water soluble impurities and then dried for use in subsequent steps. This water precipitation step was useful for removing any water soluble impurities that may contribute to toxicity.

[0758]

[0254] Example 14. Process for Crosslinking Reaction of Octadecyl / Octyl Urethane Quaternary Ammonium PEI Atty. Dkt. No. 136938-0902

[0759]

[0255] The structure for the polymer Compound (A), as shown below, is intended to be an approximation indicating that some of the unreacted hydroxyl groups in QPEI 37169-capped have been reacted with the polyisocyanate to form urethane cross-links.

[0760] QPEI 37169-capped

[0761]

[0762] Atty. Dkt. No. 136938-0902

[0763]

[0256] Using the procedure described in Example 13, 20 g of the Octadecyl / Octyl Urethane Quaternary Ammonium PEI was prepared, to which was added 1.25 g of Desmodur N3300 (50% solution in anhydrous acetone) and 0.18 g of a Dibutyltin Dilaurate 1% solution in dry toluene. The resulting mixture was mixed thoroughly and a reaction to form Compound (A) occurred in 30 min at 60 °C to provide the final crosslinked product.

[0764]

[0257] It should be noted that the above crosslinking procedure has also been carried out without the Dibutyltin Dilaurate catalyst.

[0765]

[0258] Example 15. Aqueous Solutions of HA-Q-PEI Polymers with Varied PEI Molecular Weights, Nitrogen Quaternization Groups, and Anionic Counter Ions

[0259] Various HA-Q-PEI (Hydroxy Alkyl Quaternary PEI) of the following formula:

[0766] R2

[0767] HA-Q-PEI Hydroxyalkyl Quaternary PEI

[0768]

[0769] were prepared using analogous procedures as that which is described in Example 2 (preparation of QPEI 37169). See Table 5 (Ri = methyl for each polymer).

[0770] Table 5.

[0771] sample MW R2X- 2-1 600 n- Hexyl Bromide 2-2 10,000 n- Hexyl Bromide 2-3 100,000 n- Hexyl Bromide 2-4 70,000 n- Hexyl Bromide 2-5 70,000 Benzyl Chloride 2-6 70,000 Methyl Iodide 2-7 70,000 n-Butyl Bromide 2-8 70,000 -CH2C(O)OCH2CH3 Bromide

[0772]

[0773] 2-9 70,000 -CH2C(O)Ph Bromide

[0774]

[0260] Example 16. Aqueous Solutions of HA-Q-PEI Polymers with Varied PEI Molecular Weights

[0775]

[0261] Additional HA-Q-PEI polymers (Ri = methyl, R2 = hexyl, X = bromide) of the following formula: Atty. Dkt. No. 136938-0902

[0776] HA-Q-PEI Hydroxyalkyl Quaternary PEI

[0777]

[0778] having various molecular weights were prepared using analogous procedures as that which is described in Example 2 (preparation of QPEI 37169). See Table 6.

[0779] Table 6.

[0780] sample MW (kDa)

[0781] 3-1 0.6

[0782] 3-2 0.6

[0783] 3-3 10

[0784] 3-4 10

[0785] 3-5 25

[0786] 3-6 70

[0787] 3-7 100

[0788] 3-8 270

[0789]

[0790] 3-9 270

[0791]

[0262] Example 17. Preparation of Cross-linked Compounds

[0792]

[0263] Compounds of the following formula:

[0793]

[0794] were prepared (see Table 7) using analogous procedures as that which is described in Example 14, replacing the Octadecyl / Octyl Urethane Quaternary Ammonium PEI with a HA-Q-PEI (prepared from PEI: molecular weight = 70,000 (branched), Ri = methyl, R2 = hexyl, X = bromide), and varying the amounts of crosslinker Z (DESMODUR® N100): Atty. Dkt. No. 136938-0902

[0795] o

[0796] (CH2)6

[0797]

[0798] OCN

[0799] (DESMODUR® N100).

[0800] Table 7.

[0801] sample wt.% crosslinker*

[0802] 4-1 6.5

[0803] 4-2 17.7

[0804] 4-3 26.5

[0805] 4-4 33.3

[0806] 4-5 39.2

[0807]

[0808] 4-6 44.1

[0809] *wt.% with respect to cross-linked product

[0810]

[0264] Example 18. Polyethyeleneimine Intermediates with or without Monoisocyanate Substitution

[0811]

[0265] Polyethyeleneimine intermediates with monoisocyanate substitution (MUA-Q-PEI-A polymers, wherein R3 = C alkyl or Cs alkyl) of the following formula:

[0812]

[0813] were prepared from HA-Q-PEI (prepared from PEI: molecular weight = 70,000 (branched), R1 = methyl, R2 = benzyl) and a monoisocyanate mixture (7:3 ratio of octadecylisocyanate to octylisocyanate), wherein approximately 90% of HA-Q-PEI hydroxyl groups reacted with the monoisocyanate mixture (see similar protocol in Example 13). MUA-Q-PEI-A100 polymers were also similarly prepared, in which approximately 100% of the HA-Q-PEI hydroxyl groups reacted with the monoisocyanate mixture. See Table 8.

[0814] Table 8. Atty. Dkt. No. 136938-0902

[0815] sample polymer system

[0816] 5-1 1% water solution HA-Q-PEI

[0817] 5-2 dry film MUA-Q-PEI-A

[0818] 5-3 dry film MUA-Q-PEI-A

[0819] 5-4 dry film MUA-Q-PEI-A

[0820] 5-5 dry film MUA-Q-PEI-A100

[0821] 5-6 dry film MUA-Q-PEI-A100

[0822]

[0823] 5-7 dry film MUA-Q-PEI-A100

[0824]

[0266] Example 19. Using N3300 Polyisocyanate Crosslinker

[0825]

[0267] Compounds (PUA-Q-PEI-B polymers, wherein R3= C18alkyl or C8alkyl) of the following formula:

[0826]

[0827] were prepared using analogous procedures as that which is described in Example 14. In particular, the HA-Q-PEI (prepared from PEI: molecular weight = 25,000 (Hyper Branched), Ri = methyl, R2 = hexyl, X = bromide) was reacted with a monoisocyanate mixture (7:3 ratio of octadecylisocyanate to octylisocyanate), wherein approximately 90% of HA-Q-PEI hydroxyl groups reacted with the monoisocyanate mixture, before the remaining hydroxyl groups were reacted with varying amounts of crosslinker Z (DESMODUR® N3300):

[0828] OCN-(H2C)6-(CH2)6-NCO

[0829]

[0830] (CH2)6-NCO

[0831] (DESMODUR® N3300).

[0832] Table 9.

[0833] Sample wt.% crosslinker*

[0834] 6-1 0

[0835] 6-2 1.62

[0836] 6-3 4.75

[0837] 6-4 7.61

[0838]

[0839] 6-5 10.37 Atty. Dkt. No. 136938-0902

[0840] *wt.% crosslinker with respect to PUA-Q-PEI-B polymer product

[0841]

[0268] Example 20. Compound 20-1

[0842]

[0269] Compound 20-1 is analogous to QPEI samples 3-8 and 3-9 of Example 16, and was prepared from a PEI with MW = 270 kDa. Compound 20-1 (batch 105159) contains a ratio of more than 1:1 of nitrogen functionalization by hexyl halide to nitrogen functionalization by propylene oxide (i.e., there are more hexyl groups than 2-hydroxypropyl groups on the nitrogen atoms). Compound 20-1 (batch 99367) contains a ratio of about 1:1 of nitrogen functionalization by hexyl halide to nitrogen functionalization by propylene oxide (i.e., the number of hexyl groups is about equal to the number of 2-hydroxypropyl groups on the nitrogen atoms).

