BRITTON HEIDI M (CA)
GHOLAMKHASS BOBAK (CA)
PECKHAM TIMOTHY J (CA)
CLAIMS The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 1. A method of inhibiting microorganisms on a surface, comprising applying to the surface a polymer comprising a repeating unit, the repeating unit comprising: (i) a benzimidazolium-containing moiety of Formula (I): (I) wherein: R1AA is independently selected from the group consisting of H, methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, heteroaryl group and a polymer; R2AA is independently selected from the group consisting of hydrogen, any group, and a polymer; R3AA is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, a polymer, and no group; and R5AA is independently selected from the group consisting of hydrogen, any group, and a polymer; wherein at least one of R1AA, R2AA, R3AA, and R5AA, is a polymer; (ii) an imidazolium-containing moiety having Formula (II): (II) wherein: R1XX is independently selected from the group consisting of H, methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, heteroaryl group and a polymer; R2XX is independently selected from the group consisting of hydrogen, any group, and a polymer; R3XX is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, a polymer, and no group; and R5XX is independently selected from the group consisting of hydrogen, any group, and a polymer; wherein at least one of R1XX, R2XX, R3XX, and R5XX, is a polymer, or any combination thereof. 2. The method of Claim 1, further comprising exposing the surface to the microorganism and killing the microorganism present on the surface. 3. The method of Claim 1 or Claim 2, further comprising inhibiting adhesion of the microorganism on the surface. 4. The method of any one of the preceding claims, wherein when the surface is exposed to the microorganism, the number of microorganisms on the surface is reduced by greater than 99 % after a duration of 24 hours. 5. The method of any one of the preceding claims, wherein the microorganism comprises a fungus, a bacterium, a virus, or any combination thereof. 6. The method of Claim 5, wherein when the surface is exposed to a fungus, the number of the fungus is reduced by greater than 99 % after a duration of 24 hours. 7. The method of Claim 5 or Claim 6, wherein the fungus is selected from Candida spp., Cryptococcus spp., Blastomyces spp., Coccidioides spp., Aspergillus spp., Emmonsia spp., Chrysosporium spp., Fonsecaea spp., Trychophyon spp., Histoplasma spp., Ajellomyces spp., Pneumocytis spp., Microsporum spp., Magnaporthe spp., Fusarium spp., Sporothrix spp., Cyberlindnera spp., Mucormycetes spp., Epidermophyton spp., Trichosporon spp., Paracoccidioides spp., Talaromyces spp., Uncinocarpus reesii, and Aphanoascus spp. 8. The method of Claim 5, wherein when the surface is exposed to a bacterium, the number of the bacterium is reduced by greater than 99 % after a duration of 24 hours. 9. The method of Claim 5 or Claim 8, wherein the bacterium is a gram-positive bacterium. 10. The method of Claim 5 or Claim 8, wherein the bacterium is a gram-negative bacterium. 11. The method of any one of Claims 5 and 8 to 10, wherein the microorganism is a pathogenic bacterium. 12. The method of Claim 11, wherein the pathogenic bacterium is selected from Escherichia coli, Staphylococcus aureus, Campylobacter spp., Legionella, Salmonella spp., Shigella spp., Tsukamurella, Leptospires, Mycobacterium, Pseudomonas aeruginosa, Aeromonas spp., Vibrio spp., Yersinia, Bacillus spp., Enterobacter sakazakii, Burkholderia pseudomallei, Acinetobacter spp., Helicobacter pylori, Klebsiella spp., clostridium spp., and Streptococci. 13. The method of Claim 5, wherein when the surface is exposed to a virus, the number of the virus is reduced by greater than 99 % after a duration of 24 hours. 14. The method of Claim 5 or Claim 13, wherein the virus is selected from alphacoronaviruses, betacoronaviruses (e.g., SARS-Cov2), deltacoronaviruses, gammacoronaviruses, and toroviruses; influenza virus A, influenza virus B, influenza virus C, influenza virus D, hepatitis A virus, hepatitis B virus, simplex viruses, cytomegaloviruses, mamastroviruses, mastadenoviruses, poxviruses, hepadnaviruses, asfarviridae, flaviviruses, alphaviruses, togaviruses, paramyxoviruses, rhabdovirus, bunyaviruses, filoviruses, retroviridae, coxsackieviruses (enveloped and non-enveloped), rotaviruses, polioviruses, calciviruses, orthopoxviruses, polyomaviruses, vesiculoviruses, varicelloviruses, phleboviruses, alphatorqueviruses, noroviruses, rubulaviruses, spumaviruses, rubulaviruses, hantaviruses, sapoviruses, saliviruses, rubiviruses, rosaviruses, lyssaviruses, enteroviruses, arenaviruses, orthobunyaviruses, parapoxviruses, henipaviruses, molluscipoxviruses, polyomaviruses, cardioviruses, morbilviruses, marburgviruses, deltaretroviruses, orthopneumoviruses, erythroviruses, respiroviruses, alphapapillomavirus, mupapillomaviruses, rhadinoviruses, roseoloviruses, deltaviruses, hepeviruses, hepaciviruses, orthohepadnaviruses, henipaviruses, pegiviruses, lymphocryptoviruses, ebolaviruses, nairoviruses, thogotoviruses, cosaviruses, seadornaviruses, kobuviruses, dependoviruses, and any combination thereof. 15. The method of any one of the preceding claims, wherein the polymer comprises a counterion selected from the group consisting of iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, tosylate, bisulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate. 16. The method of any one of the preceding claims, wherein the benzimidazolium-containing moiety of Formula (I), the imidazolium-containing moiety having Formula (II), or both are each independently in a main chain of the polymer. 17. The method of any one of the preceding claims, wherein the benzimidazolium-containing moiety of Formula (I), the imidazolium-containing moiety having Formula (II), or both are each independently in a pendant group of the polymer. 18. The method of any one of the preceding claims, wherein the benzimidazolium-containing moiety of Formula (I), the imidazolium-containing moiety having Formula (II), or both are each independently part of a crosslink of the polymer. 19. The method of any one of the preceding claims, wherein the polymer comprises a polymer of Formula (III): (III) wherein R1AA and R3AA are methyl groups and R2AA is hydrogen. 20. The method of any one of Claims 1 to 18, wherein the repeating unit comprises a benzimidazolium-containing moiety of Formulas (IV)-(VIII): (IV) (V) (VI) (VII) (VIII) wherein: R1 is independently selected from the group consisting of H, methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, heteroaryl group and a polymer; R2 is independently selected from the group consisting of hydrogen, any group, and a polymer; R3 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a polymer; R5 is independently selected from the group consisting of hydrogen, any group, and a polymer; wherein at least one of R1, R2, R3, and R5, is a polymer; and X is independently selected from the group consisting of alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and no group. 