[0843]

[0270] Example 21. Compound 21-1

[0844]

[0271] Compound 21-1 is analogous to compound HB37478, but is prepared from a PEI with MW = 25 kDa. Compound 21-1 contains a ratio of about 1:1 of nitrogen functionalization by hexyl halide to nitrogen functionalization by propylene oxide (i.e., the number of hexyl groups is about equal to the number of 2-hydroxypropyl groups on the nitrogen atoms).

[0845]

[0272] Example 22. Compound 22-1

[0846]

[0273] Compound 22-1 (batch 109590) is analogous to HB37478 of Example 4, but a branched 70 kDa PEI was used rather than a hyperbranched 70 kDa PEI. Compound 22-1 (batch 109590) contains a ratio of about 1:1 of nitrogen functionalization by hexyl halide to nitrogen functionalization by propylene oxide (i.e., the number of hexyl groups is about equal to the number of 2-hydroxypropyl groups on the nitrogen atoms).

[0847]

[0274] Example 23. Compound 23-1

[0848]

[0275] Compound 23-1 (batch 105402 and batch 109634) is analogous to QPEI sample 2-9 of Example 15 (prepared from a PEI with MW = 70 kDa). Compound 23-1 (batch 105402 and batch 109634) contains a ratio of about 1:1 of nitrogen functionalization by phenacyl halide to nitrogen functionalization by propylene oxide (i.e., the number of phenacyl groups is about equal to the number of 2-hydroxypropyl groups on the nitrogen atoms).

[0849]

[0276] Example 24. Compound 24-1

[0850]

[0277] Compound 24-1 (batch 109781) is analogous to QPEI 37169 of Example 2 (prepared from a PEI with MW = 70 kDa). Compound 24-1 (batch 109781) contains a ratio of about 1:1 of nitrogen functionalization by benzyl halide to nitrogen functionalization by propylene oxide (i.e., the number of benzyl groups is about equal to the number of 2-hydroxypropyl groups on the nitrogen atoms).

[0851]

[0278] Example 25. Compound 25-1 Atty. Dkt. No. 136938-0902

[0852]

[0279] Compound 25-1 (batch 110417) is analogous to compound 23-1, but is prepared from a PEI with MW = 750 kDA.

[0853]

[0280] Example 26. Compound 26-1

[0854]

[0281] Compound 26-1 (batch 109831) is analogous to polyethyleneimine intermediate 40660 of Example 11 (prepared from a PEI with MW = 70 kDa).

[0855]

[0282] Example 27. Compound 27-1

[0856]

[0283] Compound 27-1 (batch 110420) is analogous to polyethyleneimine intermediate 40818 of Example 12 (prepared from a PEI with MW = 70 kDa).

[0857]

[0284] Example 28. Compound 28-1

[0858]

[0285] Compound 28-1 corresponds to the intermediate compound in the synthesis of QPEI 37169 of Example 2, resulting from reaction of PEI (MW = 70 kDa) with propylene oxide. Accordingly, there are no quaternary amines in compound 28-1.

[0859]

[0286] Example 29. Compound 29-1

[0860] BrC3H6OH (1 mol%) BrC6H13(99 mol%) K2CO3NH2

[0861]

[0862] R R: - 1 mol% -C3H6OH, 99 mol% -C6H13

[0863]

[0287] A 1-L 3-neck round bottom flask was fitted with a dropping funnel, condenser, water bath and mechanical stirrer. The flask was flushed with nitrogen gas, and the reaction carried out under a nitrogen gas flow.

[0864]

[0288] 20 g of a 50% aqueous solution of 70 kDa branched PEI (10 g PEI polymer, 0.180 mole amine content with a ratio of primary to secondary to tertiary amines of approximately 1:2:1) was added to the flask and stirred at -200 RPM. Note that 0.180 mole nitrogen content with this ratio of primary, secondary, and tertiary amines in theory can react with 0.36 mole of alkyl halide. This is defined as “1 equivalent of alkyl halide” for this example.

[0865]

[0289] tert-Amyl alcohol (150 ml) was added to the flask at ambient temperature followed by K2CO3 (32.1 g, 0.232 mole). A mixture of bromopropanol (1.29 g, 0.0093 mole) and 1-bromohexane (151.86 g, 0.92 mole), (total alkyl halide = 0.93 mole, 2.6 equivalents with mole % content of each alkyl halide = 1% bromopropanol / 99% 1-bromohexane), was added dropwise over 1-2 hours at ambient temperature.

[0866]

[0290] The reaction temperature was increased to 96 °C, and the reaction stirred at 96 °C for 98 hours. The reaction was allowed to cool to 25-30 °C, filtered, and the filtered material Atty. Dkt. No. 136938-0902

[0867] washed with methanol (50 ml). The filtrate was evaporated to dryness under vacuum keeping the temperature below 50 °C. To the residue was added diethyl ether (200 ml), and the mixture was stirred for 30-60 minutes at room temperature after which time a light brown slurry had formed. This mixture was allowed to settle, and the supernatant decanted off. This diethyl ether trituration and decanting was repeated 3-4 times until the residual alkyl halide content in the decant layer was less than 0.5% as determined by GC analysis.

[0868]

[0291] After completing the trituration / decantation process, the mixture was evaporated to dryness under reduced pressure while keeping the temperature below 40 °C, resulting in an off-white sticky solid. This solid was dissolved in methyl ethyl ketone (100 ml) at 25-30 °C, filtered through Celite, and the filtrate evaporated to dryness under reduced pressure at 45 °C. The resulting solid was oven-dried for 4-6 hours at below 45 °C providing the product (37.8 g) as an off-white solid. Water content was measured by Karl-Fischer analysis to be 0.24%. Bromine content was measured by AgNO3titration to be 23.6%. The theoretical mole % of PEI reaction with 1 -bromopropanol and 1 -bromohexane is 1% and 99%, respectively, assuming similar alkylation rates between the two alkyl halides.

[0869]

[0292] Example 30. Compound 30-1

[0870] 0.064 equiv. Br(CH2)3OH H N Excess C18Br / C8Br (75:25 mol%)

[0871] 3 Br NH2R I R

[0872]

[0873] R R: - 6.4 mol% -(CH2)3OH, -93.6 mol% C18 / C8(75 / 25)

[0874]

[0293] A 1-L 4-neck round bottom flask was fitted with a dropping funnel, condenser, water bath and mechanical stirrer. The flask was flushed with nitrogen gas, and the reaction carried out under a nitrogen gas flow.

[0875]

[0294] 10 g of 25 kDa hyperbranched PEI (0.180 mole amine content with a ratio of primary to secondary to tertiary amines of approximately 1:1:1) was added to the flask along with water (10 ml). Note that 0.180 mole nitrogen content with this ratio of primary, secondary, and tertiary amines in theory can react with 0.36 mole of alkyl halide. This is defined as “1 equivalent of alkyl halide” for this example.

[0876]

[0295] tert-Amyl alcohol (50 ml) was added to the flask at ambient temperature, and this suspension was stirred at 160-180 RPM. After 15-30 minutes stirring, the mixture was cooled to 0-5 °C, and bromopropanol (3.2 g, 0.023 mole, 0.064 equivalents) was added dropwise over 15-30 minutes at 0-5 °C. The reaction mixture was stirred at 0-5 °C for 4-5 Atty. Dkt. No. 136938-0902

[0877] hours and then the temperature was allowed to increase to ambient temperature. The reaction was stirred at ambient temperature for 14-15 hours after which time the reaction mixture was a hazy solution.

[0878]

[0296] The water content of the reaction was reduced by azeotropic distillation of solvent (~10 mL). This volume of tert-Amyl alcohol was added to the reaction, and the distillation process repeated 3 times. Tert-Amyl alcohol was added to make up the original reaction volume, and the resulting mixture was stirred for 60-90 minutes at 50-60 °C after which time a clear solution was obtained.

[0879]

[0297] A mixture (0.928 mole, 2.6 equivalents of alkyl halide) of 1 -bromooctadecane (232.1 g, 0.696 mole) and 1-bromooctane (44.8 g, 0.232 mole) was added at 50-60 °C. The temperature was raised to 94-98 °C, and the reaction stirred at this temperature for 48 hours, resulting in a clear brown solution. The solvent was removed under reduced pressure at below 60 °C, the resulting residue cooled to 25-30 °C, and 500 mL acetone was added. The resulting suspension was stirred at 25-30 °C for 30-60 minutes. Stirring was stopped, and the suspension allowed to settle for 1 hour. The supernatant liquid was decanted away from solid, and acetone (500 ml) was added to the solid residue. This suspension was stirred at 25-30 °C for 30-60 minutes after which time the stirring was stopped, and the suspension was allowed to settle over 30-60 minutes, and the supernatant liquid decanted away from the settled solid. This suspension stirring, settling and decanting process was repeated several more times until the 1 -bromooctadecane and 1-bromooctane in the supernatant was less than 0.5% as measured by GC analysis.

[0880]

[0298] The remaining solvent was removed under reduced pressure at below 35 °C. The solid product was further dried for 8-10 hours at below 35 °C, affording 40.6 g of the QPEI product as a light brown solid. Bromine content was determined to be -23% as measured by AgNO3titration. The theoretical mole % of reaction with 1 -bromopropanol and the 75 / 25 mixture of 1 -bromooctadecane and 1-bromooctane is 6.4% and 93.6%, respectively.

[0881]

[0299] Example 31. Compound 31-1

[0882] 0.2 equiv. caprolactone

[0883] Excess bromohexane

[0884]

[0885]

[0886] NH2

[0887]

[0888] R: - 7 mol% -C(O)-(CH2)5-OH, -93 mol% -C6H13 Atty. Dkt. No. 136938-0902

[0889]

[0300] A 0.5-L 4-neck round bottom flask was fitted with a dropping funnel, condenser, water bath and mechanical stirrer. The flask was flushed with nitrogen gas and the reaction carried out under a nitrogen gas flow.

[0890]

[0301] 10 g of 25 kDa hyperbranched PEI (0.180 mole amine content with a ratio of primary to secondary to tertiary amines of approximately 1:1:1) was added to the flask and stirred at 160-180 RPM. Note that 0.180 mole nitrogen content with this ratio of primary, secondary, and tertiary amines in theory can react with 0.120 mole of caprolactone (“1 equivalent of caprolactone” for this example) and 0.360 mole of 1-bromohexane (“1 equivalent of 1-bromohexane” for this example).

[0891]

[0302] Water (10 g) was added to the flask along with tert-amyl alcohol (50 ml), and the resulting solid suspension was cooled to 0-5 °C.

[0892]

[0303] Caprolactone (2.65 g, 0.0238 mole, 0.2 equivalent) was added dropwise over 15-30 minutes at 0-5 °C. The resulting mixture was stirred at 0-5 °C for 4-5 hours. The temperature was increased to 25-30 °C, and the reaction was stirred at this temperature for 14-15 hours resulting in a hazy solution.

[0893]

[0304] tert-Amyl alcohol was distilled off to azeotropically remove water from the reaction mixture, and fresh tert-amyl alcohol was added to replace the solvent that was distilled off. The reaction temperature was increased to 50-60 °C, and the reaction stirred for 60-90 minutes resulting in a clear solution. 1-Bromohexane (153.2 g, 0.928 mole, 2.6 equivalents) was added. The resulting reaction mixture was stirred for 15-30 minutes at 50-60 °C and then the temperature was increased to 94-98 °C. The reaction was stirred at this temperature for 48 hours resulting in a solid suspension.

[0894]

[0305] The reaction was cooled to 25-30 °C. Diethyl ether (100 ml) was added dropwise, and the resulting suspension was stirred at 25-30 °C for 30-60 minutes. Stirring was stopped and the suspension was allowed to settle for 1 hour. The supernatant liquid was decanted away from the settled solid, and fresh diethyl ether (100 ml) was added. This suspension stirring, settling and decanting process was repeated several times until the 1-bromohexane content in the decanted liquid was less than 0.5% as measured by GC analysis.

[0895]

[0306] The remaining solvent was removed under reduced pressure at less than 35 °C. The crude solid product was further dried for 10-12 hours at below 35 °C, affording the QPEI product (32 g) as a beige solid. The water content was measured to be 1200 PPM as measured by Karl Fischer analysis. The bromine content was determined to be -35% as measured by AgNO3titration. Atty. Dkt. No. 136938-0902

[0896]

[0307] The theoretical mole % of PEI reaction with caprolactone and 1 -bromohexane is ~7% and -93%, respectively, assuming that the caprolactone primarily reacts with the primary amines.

[0897]

[0308] Example 32. Additional compounds

[0898]

[0309] The following compounds were prepared using procedures analogous to those in the R60

[0899] R60 | RR6n0above-described examples. A

[0900]

[0901] = R60Compound General Structure PEI MW* R60(mole %)**

[0902] 32-1 B 70 kDa -(CH2)3OH (10%)

[0903] (branched) -C6H13(90%)

[0904] 32-2 B 70 kDa -(CH2)3OH (5%)

[0905] (branched) -C6H13(95%)

[0906] 32-3 B 70 kDa -CH2CH(CH3)OH (5%)

[0907] (branched) -C6H13(95%)

[0908] 32-4 B 70 kDa -C(O)(CH2)5OH (7.5%)

[0909] (branched) -C6H13(92.5%)

[0910] 32-5 A 25 kDa -CH2CH(CH3)OH (50%)

[0911] (hyperbranched) 50:50 -Ci8H37:-C8H17(50%) 32-6 B 72 kDa -(CH2)3OH (13%)

[0912] (branched) 75:25 -Ci8H37:-C8H17(87%) 32-7 B 72 kDa -C(O)(CH2)5OH (6.5%)

[0913] (branched) 75:25 -Ci8H37:-C8H17(93.5%) 32-8 A 25 kDa -C(O)(CH2)5OH (7%)

[0914] (hyperbranched) 75:25 -Ci8H37:-C8H17(93%) 32-9 A 25 kDa -CH2CH(CH3)OH (50%)

[0915] (hyperbranched) 25:75 -Ci8H37:-C8H17(50%) 32-10 A 25 kDa -C(O)(CH2)5OH (11%)