21. The method of any one of Claims 1 to 18 and 20, wherein the polymer comprises a polymer of Formula (IX): (IX) wherein: R11a, R11b, R11c, R11d, R21a, R21b, R21c, R21d, R31a, R31b, R31c, and R31d are each independently selected from H, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl; R12a, R12b, R12c, R12d, R22a, R22b, R22c, R22d, R32a, R32b, R32c, and R32d are each independently selected from H, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl; R13a, R13b, R14a, and R14b are each independently selected from absent, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that two of R13a, R13b, R14a, and R14b are absent, and the remaining two are present and independently selected from C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl. R23a, R23b, R24a, and R24b are each independently selected from absent, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that one of R23a, R23b, R24a and R24b is absent, and the remaining three are present and independently selected from C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl; R33a, R33b, R34a, and R34b are each independently selected from C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl; R15a, R15b, R15c, R15d, R15e, R15f, R25a, R25b, R25c, R25d, R25e, R25f, R35a, R35b, R35c, R35d, R35e, and R35f are each independently selected from H, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halo, aryl, and heteroaryl; X11, X21, and X31 are each independently selected from the group consisting of absent, C1-6 alkylene, C1-6 haloalkylene, arylene, and heteroarylene; and a, b, and c are mole percentages, wherein a is from 0 mole percent to 45 mole percent, b+c is 55 mole percent to 100 mole percent, b and c are each more than 0 percent, and a+b+c=100%. 22. The method of any one of Claims 1 to 18, wherein the repeating unit comprises an imidazolium-containing moiety of Formula (X): (X) wherein: R1XY, R2XY, R4XY, and R5XY are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; provided that at least one of R1XY and R2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl, when one of R1XY and R2XY is absent, the imidazolyl group to which the absent R1XY or R2XY is connected is charge-neutral; and at least one of R4XY and R5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and when one of R4XY and R5XY is absent, the imidazolyl group to which the absent R4XY or R5XY is connected is charge neutral; R3XY and R6XY are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R15XY is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R16XY is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R7XY, R10XY, R11XY, and R14XY are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R8XY, R9XY, R12XY, and R13XY are each independently selected from hydrogen, alkyl, perfluoroalkyl, and heteroalkyl. 23. The method of any one of Claims 1 to 18, wherein the repeating unit comprises a moiety of Formula (XI) (XI). 24. The method of any one of Claims 1 to 18 and 23, wherein the repeating unit comprises a moiety of Formula (XII) (XII). 25. The method of any one of Claims 1 to 18, wherein the repeating unit comprises a moiety of Formula (XIII) ĨXIII). 26. The method of any one of the preceding claims, wherein the polymer is in the form of a coating or a membrane. 27. The method of any one of the preceding claims, wherein the polymer is in the form of spun fibers, electrospun fibers, solution cast coating, extruded fibers, nanofibers, or any combination thereof. 28. The method of any one of the preceding claims, wherein the polymer is in the form of a microporous film, nanoporous film, non-woven sheet, woven sheet, mat, fabric, or any combination thereof. 29. The method of any one of the preceding claims, wherein the polymer is in a blend. 30. The method of Claim 29, wherein the blend is a polymer blend. 31. The method of any one of the preceding claims, wherein the polymer is a graft copolymer, an interpenetrating network, an aerogel, or a hydrogel. 32. The method of any one of the preceding claims, wherein the surface comprises a surface of a medical device or a portion thereof. 33. The method of Claim 32, wherein the medical device is selected from an urinary catheter, a percutaneous catheter, a central venous catheter, a vascular access device, a heart valve, a stent, a vascular prosthesis, a skeletal joint, a dental filling, a dental implant, an oxygen transport membrane, a suture, an intravenous delivery site, a drug delivery catheter, a drain, a gastric feeding tube, a tracheotomy tube, a contact lens, an intraocular lens, an orthopedic implant, a neuro-stimulation lead, a pacemaker lead, a blood bag, an air filter, and a drug diffusion matrix (e.g., membranes, films, rods, beads, or any combination thereof). |
Formula (II-B) Given the multiple available locations on the moieties for attachment to a polymer main chain, the moieties can be attached to multiple polymer chains (e.g., as part of a crosslink). An exemplary embodiment illustrating crosslinking between two polymer chains, P 1XX and P 2XX , via the R 3XX positions, is illustrated in Formula (II-C) below. It will be appreciated that the crosslinking capabilities of the moieties are not limited to the illustrated embodiment. Formula (II-C) In one embodiment, the moiety M1 is grafted onto an already-formed polymer. For example, using a benzimidazole with a monosubstituted R 3AA position (Formula I-D), mixed with P 1AA and heated can produce a pendant benzimidazolium (Formula I-C) connected at the formerly vacant R 3AA position. Examples of P 1AA include alkylhalide-containing polymers such as chloromethylated polysulfone and poly(chloromethylstyrene), including perfluorinated polymers containing haloalkyl groups. In addition, perfluorinated sulfonyl halide-containing polymers, or polymers containing acyl halides can be functionalized using this method. Formula (I-D) Alternatively, the moiety M2 is grafted onto an already-formed polymer using an imidazole with a monosubstituted R 3 position (Formula II-D) to produce the pendant imidazolium (Formula II-C). Formula (II-D) In certain embodiment, the disclosed cationic moieties form a salt with an anion. Any anion sufficient to balance the charge of the moiety-containing polymer can be used. Representative anions include iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, tosylate, bisulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate. The polymers containing the moieties can be of any size known to those of skill in the art. In some embodiments, the polymer is a polymer of Formula III: Formula (III) In one embodiment, in Formula (III), R 1AA and R 3AA are methyl groups and R 2AA is hydrogen. In some embodiments, the polymers of the present disclosure can include one or more repeating units, wherein at least one of the repeating units includes one or more benzimidazolium-containing moieties of Formulas (IV)-(VIII):
(IV) (V) (VI) (VII) (VIII) wherein: R 1 is independently selected from the group consisting of H, methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, heteroaryl group, and a polymer; R 2 is independently selected from the group consisting of hydrogen, any group, and a polymer; R 3 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a polymer; R 5 is independently selected from the group consisting of hydrogen, any group, and a polymer; wherein at least one of R 1 , R 2 , R 3 , and R 5 , is a polymer; and X is independently selected from the group consisting of alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and no group. In some embodiments, the polymer is a salt formed with an anion selected from the group consisting of iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, tosylate, bicarbonate, bisulfate, hydrogen phosphate, and dihydrogen phosphate. In some embodiments, the benzimidazolium-containing moiety is included in a main chain (i.e., the backbone) of the polymer. In some embodiments, the benzimidazolium-containing moiety is included in a pendant group of the polymer. In some embodiments, the benzimidazolium-containing moiety is part of a crosslink of the polymer. In some embodiments, the polymers having at least one of the repeating units including one or more benzimidazolium-containing moieties of Formulas (IV)-(VIII) can further include a second repeating unit defined by Formula (IV-A): (IV-A) wherein: R 1 is independently selected from the group consisting of H, methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, heteroaryl group and a polymer; R 2 is independently selected from the group consisting of hydrogen, any group, and a polymer; R 3 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a polymer; R 5 is independently selected from the group consisting of hydrogen, any group, and a polymer; wherein at least one of R 1 , R 2 , R 3 , and R 5 , is a polymer; and X is independently selected from the group consisting of alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and no group. The benzimidazolium-containing moieties can be incorporated into a polymer in any manner known to those of skill in the art. Particularly, the moieties can be attached to a polymer chain at any of the R 1 , R 2 , R 3 , or R 5 positions. As used herein, when an R-group is defined as a "polymer", that R-group location connects one of the benzimidazolium- containing moieties to a polymer chain. As discussed further herein, multiple R-groups can be "polymer" and the benzimidazolium-containing moieties can be incorporated into a polymer in a number of ways, including as part of the polymer backbone and/or as a pendant moiety. In one embodiment, the benzimidazolium-containing moieties are incorporated in the polymer backbone, as described in further experimental detail below. As used herein, a monomer that is part of the main chain (or backbone) of a polymer is a repeating unit that is connected on at least two ends to the polymer chain. It will be appreciated that the moiety can be the only moiety in the backbone monomer: -[benzimidazolium-containing moiety] x . Alternatively, the moiety can be one of a plurality of moieties in the backbone of the monomer: [benzimidazolium-containing moiety] x [A] y [B] z , In one embodiment, the benzimidazolium-containing moiety is incorporated as a pendant moiety attached to the backbone of the polymer. As used herein, the term "pendant" refers to a moiety that is attached at only one end to a polymer backbone. It will be appreciated that the benzimidazolium-containing moieties may be directly connected to the polymer backbone or there may be additional moieties (e.g., linker groups) in between the moiety and the polymer backbone. Once again, attachment can come at any of the R 1 , R 2 , R 3 , or R 5 positions. Given the multiple available locations on the moieties for attachment to a polymer main chain, the moieties can be attached to multiple polymer chains (e.g., as part of a crosslink). An exemplary embodiment illustrating crosslinking between two polymer chains, P 1 and P 2 , via the R 3 positions, is illustrated in Formula (IV-B) below. It will be appreciated that the crosslinking capabilities of the moieties are not limited to the illustrated embodiment. As described above, the polymer of the present disclosure includes one or more repeating units, wherein at least one of the repeating units includes one or more benzimidazolium-containing moieties of Formulas (IV)-(VIII), in any combination. In some embodiments, the polymer includes one or more repeat units, wherein at least one of the repeat units includes a benzimidazolium-containing moiety of Formula (IV). In some embodiments, the polymer includes one or more repeat units, wherein at least one of the repeat units includes a benzimidazolium-containing moiety of Formula (V). In some embodiments, the polymer includes one or more repeat units, wherein at least one of the repeat units includes a benzimidazolium-containing moiety of Formula (VI). In some embodiments, the polymer includes one or more repeat units, wherein at least one of the repeat units includes a benzimidazolium-containing moiety of Formula (VII). In some embodiments, the polymer includes one or more repeat units, wherein at least one of the repeat units includes a benzimidazolium-containing moiety of Formula (VIII). In some embodiments, the polymer includes one or more repeat units, wherein the one or more repeat units includes benzimidazolium-containing moieties of Formulas (IV) and (V); Formulas (IV) and (VI); Formulas (IV) and (VII); Formulas (IV) and (VIII); Formulas (IV) and (IV-A); Formulas (V) and (VI); Formulas (V) and (VII); Formulas (V) and (VIII); Formulas (V) and (IV-A); Formulas (VI) and (VII); Formulas (VI) and (VIII); Formulas (VI) and (IV-A); Formulas (VII) and (VIII); Formulas (VII) and (IV-A); or Formulas (VIII) and (IV-A). In some embodiments, the polymer includes one or more repeat units, wherein the one or more repeat units include benzimidazolium-containing moieties of 3 of Formulas (IV), (V), (VI), (VII), (VIII), and (IV-A). In some embodiments, the polymer includes one or more repeat units, wherein the one or more repeat units include benzimidazolium-containing moieties of Formulas (IV), (VIII), and (IV-A). In some embodiments, the one or more repeat units of the polymer include benzimidazolium-containing moieties of Formulas (V), (VI), (VII), (VIII), and (IV- A). In certain embodiments, the one or more repeat units of the polymer include benzimidazolium-containing moieties of Formulas (V), (VIII), and (IV-A). The polymers as described above can have the following embodiments and features. In some embodiments, R 1 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, and heteroaryl. In some embodiments, R 1 