[0916] (hyperbranched) -C6H13(89%)

[0917] 32-11 B 70 kDa -C(O)(CH2)5OH (9%)

[0918] (branched) -C6H13(91%)

[0919] 32-13 B 70 kDa -(CH2)3OH (7%)

[0920] (branched) 75:25 -Ci8H37:-C8H17(93%) 32-14 A 25 kDa -(CH2)3OH (7%)

[0921] (hyperbranched) 75:25 -Ci8H37:-C8H17(93%) 32-15 B 70 kDa -C(O)(CH2)5OH (9%)

[0922] (branched) 75:25 -Ci8H37:-C8H17(91%) 32-16 A 25 kDa -C(O)(CH2)5OH (11%)

[0923] (hyperbranched) 75:25 -Ci8H37:-C8H17(89%) 32-17 B 70 kDa -C6H13(100%)

[0924] (branched)

[0925] 32-18 A 25 kDa -C6H13(100%)

[0926]

[0927] (hyperbranched) Atty. Dkt. No. 136938-0902

[0928] * indicates molecular weight of polyethyleneimine precursor

[0929] ** theoretical stoichiometric ratio (based on amount of reactants used in the synthetic protocol)

[0930]

[0310] Compounds 32-1 and 32-2 were prepared in a similar manner as described in Example 29. The general steps for the synthesis of compounds 32-1 and 32-2 were as follows.

[0931] (1) A mixture of a water solution of 70 kDa PEI, bromopropanol, bromohexane and K2CO3 and f-amyl alcohol was heated at 96-98 °C for 4 days and then allowed to cool to room temperature.

[0932] (2) The resulting mixture was filtered to remove inorganic salts and the filtered solid was washed with f-amyl alcohol.

[0933] (3) The filtrate was evaporated under reduced pressure.

[0934] (4) The residue was triturated 5-6 times with diethyl ether.

[0935] (5) The resulting crude product was dissolved in methyl ethyl ketone, filtered and evaporated to dryness under reduced pressure.

[0936]

[0311] The stoichiometric ratio of R60groups for each of the following compounds (32-1A, 32-1 B, and 32-2A to 32-2I) is a theoretical value calculated based on amount of reactants used in the synthetic protocol, unless otherwise indicated.

[0937]

[0312] Compound 32-1A [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (10%), -C6H13(90%)] was synthesized in a similar manner to compound 32-1, but the crude product dissolved in methyl ethyl ketone was treated with aqueous sodium bicarbonate to increase the pH of the QPEI product closer to neutral prior to filtration and evaporation to dryness.

[0938]

[0313] Compound 32-1 B [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (10%), -C6H13(90%)] was synthesized in a similar manner to compound 32-1, but the residue from step (3) was dissolved in dichloromethane and washed with aqueous sodium bicarbonate before the dichloromethane layer was separated from the aqueous layer and evaporated to dryness under reduced pressure. The crude product was then used in steps (4) and (5).

[0939]

[0314] Compound 32-2A [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (5%), -C6H13(95%)] was synthesized in a similar manner to compound 32-2, but the crude product dissolved in methyl ethyl ketone was treated with aqueous sodium bicarbonate to increase the pH of the QPEI product closer to neutral prior to filtration and evaporation to dryness. Atty. Dkt. No. 136938-0902

[0940]

[0315] Compound 32-2B [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (5%), -C6H13(95%)] was synthesized in a similar manner to compound 32-2, but the residue from step (3) was dissolved in dichloromethane and washed with aqueous sodium bicarbonate before the dichloromethane layer was separated from the aqueous layer and evaporated to dryness under reduced pressure. The crude product was then used in steps (4) and (5).

[0941]

[0316] Compound 32-2C [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (15%), -C6H13(85%) — actual determination via NMR analysis] was synthesized in a similar manner to compound 32-2, but the residue from step (3) was dissolved in an aqueous KOH / ethanol solution, filtered, and concentrated under reduced pressure. The crude product was then used in steps (4) and (5).

[0942]

[0317] Compound 32-2D [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (5%), -C6H13(95%)] was synthesized in a similar manner to compound 32-2, but additional water was added to the initial reaction mixture of step (1).

[0943]

[0318] Compound 32-2E [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (12%), -C6H13(88%) — actual determination via NMR analysis] was synthesized in a similar manner to compound 32-2C, wherein the residue from step (3) was dissolved in an aqueous KOH / ethanol solution, filtered, and concentrated under reduced pressure. The crude product was then used in steps (4) and (5).

[0944]

[0319] Compound 32-2F [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (5%), -C6H13(95%)] was synthesized in a similar manner to compound 32-2, but the mixture in step (1) was heated to 80 °C rather than 96-98 °C.

[0945]

[0320] Compound 32-2G [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (5%), -C6H13(95%)] was synthesized in a similar manner to compound 32-2, but the mixture in step (1) was heated to 80 °C rather than 96-98 °C, and trituration in step (4) was performed using methyl t-butyl ether (MTBE) rather than diethyl ether.

[0946]

[0321] Compound 32-2H [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (5%), -C6H13(95%)] was synthesized in a similar manner to compound 32-2, but the mixture in step (1) had / -propyl alcohol rather than t-amyl alcohol, the mixture in step (1) was heated to 80 °C rather than 96-98 °C, and trituration in step (4) was performed using methyl t-butyl ether (MTBE) rather than diethyl ether.

[0947]

[0322] Compound 32-2I [general structure B; 70 kDa PEI (branched); R60: -(CH2)3OH (5%), -C6H13(95%)] was synthesized in a similar manner to compound 32-2, but the mixture in step (1) had / -propyl alcohol rather than t-amyl alcohol, and the mixture in step (1) was heated to 80 °C rather than 96-98 °C. Atty. Dkt. No. 136938-0902

[0948]

[0323] All patents and other publications; including literature references, issued patents, published patent applications, and co-pending patent applications; cited throughout this application are expressly incorporated herein by reference for the purpose of describing and disclosing, for example, the methodologies described in such publications that might be used in connection with the technology described herein. These publications are provided solely for their disclosure prior to the filing date of the present application. Nothing in this regard should be construed as an admission that the inventors are 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 is based on the information available to the applicants and does not constitute any admission as to the correctness of the dates or contents of these documents.

[0949]

[0324] The foregoing written specification is considered to be sufficient to enable one skilled in the art to practice the present aspects and embodiments. The present aspects and embodiments are not to be limited in scope by examples provided, since the examples are intended as a single illustration of one aspect and other functionally equivalent embodiments are within the scope of the disclosure. Various modifications in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description and fall within the scope of the appended claims. The advantages and objects 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.

Claims

Atty. Dkt. No. 136938-0902CLAIMS1. A microfiber or nanofiber comprising a blend, composite, or interpenetrating polymer network comprising:(1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents; and(2) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

2. The microfiber or nanofiber of claim 1, wherein the polyethyleneimine intermediate and the hydroxy-functionalized oligomer, polymer, or copolymer are non-covalently blended together.