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, alkoxy, and perfluoroalkoxy. In some embodiments, R 1 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, R 1 is independently selected from the group consisting of alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, R 1 is alkyl. In some embodiments, R 1 is methyl. In some embodiments, R 2 is independently selected from the group consisting of hydrogen and any group. In some embodiments, R 2 is independently selected from the group consisting of hydrogen and alkyl. In some embodiments, R 2 is independently selected from the group consisting of hydrogen and methyl. In some embodiments, R 3 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl. In some embodiments, R 3 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, heteroalkyl, and aryl. In some embodiments, R 3 is independently selected from the group consisting of methyl, trifluoromethyl, alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, R 3 is independently selected from the group consisting of alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, R 3 is alkyl. In some embodiments, R 3 is methyl. In some embodiments, R 5 is independently selected from the group consisting of hydrogen, alkyl, and a polymer. In some embodiments, R 5 is independently selected from the group consisting of hydrogen and a polymer. In some embodiments, X is independently selected from the group consisting of alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and no group. In some embodiments, X is independently selected from the group consisting of alkylene, arylene, and aralkylene. In some embodiments, X is independently selected from the group consisting of alkylene and arylene. In some embodiments, X is arylene. In some embodiments, X is phenylene (e.g., 1,4-phenylene). The polymer can be a copolymer of Formula (IX)
ĨIX) wherein: R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl. R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that one of R 23a , R 23b , R 24a and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; X 11 , X 21 , and X 31 are each independently selected from the group consisting of absent, C 1-6 alkylene, C 1-6 haloalkylene, arylene, and heteroarylene; and a, b, and c are mole percentages, wherein a is from 0 mole percent to 45 mole percent, b+c is 55 mole percent to 100 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, the copolymer of Formula (IX) is a copolymer of Formula (IXa) (IXa) wherein: R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl. R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that one of R 23a , R 23b , R 24a and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl; X 11 , X 21 , and X 31 are each independently selected from the group consisting of absent, C 1-6 alkylene, C 1-6 haloalkylene, arylene, and heteroarylene; and a, b, and c are mole percentages, wherein a is from 0 mole percent to 45 mole percent, b+c is 55 mole percent to 100 mole percent, b and c are each more than 0 percent, and a+b+c=100%. The copolymers of Formula (IX) (and Formula (IXa)) as described above can have the following embodiments and features. In some embodiments, the copolymers of Formula (IX) (and Formula (IXa)) are random copolymers. In some embodiments, the copolymers of Formula (IX) (and Formula (IXa)) are block copolymers. Block copolymers can be made, for example, as described in Maity S. and Jana T., Appl. Mater. Interfaces, 2014, 6 (9), pp 6851–6864. For example, two separate homopolymers can be synthesized and then reacted together in another polymerization to provide a block copolymer. Post-polymerization functionalization (described in greater detail below) can then provide block copolymers having ionic amine backbones, where N- substitution is randomly distributed along the polymer chain. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl and C 1-6 haloalkyl. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from methyl and ethyl. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each methyl. In some embodiments, R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo. In some embodiments, R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy. In some embodiments, R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H, C 1-6 alkyl, and C 1-6 haloalkyl. In some embodiments, R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H and C 1-6 alkyl. In some embodiments, R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H, methyl, and ethyl. In some embodiments, R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H and methyl. In some embodiments, R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo. In some embodiments, R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy. In some embodiments, R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, C 1-6 alkyl, and C 1-6 haloalkyl. In some embodiments, R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and C 1-6 alkyl. In some embodiments, R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, methyl, and ethyl. In some embodiments, R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and methyl. In some embodiments, R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo. In some embodiments, R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy. In some embodiments, R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, and C 1-6 haloalkyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl and C 1-6 haloalkyl. In some embodiments, R 13a , R 13b , R 14a , and R 14b are each independently selected from absent and C 1-6 alkyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl. In some embodiments, R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, methyl, and ethyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from methyl and ethyl. In some embodiments, R 13a , R 13b , R 14a , and R 14b are each independently selected from absent and methyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and are methyl. In some embodiments, R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo. In some embodiments, R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy. In some embodiments, R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, and C 1-6 haloalkyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl and C 1-6 haloalkyl. In some embodiments, R 23a , R 23b , R 24a , and R 24b are each independently selected from absent and C 1-6 alkyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl. In some embodiments, R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, methyl, and ethyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from methyl and ethyl. In some embodiments, R 23a , R 23b , R 24a , and R 24b are each independently selected from absent and methyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and are methyl. In some embodiments, R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo. In some embodiments, R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, and C 1-6 haloalkoxy. In some embodiments, R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl and C 1-6 haloalkyl. In some embodiments, R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl. In some embodiments, R 33a , R 33b , R 34a , and R 34b are each independently selected from methyl and ethyl. In some embodiments, R 33a , R 33b , R 34a , and R 34b are each independently methyl. In some embodiments, R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and halo. In some embodiments, R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H, C 1-6 alkyl, and C 1-6 haloalkyl. In some embodiments, R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H and C 1-6 alkyl. In some embodiments, R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each H. In some embodiments, X 11 , X 21 , and X 31 are each independently selected from the group consisting of C 1-6 alkylene, C 1-6 haloalkylene, arylene, and heteroarylene. In some embodiments, X 11 , X 21 , and X 31 are each independently selected from the group consisting of arylene and heteroarylene. In some embodiments, X 11 , X 21 , and X 31 are each independently selected from arylene. In some embodiments, X 11 , X 21 , and X 31 are each phenylene (e.g., 1,4-phenylene). In some embodiments, a, b, and c are mole percentages, wherein a is 5 mole percent or more, b+c is 95 mole percent or less, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, a, b, and c are mole percentages, wherein a is from 5 mole percent to 45 mole percent, b+c is 55 mole percent to 95 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, a, b, and c are mole percentages, wherein a is from 2 mole percent to 45 mole percent, b+c is 55 mole percent to 98 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, a, b, and c are mole percentages, wherein a is from 0 mole percent to 45 mole percent, b+c is 55 mole percent to 100 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and C 1-6 alkyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, and C 1-6 haloalkyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl and C 1-6 haloalkyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, and C 1-6 haloalkyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl and C 1-6 haloalkyl; R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl and C 1-6 haloalkyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H and C 1-6 alkyl; X 11 , X 21 , and X 31 are each independently selected from arylene; a, b, and c are mole percentages, wherein a is from 2 mole percent to 45 mole percent, b+c is 55 mole percent to 98 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and C 1-6 alkyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent and C 1-6 alkyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent and C 1-6 alkyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl; R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H and C 1-6 alkyl; X 11 , X 21 , and X 31 are each independently selected from arylene; a, b, and c are mole percentages, wherein a is from 2 mole percent to 45 mole percent, b+c is 55 mole percent to 98 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from methyl and ethyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, methyl, and ethyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, methyl, and ethyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from methyl and ethyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, methyl, and ethyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from methyl and ethyl; R 33a , R 33b , R 34a , and R 34b are each independently selected from methyl and ethyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each H; X 11 , X 21 , and X 31 are each independently selected from arylene; a, b, and c are mole percentages, wherein a is from 0 mole percent to 45 mole percent, b+c is 55 mole percent to 100 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each independently selected from methyl and ethyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, methyl, and ethyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, methyl, and ethyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from methyl and ethyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, methyl, and ethyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and independently selected from methyl and ethyl; R 33a , R 33b , R 34a , and R 34b are each independently selected from methyl and ethyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each H; X 11 , X 21 , and X 31 are each independently selected from arylene; a, b, and c are mole percentages, wherein a is from 2 mole percent to 45 mole percent, b+c is 55 mole percent to 98 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each methyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and methyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent and methyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and are methyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent and methyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and are methyl; R 33a , R 33b , R 34a , and R 34b are each independently methyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each H; X 11 , X 21 , and X 31 are each independently selected from arylene; a, b, and c are mole percentages, wherein a is from 2 mole percent to 45 mole percent, b+c is 55 mole percent to 98 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each methyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and methyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent and methyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and are methyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent and methyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and are methyl; R 33a , R 33b , R 34a , and R 34b are each independently methyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each H; X 11 , X 21 , and X 31 are each independently selected from arylene; a, b, and c are mole percentages, wherein a is from 0 mole percent to 45 mole percent, b+c is 55 mole percent to 100 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each methyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and methyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent and methyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and are methyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent and methyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and are methyl; R 33a , R 33b , R 34a , and R 34b are each independently methyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each H; X 11 , X 21 , and X 31 are each phenylene (e.g., 1,4-phenylene); a, b, and c are mole percentages, wherein a is from 2 mole percent to 45 mole percent, b+c is 55 mole percent to 98 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, R 11a , R 11b , R 11c , R 11d, R 21a , R 21b , R 21c , R 21d, R 31a , R 31b , R 31c , and R 31d are each