3. A microfiber or nanofiber comprising a polymer or interpenetrating polymer network comprising a polymerization / crosslinking product of reagents comprising:(1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents;(2) a multifunctional crosslinker; and(3) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

4. A microfiber or nanofiber comprising a polymer or interpenetrating polymer network comprising a polymerization / crosslinking product of reagents comprising:Atty. Dkt. No. 136938-0902(1) a polyethyleneimine intermediate, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and one or more alkylating agents; at least one of the one or more alkylating agents introduces hydroxyl or thiol group functionality on the polyethyleneimine intermediate; and nitrogen atoms present in the polyethyleneimine intermediate are partially or completely quaternized by the one or more alkylating agents;(2) an adduct of a quaternary ammonium salt and a multifunctional crosslinker; and(3) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

5. The microfiber or nanofiber of claim 3 or claim 4, wherein the polymer or interpenetrating polymer network are comprised in a blend or composite within the microfiber or nanofiber.

6. The microfiber of claim 3 or claim 4, wherein the polymer is comprised in an interpenetrating polymer network within the microfiber or nanofiber.

7. The microfiber or nanofiber of any one of claims 1-6, wherein the polyethyleneimine intermediate is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 50 wt.%.

8. The microfiber or nanofiber of any one of claims 1-7, wherein the polyethyleneimine intermediate is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 10 wt.%.

9. The microfiber or nanofiber of any one of claims 1-8, wherein the polyethyleneimine intermediate comprises hydroxyalkylene functionality.

10. The microfiber or nanofiber of claim 9, wherein the hydroxyalkylene functionality is optionally substituted with Ci-Ce alkyl optionally substituted with a substituent selected from -N+(R20)3X-, -(C6-C10aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH, -(Ci-Ce alkoxy), -(C6-C10aryl) optionally substituted with -(Ci-Ce alkyl), and carboxy; each R20is independently selected from a group consisting of C1-C18 alkyl; C1-C18 heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10aryl optionally substituted with -(C1-C6alkyl), -(Ci-Ce alkoxy), -C(O)O-(Ci-Ce alkyl), -C(O)NH(CI-C6alkyl), -C(O)N(CI-C6alkyl)2, or -OC(O)-(Ci-C6alkyl); and each X- is independently selected from a group consisting of acetate, halide, sulfate, sulfonate,Atty. Dkt. No. 136938-0902phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

11. The microfiber or nanofiber of claim 9 or claim 10, wherein the hydroxyalkylene functionality is hydroxyethylene, hydroxypropylene, hydroxybutylene, or an oligomer thereof.

12. The microfiber or nanofiber of any one of claims 1-11, wherein the polyethyleneimine intermediate comprises a reaction product of reagents comprising a polyethyleneimine and two alkylating agents.

13. The microfiber or nanofiber of any one of claims 1-12, wherein the one or more alkylating agents, which introduce hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate, comprise a hydroxyl group.

14. The microfiber or nanofiber of any one of claims 1-13, wherein the one or more alkylating agents, which introduce hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate, comprise a primary hydroxyl group.

15. The microfiber or nanofiber of claim 13 or claim 14, wherein the one or more alkylating agents, which introduce hydroxyl group functionality or thiol group functionality on the polyethyleneimine intermediate, comprise a spacer of at least three carbon atoms between a leaving group and the hydroxyl group.

16. The microfiber or nanofiber of any one of claims 1-11, wherein at least one of the one or more alkylating agents is selected from a group consisting of a mono-epoxide, lactone, and R21-LG, wherein:the mono-epoxide is optionally substituted with:(i) Ci-Ce alkyl optionally substituted with a substituent selected from -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with hydroxy, Ci-Ce alkoxy, C6-C10aryl optionally substituted with Ci-Ce alkyl, and carboxy; or(ii) -(C1-C6 alkyl)-N+(R20)3X-; each R20is independently selected from a group consisting of C1-C18 alkyl; C1-C18 heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and C6-C10 aryl optionally substituted with -(C1-C6 alkyl), -(C1-C6 alkoxy), -C(O)O-(C1-C6 alkyl), -C(O)NH(C1-C6 alkyl), -C(O)N(C1-C6 alkyl)2, or -OC(O)-(C1-C6 alkyl); and each X' is independently selected from the group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate,Atty. Dkt. No. 136938-0902hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo- substituted derivatives; andeach R21is independently selected from Ci-Ce alkyl optionally substituted with a substituent selected from -OH, -(Ci-Ce alkoxy), carboxy, -(C6-C10aryl), -C(O)O(Ci-Ce alkyl), -C(O)-(Ce- C aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH; and each LG is a leaving group.

17. The microfiber or nanofiber of claim 16, wherein the leaving group is selected from a group consisting of iodide, bromide, chloride, mesylate, tosylate, nonaflate, and triflate.

18. The microfiber or nanofiber of claim 16 or claim 17, wherein at least one of the one or more alkylating agents is selected from R21-LG.

19. The microfiber or nanofiber of any one of claims 16-18, wherein the one or more alkylating agents comprise a C1-C6 alkyl halide and a haloalkanol, wherein the haloalkanol is X30-(C2-C6 alkylene)-OH, wherein X30is Cl, Br, or I.

20. The microfiber or nanofiber of claim 19, wherein the one or more alkylating agents comprise 1 -bromohexane and 3-bromopropanol.

21. The microfiber or nanofiber of claim 16, wherein the lactone is caprolactone or butyrolactone.

22. The microfiber or nanofiber of any one of claims 1-21, wherein the polyethyleneimineAtty. Dkt. No. 136938-0902or a copolymer of any two or more thereof, wherein:each Y3is independently H or -OH, wherein every Y3cannot be H;each n is an integer independently selected from 1 to 3000, preferably an integer independently selected from 10 to 1000;Z is -(C2-C6 alkylene)-;each R10is independently selected from hydrogen; Ci-Ce alkyl optionally substituted with a substituent selected from -N(R20)3, -(Ce-Cw aryl), and -(Ci-Ce alkoxy) optionally substituted with -OH, -(Ci-Ce alkoxy), -(C6-C10aryl) optionally substituted with -(Ci-Ce alkyl), and carboxy; and each R20is independently selected from a group consisting of C1-C18 alkyl; C1-C18 heteroalkyl having 1 to 4 heteroatoms independently selected from O, S, Si and tertiary-substituted N; and Ce-Cw aryl optionally substituted with -(Ci-Ce alkyl), -(Ci-Ce alkoxy), -C(O)O-(Ci-C6alkyl), -C(O)NH(Ci-Cealkyl), -C(O)N(Ci-Cealkyl)2, or -OC(O)-(Ci-C6alkyl);each R21is independently selected from C1-C6alkyl optionally substituted with a substituent selected from -OH, -(C1-C6alkoxy), carboxy, -(C6-C10aryl), -C(O)O(C1-C6alkyl), -C(O)-(C6-C10aryl), and -(C1-C6alkoxy) optionally substituted with -OH;each R30is independently selected from (1) C6-C20 alkyl optionally substituted with 1-3 substituents independently selected from halogen, -SiRa(ORb)(ORc), and -(C6-C10 aryl); and (2) C6-C10 aryl optionally substituted with 1-3 substituents independently selected from halogen, -(C1-C6 alkyl), and -SiRa(ORb)(ORc); wherein each Rais independently -Atty. Dkt. No. 136938-0902(C1-C6 alkyl); and each Rband each Rcare independently selected from -(C1-C6 alkyl) and -Si(C1-C6 alkyl)3; andeach X’ is independently selected from a group consisting of acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, and borate, and their organo-substituted derivatives.