methyl; R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H and methyl; R 13a , R 13b , R 14a , and R 14b are each independently selected from absent and methyl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and are methyl; R 23a , R 23b , R 24a , and R 24b are each independently selected from absent and methyl, provided that one of R 23a , R 23b , R 24a , and R 24b is absent, and the remaining three are present and are methyl; R 33a , R 33b , R 34a , and R 34b are each independently methyl; R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each H; X 11 , X 21 , and X 31 are each phenylene (e.g., 1,4-phenylene); a, b, and c are mole percentages, wherein a is from 0 mole percent to 45 mole percent, b+c is 55 mole percent to 100 mole percent, b and c are each more than 0 percent, and a+b+c=100%. In some embodiments, the degree of N-substitution (e.g., N-alkylation) in the polymers of the present disclosure is from greater than 50 mole percent (e.g., from 60 mole percent, from 70 mole percent, from 80 mole percent, or from 90 mole percent) to about 95 mole percent (to about 92 mole percent, to about 90 mole percent, to about 80 mole percent, to about 70 mole percent, or to about 60 mole percent). In certain embodiment, the described cationic benzimidazolium-containing moieties or the polymer of Formula (IX) or (IXa) form a salt with an anion. Any anion sufficient to balance the charge of the moiety-containing polymer can be used. Representative anions include iodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, triiodide, phosphate, triflate, tosylate, bisulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate. The polymers containing the moieties and the polymers of Formula (IX) or (IXa) can be of any size known to those of skill in the art. The polymers of the present disclosure are described, for example, in PCT publication No. WO2015/157848, incorporated herein by reference in its entirety. In some embodiments, the present disclosure features a polymer including (or consisting essentially of, or consisting of) a repeating unit of Formula (X): (X) wherein: R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; provided that at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl, when one of R 1XY and R 2XY is absent, the imidazolyl group to which the absent R 1XY or R 2XY is connected (i.e., the imidazolyl group having one of R 1XY or R 2XY , but not the other) is neutral; and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and when one of R 4XY and R 5XY is absent, the imidazolyl group to which the absent R 4XY or R 5XY is connected (i.e., the imidazolyl group having one of R 4XY or R 5XY , but not the other) is neutral; R 3XY and R 6XY are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R 15XY is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 16XY is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 7XY , R 10XY , R 11XY , and R 14XY are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R 8XY , R 9XY , R 12XY , and R 13XY are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, the polymer including (or consisting essentially of, or consisting of) a repeating unit of Formula (x) includes a repeating unit of Formula (X-A):
(X-A) wherein: R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; provided that at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl, when one of R 1XY and R 2XY is absent, the imidazolyl group to which the absent R 1XY or R 2XY is connected (i.e., the imidazolyl group having one of R 1XY or R 2XY , but not the other) is neutral; at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and when one of R 4XY and R 5XY is absent, the imidazolyl group to which the absent R 4XY or R 5XY is connected (i.e., the imidazolyl group having one of R 4XY or R 5XY , but not the other) is neutral; R 3XY and R 6XY are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R 15XY is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 16XY is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 7XY , R 10XY , R 11XY , and R 14XY are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R 8XY , R 9XY , R 12XY , and R 13XY are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, the polymer including (or consisting essentially of, or consisting of) a repeating unit of Formula (X) includes, or the polymer including repeating unit(s) of Formula (X-A) further includes, a repeating unit of Formula (X-B): wherein: R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; provided that at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl, when one of R 1XY and R 2XY is absent, the imidazolyl group to which the absent R 1XY or R 2XY is connected (i.e., the imidazolyl group having one of R 1XY or R 2XY , but not the other) is neutral; and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and when one of R 4XY and R 5XY is absent, the imidazolyl group to which the absent R 4XY or R 5XY is connected (i.e., the imidazolyl group having one of R 4XY or R 5XY , but not the other) is neutral; R 3XY and R 6XY are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R 15XY is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 16XY is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 7XY , R 10XY , R 11XY , and R 14XY are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R 8XY , R 9XY , R 12XY , and R 13XY are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, the polymer including (or consisting essentially of, or consisting of) a repeating unit of Formula (X) includes, or the polymer including repeating unit(s) of Formula (X-A) and/or Formula (X-B) further includes a repeating unit of Formula (X-C): (X-C) wherein: R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; provided that at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl, when one of R 1XY and R 2XY is absent, the imidazolyl group to which the absent R 1XY and R 2XY is connected (i.e., the imidazolyl group having one of R 1XY or R 2XY , but not the other) is neutral; and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and when one of R 4XY and R 5XY is absent, the imidazolyl group to which the absent R 4XY or R 5XY is connected (i.e., the imidazolyl group having one of R 4XY or R 5XY , but not the other) is neutral; R 3XY and R 6XY are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R 15XY is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 16XY is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 7XY , R 10XY , R 11XY , and R 14XY are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R 8XY , R 9XY , R 12XY , and R 13XY are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, the polymer including (or consisting essentially of, or consisting of) a repeating unit of Formula (X) includes, or the polymer including repeating unit(s) of Formula (X-A), Formula (X-B), and/or Formula (X-C) further includes a repeating unit of Formula (X-D): (X-D) wherein: R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; provided that at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl, when one of R 1XY and R 2XY is absent, the imidazolyl group to which the absent R 1XY or R 2XY is connected (i.e., the imidazolyl group having one of R 1XY or R 2XY , but not the other) is neutral; and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and when one of R 4XY and R 5XY is absent, the imidazolyl group to which the absent R 4XY or R 5XY is connected (i.e., the imidazolyl group having one of R 4XY or R 5XY , but not the other) is neutral; R 3XY and R 6XY are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R 15XY is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 16XY is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo; R 7XY , R 10XY , R 11XY , and R 14XY are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R 8XY , R 9XY , R 12XY , and R 13XY are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl. The polymer of Formula (X) can have a mixture of repeating units of Formulas (X- A), (X-B), (X-C), and/or (X-D). For example, the polymer can include repeating units of Formulas (X-A), (X-B), (X-C), and (X-D); Formulas (X-A), (X-B), and (X-C); Formulas (X- A), (X-B), and (X-D); Formulas (X-A), (X-C), and (X-D); Formulas (X-B), (X-C), (X-D); Formulas (X-A) and (X-B); Formulas (X-A) and (X-C); Formulas (X-A) and (X-D); Formulas (X-B) and (X-C); Formulas (X-B) and (X-D); Formulas (X-C) and (X-D); Formula (X-A); Formula (X-B); Formula (X-C); or Formula (X-D). In any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (I); or including repeating unit(s) of Formula (X-A), (X-B), (X-C), and/or (X-D), R 1XY , R 2XY , R 4XY , and R 5XY can each be independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, and aryl; provided that: at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, and aryl; and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, and aryl. For example, R 1XY , R 2XY , R 4XY , and R 5XY can each independently be selected from absent, alkyl, perfluoroalkyl, and heteroalkyl; provided that: at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, and heteroalkyl; and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, methyl, and trifluoromethyl; provided that: at least one of R 1XY and R 2XY is selected from methyl and trifluoromethyl; and at least one of R 4XY and R 5XY is selected from methyl and trifluoromethyl. In any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (X); or including repeating unit(s) of Formula (X-A), (X-B), (X-C), and/or (X-D), R 3XY and R 6XY can each independently aryl. For example, R 3XY and R 6XY can each independently phenyl. In some embodiments, R 3XY and R 6XY are each independently ethyl or methyl. In some embodiments, R 3XY and R 6XY are each independently methyl. In any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (X); or including repeating unit(s) of Formula (X-A), (X-B), (X-C), and/or (X-D), R 15XY and R 16XY can each independently be selected from arylene and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo. For example, R 15XY and R 16XY can each independently be arylene, optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo. For example, R 15XY and R 16XY can each be phenylene, optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In some embodiments, R 15XY and R 16XY are each phenylene. In any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (X); or including repeating unit(s) of Formula (X-A), (X-B), (X-C), and/or (X-D), R 7XY , R 10XY , R 11XXY , and R 14XY can each independently be alkyl. For example, R 7XY , R 10XY , R 11XY , and R 14XY can each independently be methyl or ethyl. For example, R 7XY , R 10XY , R 11XY , and R 14XY can each independently be methyl. In any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (X); or including repeating unit(s) of Formula (X-A), (X-B), (X-C), and/or (X-D), the polymer can include a counterion selected from the group consisting of iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, tosylate, bisulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate. In any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (X); or including repeating unit(s) of Formula (X-A), (X-B), (X- C), and/or (X-D), the polymer can include one or more anions X- selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, cyanide, acetate, nitrate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more anions X- selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more anions X- selected from iodide, bromide, chloride, fluoride, hydroxide, carbonate, bicarbonate, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more anions X- selected from iodide, bromide, chloride, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more anions X- selected from iodide, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more hydroxide, where the one or more hydroxide counterbalance one or more positive charges in the polymer. The present disclosure also provides a polymer including (or consisting essentially of, or consisting of) a repeating unit of Formula (XI): (XI) wherein: R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; provided that at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl, when one of R 1XY and R 2XY is absent, the imidazolyl group to which the absent R 1XY or R 2XY is connected (i.e., the imidazolyl group having one of R 1XY or R 2XY , but not the other) is neutral; and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and when one of R 4XY and R 5XY is absent, the imidazolyl group to which the absent R 4XY or R 5XY is connected (i.e., the imidazolyl group having one of R 4XY or R 5XY , but not the other) is neutral; R 3XY and R 6XY are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R 7XY , R 10XY , R 11XY , and R 14XY are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R 8XY and R 12XY are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, for the above-described polymer including (or consisting essentially of, or consisting of) a repeating unit of Formula (XI), R 1XY , R 2XY , R 4XY , and R 5XY are each independently selected from absent, alkyl, perfluoroalkyl, and heteroalkyl; provided that: at least one of R 1XY and R 2XY is selected from alkyl, perfluoroalkyl, and heteroalkyl, and at least one of R 4XY and R 5XY is selected from alkyl, perfluoroalkyl, and heteroalkyl. For example, R 1XY , R 2XY , R 4XY , and R 5XY can each independently selected from absent, methyl, and trifluoromethyl; provided that: at least one of R 1XY and R 2XY is selected from methyl and trifluoromethyl, and at least one of R 4XY and R 5XY is selected from methyl and trifluoromethyl. In some embodiments, for any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (XI), R 3XY and R 6XY are each independently aryl. For example, R 3XY and R 6XY can each be independently phenyl. In some embodiments, R 3XY and R 6XY are each independently methyl or ethyl. In some embodiments, R 3XY and R 6XY are each independently methyl. In some embodiments, for