23. The microfiber or nanofiber of any one of claims 1-22, wherein the polyethyleneimine has a molecular weight of about 300 to about 270,000 daltons.

24. The microfiber or nanofiber of any one of claims 1-23, wherein the polyethyleneimine has a molecular weight of about 10,000 to about 200,000 daltons.

25. The microfiber or nanofiber of any one of claims 1-24, wherein the polyethyleneimine has a molecular weight of about 25,000 to about 120,000 daltons.

26. The microfiber or nanofiber of any one of claims 1-25, wherein the polyethyleneimine is branched.

27. The microfiber or nanofiber of any one of claims 1-25, wherein the polyethyleneimine is hyperbranched.

28. The microfiber or nanofiber of any one of claims 1-27, wherein the polyethyleneimine has a ratio of primary to secondary to tertiary amines of about 1:2: 1 to about 1:1:1.

29. The microfiber or nanofiber of any one of claims 1-28, wherein the polyethyleneimine has a ratio of primary to secondary to tertiary amines of about 1: 1:0.7.

30. The microfiber or nanofiber of any one of claims 1-29, wherein the polyethyleneimine is QPEI-C3OHC6.

31. A microfiber or nanofiber comprising polymer or interpenetrating polymer network comprising a polymerization / crosslinking product of reagents comprising:(1) an adduct of a quaternary ammonium salt and a multifunctional crosslinker; and(2) a hydroxy-functionalized oligomer, polymer, or copolymer comprising pendant and / or terminal hydroxy group(s).

32. The microfiber or nanofiber of claim 31, wherein the polymer or interpenetrating polymer network are comprised in a blend or composite within the microfiber or nanofiber.Atty. Dkt. No. 136938-090233. The microfiber or nanofiber of claim 31, wherein the polymer is comprised in an interpenetrating polymer network within the microfiber or nanofiber.

34. The microfiber or nanofiber of any one of claims 4-33, wherein the quaternary R1v- R2^ I +Xammonium salt has a chemical structure ofR A wherein:R1is selected from a group consisting of -(C8-C30alkyl), -(C8-C30heteroalkyl), -(C8-C30heteroalkyl)-(C6-C10aryl), -(C6-C10aryl), -(C6-C10aryl)-(C8-C30alkyl), -(C6-C10aryl)-(C8-C30heteroalkyl), -(CRmRn)x10-W10-(CRpRq)y10-H, and -(CRmRn)x11-W11-(CRpRq)y11-H; wherein -(C8-C30heteroalkyl), -(C8-C30heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl)-(C8-C30heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;R2is selected from a group consisting of -(C1-C4 alkyl), -(C1-C4 heteroalkyl), -(C1-C4 heteroalkyl)-(C6-C10aryl), -(C6-C10aryl), -(C6-C10aryl)-(C1-C4 alkyl), -(C6-C10aryl)-(C1-C4 heteroalkyl); -(CRmRn)x20-W20-(CRpRq)y20-H, and -(CRmRn)x21-W21-(CRpRq)y21-H; wherein -(C1-C4 heteroalkyl), -(C1-C4 heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl)-(C1-C4 heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;R3is selected from a group consisting of -(C1-C30alkyl), -(C1-C30heteroalkyl), -(C1-C30heteroalkyl)-(C6-C10aryl), -(C6-C10aryl), -(C6-C10aryl)-(C1-C30alkyl), -(C6-C10aryl)-(C1-C30heteroalkyl), -(CRmRn)x30-W30-(CRpRq)y30-H, and -(CRmRn)x31-W31-(CRpRq)y31-H; wherein -(C1-C30heteroalkyl), -(C1-C30heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl)-(C1-C30heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si;A is a linking group selected from a group consisting of -(C3-C20alkylene)-, -(C3-C20heteroalkylene)-, -(C6-C10arylene)-(C3-C20alkylene)-, -(CRmRn)x40-W40-(CRpRq)y40-, and -(CRmRn)x41-W41-(CRpRq)y41-, wherein -(C3-C20heteroalkylene)- has 1 to 4 heteroatoms independently selected from O, S, and Si; and -(C3-C20alkylene)- and -(C3-C20heteroalkylene)- are optionally substituted with 1 to 6 substituents independently selected from -(C6-C10aryl)-(C1-C3alkyl), -(C6-C10aryl)-(C1-C3heteroalkyl), -(C1-C3alkyl)-(C6-C10aryl), -(C1-C3heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl);each Rm, Rn, Rp, and Rqis independently selected from H and C1-C4 alkyl;W10, W20, W30, and W40are independently selected from -C(O)-; -C(O)O-; -OC(O)-; -C(O)NH-; and -NHC(O)-;Atty. Dkt. No. 136938-0902W11, W21, W31, and W41are independently selected from 5- to 6-membered cycloalkyl, Ce-Cw aryl, 5- to 6-membered heterocycloalkyl, and 5- to 6-membered heteroaryl, wherein the heterocycloalkyl contains 1-2 ring heteroatoms selected from O, N, S, and Si; and the heteroaryl contains 1-3 ring heteroatoms selected from O, N, S, and Si;x10 is an integer from 1 to 30 and y10 is an integer from 0 to 29, wherein 8 ≤ (x10 + y10) ≤ 30;x11 is an integer from 1 to 30 and y11 is an integer from 0 to 29, wherein 8 ≤ (x11 + y11) ≤ 30;x20 is an integer from 1 to 4 and y20 is an integer from 0 to 3, wherein x20 + y20 ≤ 4;x21 is an integer from 1 to 4 and y21 is an integer from 0 to 3, wherein x21 + y21 ≤ 4;x30 is an integer from 1 to 30 and y30 is an integer from 0 to 29, wherein x30 + y30 ≤ 30;x31 is an integer from 1 to 30 and y31 is an integer from 0 to 29, wherein x31 + y31 ≤ 30;x40 is an integer from 1 to 19 and y40 is an integer from 1 to 19, wherein 3 ≤ (x40 + y40) ≤ 20;x41 is an integer from 1 to 20, and y41 is an integer from 0 to 19, wherein 3 ≤ (x41 + y41) ≤ 20;Y is selected from a group consisting of -OH, -NHR4, -SH, -CO2H, -C(O)NHR4, -C(S)NHR4,R4each R4is independently selected from a group consisting of H, -(C6-C10aryl)-(Ci-C3alkyl), - (Ce-Cw aryl)-(Ci-C3heteroalkyl), -(Ci-C3alkyl)-(C6-Cwaryl), -(Ci-C3heteroalkyl)-(C6-Cw aryl), and -(Ce-Cw aryl), wherein -(Ce-Cw aryl)-(Ci-C3heteroalkyl) and -(Ci-C3heteroalkyl)-(Ce-Cw aryl) have 1 to 4 heteroatoms independently selected from O, S, and Si; andX’ is independently acetate, halide, sulfate, sulfonate, phosphate, phosphonate, carbonate, silicate, hexafluorophosphate, hexafluoroantimonate, triflate, borate, or an organo- substituted derivative of any of the foregoing.Atty. Dkt. No. 136938-090235. The microfiber or nanofiber of claim 34, wherein R1is selected from a group consisting of -(Ci2-Cso alkyl), -(C12-C30 heteroalkyl), -(Ci2-C3oalkyl)-(Ce-Cw aryl), -(C12-C30 heteroal kyl)-(Ce-Cw aryl), -(Ce-Cw aryl)-(Ci2-Cso alkyl), and -(Ce-Cw aryl)-(Ci2-Cso heteroalkyl); wherein -(C12-C30 heteroalkyl), -(C12-C30 heteroalkyl)-(Ce-Cw aryl), and -(C6-C10aryl)-(Ci2-Cso heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si.

36. The microfiber or nanofiber of claim 34 or claim 35, wherein R3is selected from a group consisting of -(Ci-C4 alkyl), -(C1-C4 heteroalkyl), -(Ci-C4alkyl)-(C6-C10aryl), -(C1-C4 heteroal kyl)-(C6-Cw aryl), -(C6-Cw aryl)-(Ci-C4alkyl), and -(C6-Cw aryl)-(Ci-C4heteroalkyl); wherein -(C1-C4 heteroalkyl), -(C1-C4heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl)-(C1-C4heteroalkyl) have 1 to 4 heteroatoms independently selected from O, S, and Si.

37. The microfiber or nanofiber of any one of claims 34-36, wherein R2and R3are methyl.

38. The microfiber or nanofiber of any one of claims 34-37, wherein A is -(CH2)m- or - (CH2CHR5-O-)nCH2CHR5-, wherein m is an integer from 2 to 20; n is 0, 1, 2, 3, 4, or 5; and each R5is independently selected from a group consisting of H, -(C6-C10aryl)-(C1-C3alkyl), -(C6-C10aryl)-(C1-C3heteroalkyl), -(C1-C3 alkyl)-(C6-C10aryl), -(C1-C3 heteroalkyl)-(C6-C10aryl), and -(C6-C10aryl), wherein -(C6-C10aryl)-(C1-C3heteroalkyl) and -(C1-C3 heteroalkyl)-(C6-C10aryl) have 1 to 4 heteroatoms independently selected from O, S, and Si.

39. The microfiber or nanofiber of claim 38, wherein R5is H or methyl.

40. The microfiber or nanofiber of any one of claims 4-39, wherein the quaternaryCl8H37'- l +BrC18H37X I +BrBr ammonium salt is / C16H33J+BRBr C14H29J + / N.BrC12H25J+Br’C12H25. II+, or a combination of two or more thereof.

41. The microfiber or nanofiber of any one of claims 4-40, wherein the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of about 5 wt.% to about 50 wt.%.

42. The microfiber or nanofiber of any one of claims 4-40, wherein the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of about 1.0Atty. Dkt. No. 136938-0902x1 O’4to about 1.2 x1 O'3mole of the quaternary ammonium group per gram of the dried microfiber or the dried nanofiber.

43. The microfiber or nanofiber of any one of claims 4-42, wherein the multifunctional crosslinker is present in the dried microfiber or dried nanofiber in an amount of about 3 wt.% to about 20 wt.%.

44. The microfiber or nanofiber of any one of claims 4-43, wherein the multifunctional crosslinker is a multifunctional isocyanate, isothiocyanate, epoxide, or a precursor thereof.

45. The microfiber or nanofiber of any one of claims 4-44, wherein the multifunctional crosslinker is a polyisocyanate.

46. The microfiber or nanofiber of claim 45, wherein the polyisocyanate has an average isocyanate functionality of 2 to 5 or 3 to 4.

47. The microfiber or nanofiber of claim 45 or claim 46, wherein the polyisocyanate is prepared from a diisocyanate independently selected from a group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylenediisocyanate (XDI), methylene-bis-(4-cyclohexylisocyanate) (H12MDI), meta-tetramethylxylene diisocyanate (TMXDI ), and trimethylhexamethylene diisocyanate (TMDI).

48. The microfiber or nanofiber of any one of claims 45-47, wherein the polyisocyanate is selected from a group consisting of DESMODUR® N-3300, DESMODUR® N-100, DESMODUR® Z4470SN, WANNATE®T series polyisocyanates, and LUPRANATE® M series polyisocyanates.

49. The microfiber or nanofiber of any one of claims 4-48, wherein the adduct further comprises a chain extender.

50. The microfiber or nanofiber of claim 49, wherein the chain extender comprises polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), or a combination of two or more thereof, or a copolymer of one or more thereof with polyester, polycaprolactone, polybutadiene, poly(acrylonitrile-butadiene), polysiloxane, or polyacrylate.

51. The microfiber or nanofiber of claim 49 or claim 50, wherein the chain extender is PTMG.Atty. Dkt. No. 136938-090252. The microfiber or nanofiber of any one of claims 4-51, wherein the hydroxyfunctionalized oligomer, polymer, or copolymer is a polymer, copolymer or oligomer of a hydroxy-functionalized monomer or a precursor thereof selected from a group consisting of ethylene oxide, propylene oxide, tetrahydrofuran (THF), caprolactone, butyrolactone, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N-methylol acrylamide, N-methylol methacryamide, allyl alcohol, triethanol amine, diethanol alkylamine, and N, N, N’N’-tetrakis(2-hydroxyalkyl) ethylenediamine.

53. The microfiber or nanofiber of any one of claims 4-52, wherein the hydroxyfunctionalized oligomer, polymer, or copolymer is a copolymer of 2-hydroxyethyl methacrylate.

54. The microfiber or nanofiber of any one of claims 4-53, wherein the hydroxyfunctionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 300 to about 100,000.

55. The microfiber or nanofiber of any one of claims 4-54, wherein the hydroxyfunctionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 400 to about 10,000.

56. The microfiber or nanofiber of any one of claims 4-55, wherein the hydroxyfunctionalized oligomer, polymer, or copolymer has a weight average molecular weight from about 600 to about 3,000.

57. The microfiber or nanofiber of any one of claims 4-56, wherein the hydroxyfunctionalized oligomer, polymer, or copolymer is present in the dried polymer or interpenetrating polymer network in an amount of about 1 wt.% to about 20 wt.%.

58. The microfiber or nanofiber of any one of claims 4-57, wherein:(1) the polyethyleneimine intermediate and the quaternary ammonium salt are present in the dried microfiber or dried nanofiber in a combined amount of less than 35 wt.%; or(2) in the absence of any polyethyleneimine intermediate, the quaternary ammonium salt is present in the dried microfiber or dried nanofiber in an amount of less than 35 wt.%.

59. The microfiber or nanofiber of any one of claims 4-57, wherein:Atty. Dkt. No. 136938-0902(1) the polyethyleneimine intermediate and the quaternary ammonium salt are present in a combined amount of less than 1.2 x10-3mole of the quaternary ammonium group per gram of the dried polymer or interpenetration network, or(2) in the absence of any polyethyleneimine intermediate, the quaternary ammonium salt is present in an amount of less than 1.2 x10-3mole of the quaternary ammonium group per gram of the dried microfiber or dried nanofiber.

60. The microfiber or nanofiber of any one of claims 4-59, further comprising covalent attachment of a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof.

61. The microfiber or nanofiber of any one of claims 1-60, wherein the hydroxyfunctionalized oligomer, polymer, or copolymer is present in the microfiber or the nanofiber in an amount of about 25 wt.% to about 50 wt.%.

62. The microfiber or nanofiber of any one of claims 1-60, wherein the microfiber or the nanofiber has a total quaternary ammonium salt density of at least 3.0 x10-4mole, preferably at least 5.0 x10-4mole, of total quaternary ammonium salt functionality per gram of dried microfiber or dried nanofiber.

63. The microfiber or nanofiber of any one of claims 1-60, wherein the microfiber or the nanofiber is a core-shell microfiber or nanofiber.

64. The microfiber or nanofiber of claim 63, wherein quaternary ammonium salt density of the shell is different from quaternary ammonium salt density of the core.

65. The microfiber or nanofiber of claim 63, wherein quaternary ammonium salt density of the shell is higher than quaternary ammonium salt density of the core.

66. The microfiber or nanofiber of claim 1, comprising a blend, composite, or interpenetrating polymer network consisting of (1) QPEI-C3OHC6; and (2) a HEMA polyol.

67. The microfiber of nanofiber of claim 3, comprising a polymer or interpenetrating polymer network comprising of a polymerization product of reagents and / or a crosslinking product of reagents consisting of (1) QPEI-C3OHC6; (2) DESMODUR® N100; and (3) a HEMA polyol.Atty. Dkt. No. 136938-090268. The microfiber of nanofiber of claim 49, comprising a polymer or interpenetrating polymer network comprising a polymerization product of reagents and / or a crosslinking product of reagents consisting of (1) QPEI-C3OHC6; (2) an adduct of C18DMDEG, DESMODUR® N100, and PTMG-1000; and (3) a HEMA polyol.

69. The microfiber of nanofiber of claim 60, comprising a polymer or interpenetrating polymer network comprising a polymerization product of reagents and / or a crosslinking product of reagents consisting of (1) QPEI-C3OHC6; (2) an adduct of C18DMDEG, DESMODUR® N100, and PTMG-1000; (3) a HEMA polyol; and (4) 3-aminopropyltriethoxysilane.

70. The microfiber of nanofiber of claim 49, comprising a polymer or interpenetrating polymer network comprising a polymerization product of reagents and / or a crosslinking product of reagents consisting of (1) an adduct of C18DMDEG, DESMODUR® N100, and PTMG-1000; and (2) a HEMA polyol.

71. A nonwoven fabric comprising the microfiber or nanofiber of any one of claims 1-70.

72. The nonwoven fabric of claim 71, wherein the nonwoven fabric has a coverage of microfibers or nanofibers of at least 3 g / m2, preferably at least 5 g / m2.

73. The nonwoven fabric of claim 71 or claim 72, wherein the nonwoven fabric is deposited on a support to form a composite nonwoven fabric.

74. The nonwoven fabric of claim 73, wherein the support is a non-antimicrobial nonwoven fabric having a coverage of microfibers or nanofibers of at least 3 g / m2, preferably at least 5 g / m2.

75. The nonwoven fabric of claim 73, wherein the support is a second nonwoven fabric with the same coverage of microfibers or nanofibers as the nonwoven fabric.

76. The nonwoven fabric of claim 73, wherein the support is a second nonwoven fabric with different coverage of microfibers or nanofibers compared to the nonwoven fabric.

77. The nonwoven fabric of claim 73, wherein the support is a second nonwoven fabric with the same quaternary ammonium salt density as the nonwoven fabric.

78. The nonwoven fabric of claim 73, wherein the support is a second nonwoven fabric with different quaternary ammonium salt density compared to the nonwoven fabric.Atty. Dkt. No. 136938-090279. An apparatus or accessory comprising the nonwoven fabric of any one of claims 71-78.

80. The apparatus or accessory of claim 79, wherein the apparatus or accessory is selected from a group consisting of a filter, a mask, a membrane, a diaper, a wound care dressing, a super absorbent, a humectant, a synthetic skin, a synthetic organ, a skincare product, and a scaffold for controlled release of a fertilizer, a nutritional supplement, a pesticide, or a pharmaceutically active agent.

81. The apparatus or accessory of claim 80, wherein the wound care dressing comprises a film, a gel, a matrix product, a wound therapy system, a placental membrane, a non-silver wound dressing product, a negative-pressure wound therapy system, a surgical dressing, an adhesive antimicrobial dressing, a barrier dressing, an adhesive or non-adhesive hydrocellular foam dressing, a gelling fiber wound dressing, or a low adherent absorbent dressing.

82. A method to prepare the microfiber or nanofiber of claim 1 or claim 2, the method comprising:preparing a solution comprising (1) the polyethyleneimine intermediate, and (2) the hydroxyfunctionalized oligomer, polymer, or copolymer; andelectrospinning the solution to form the microfiber or nanofiber.

83. A method to prepare the microfiber or nanofiber of claim 3, the method comprising:preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the multifunctional crosslinker; and (3) the hydroxy-functionalized oligomer, polymer, or copolymer; andelectrospinning the solution to form the microfiber or nanofiber.

84. A method to prepare the microfiber or nanofiber of claim 4, the method comprising:preparing a solution comprising (1) the polyethyleneimine intermediate; (2) the adduct of the quaternary ammonium salt and the multifunctional crosslinker; and (3) the hydroxyfunctionalized oligomer, polymer, or copolymer; andelectrospinning the solution to form the microfiber or nanofiber.Atty. Dkt. No. 136938-090285. The method of claim 84, wherein the solution further comprises a trialkoxysilane selected from a group consisting of 3-hydroxypropyl trimethoxysilane, 3-hydroxypropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, and a combination of two or more thereof; and optionally a catalyst selected from a group consisting of citric acid, oxalic acid, and XK-651 (bismuth carboxylate catalyst).

86. A method to prepare the microfiber or nanofiber of claim 4, the method comprising:preparing a first solution comprising (1) the polyethyleneimine intermediate; and (2) the adduct of the quaternary ammonium salt and the multifunctional crosslinker;preparing a second solution comprising the hydroxy-functionalized oligomer, polymer, or copolymer; andcombining the first solution and the second solution via in-line mixing to form a third solution; andelectrospinning the third solution to form the microfiber or nanofiber.

87. The method of any one of claims 84-86, wherein the adduct further comprises a chain extender.

88. The method of any one of claims 82-87, wherein the microfiber or nanofiber has a total quaternary ammonium salt density of at least 3.0 x10-4mole of total quaternary ammonium salt functionality per gram of dried microfiber or dried nanofiber.

89. The method of any one of claims 82-88, wherein the hydroxy-functionalized oligomer, polymer, or copolymer is present in the dried microfiber or dried nanofiber in an amount of about 20 wt.% to about 50 wt.%.

90. The method of any one of claims 82-89 further comprising curing the microfiber or nanofiber.

91. The method of any one of claims 82-90, further comprising washing the microfiber or nanofiber.

92. The method of any one of claims 82-91, wherein the microfiber or nanofiber is electrospun onto a temporary substrate and released as a free-standing nonwoven fabric.Atty. Dkt. No. 136938-090293. The method of any one of claims 82-91, wherein the microfiber or nanofiber is electrospun onto an inert nonwoven support to form a composite nonwoven fabric.

94. The method of any one of claims 82-91, wherein the microfiber or nanofiber is electrospun onto a surface of a nonwoven fabric support to create a nonwoven surface layer to form a composite nonwoven fabric.

95. The method of claim 94, wherein the nonwoven surface layer has the same quaternary ammonium salt density as the nonwoven fabric support.

96. The method of claim 94, wherein the nonwoven surface layer has different quaternary ammonium salt density compared to the nonwoven fabric support.

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