any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (XI), R 7XY , R 8XY , R 10XY , R 11XY , R 12XY , and R 14XY are each independently alkyl. For example, R 7XY , R 8XY , R 10XY , R 11XY , R 12XY , and R 14XY are each independently methyl or ethyl. For example, R 7XY , R 8XY , R 10XY , R 11XY , R 12XY , and R 14XY are each independently methyl. In some embodiments, for any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (XI), the polymer includes one or more counterions selected from the group consisting of iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, tosylate, bisulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate. In some embodiments, for any of the above-mentioned embodiments of polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (XI), the polymer includes one or more anions X- selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, cyanide, acetate, nitrate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. For example, the one or more anions X- can be selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, one or more anions X- are selected from iodide, bromide, chloride, fluoride, hydroxide, carbonate, bicarbonate, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more anions X- selected from iodide, bromide, chloride, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more anions X- selected from iodide, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes one or more hydroxide, where the one or more hydroxide counterbalance one or more positive charges in the polymer. The present disclosure further provides a polymer including a repeating unit of Formula (XII-A): N N N N (XII-A). In some embodiments, the polymer including a repeating unit of Formula (XII-A) further includes a repeating unit of Formula (XII-B):
(XII-B). In some embodiments, the polymer including a repeating unit of Formula (XII-A), or including repeating units of Formulas (XII-A) and (XII-B), further includes a repeating unit of Formula (XII-C): (XII-C) wherein one of R 1d and R 4d is absent, and the remaining R 1d or R 4d is methyl; and the imidazolyl group to which the absent R 1d or R 4d is connected (i.e., the imidazolyl group where one of its R 1d or R 4d is absent) is neutral. In some embodiments, for any of the above-described polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (XII-A), (XII-B), and/or (XII-C), the polymer includes one or more counterions selected from the group consisting of iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, tosylate, bisulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate. In some embodiments, for any of the above-described polymers including (or consisting essentially of, or consisting of) a repeating unit of Formula (XII-A), (XII-B), and/or (XII-C), the polymer includes one or more anions X- selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, cyanide, acetate, nitrate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, where the one or more anions X- counterbalances one or more positive charges in the polymer. In some embodiments, one or more anions X- are selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. For example, one or more anions X- can be selected from iodide, bromide, chloride, fluoride, hydroxide, carbonate, bicarbonate, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, one or more anions X- is selected from iodide, bromide, chloride, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, one or more anions X- is selected from iodide, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. For example, for any of the above-described polymers including a repeating unit of Formula (XII-A), (XII-B), and/or (XII-C), the polymer can include one or more hydroxide anions, where the one or more hydroxide anions counterbalance one or more positive charges in the polymer. The present disclosure further provides a random polymer, including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII -B), and (XIII -C): (XIII -A) (XIII -B)
(XIII -C) wherein one of R 1a and R 2a is absent and the remaining R 1a or R 2a is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; one of R 4a and R 5a is absent and the remaining R 4a or R 5a is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; one of R 1b , R 2b , R 4b , and R 5b is absent and the imidazolyl group to which the absent R 1b , R 2b , R 4b , or R 5b is connected (i.e., the imidazolyl group where one of its R 1b , R 2b , R 4b , or R 5b is absent) is neutral, and the remaining three of R 1b , R 2b , R 4b , and R 5b are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; R 1c , R 2c , R 4c , and R 5c are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; R 3a , R 6a , R 3b , R 6b , R 3c , and R 6c are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R 7a , R 10a , R 11a , R 14a , R 7b , R 10b , R 11b , R 14b , R 7c , R 10c , R 11c , and R 14c are each independently selected from H, alkyl, perfluoroalkyl, and heteroalkyl; and R 8a , R 12a , R 8b , R 12b , R 8c , and R 12c are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl; wherein the polymer includes m mole percentage repeating units of Formula (XIII- A), n mole percentage repeating units of Formula (XIII-B), and p mole percentage repeating units of Formula (XIII-C), and m is from 0 mole percent to 60 mole percent, n+p is 40 mole percent to 100 mole percent, and m+n+p=100%. In some embodiments, for the random polymer including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C) described above, one of R 1a and R 2a is absent and the remaining R 1a or R 2a is selected from methyl and trifluoromethyl; and one of R 4a and R 5a is absent and the remaining R 4a or R 5a is selected from methyl and trifluoromethyl. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), one of R 1b , R 2b , R 4b , and R 5b is absent and the imidazolyl group to which the absent R 1b , R 2b , R 4b , or R 5b is connected (i.e., the imidazolyl group where one of its R 1b , R 2b , R 4b , or R 5b is absent) is neutral, and the remaining three of R 1b , R 2b , R 4b , and R 5b are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl. In some embodiments, one of R 1b , R 2b , R 4b , and R 5b is absent and the imidazolyl group to which the absent R 1b , R 2b , R 4b , or R 5b is connected (i.e., the imidazolyl group where one of its R 1b , R 2b , R 4b , or R 5b is absent) is neutral, and the remaining three of R 1b , R 2b , R 4b , and R 5b are each independently selected from methyl, and trifluoromethyl. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), R 1c , R 2c , R 4c , and R 5c are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl. For example, R 1c , R 2c , R 4c , and R 5c can each be independently selected from methyl and trifluoromethyl. In some embodiments, R 1c , R 2c , R 4c , and R 5c are each independently methyl or ethyl. In some embodiments, R 1c , R 2c , R 4c , and R 5c are each methyl. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), R 3a , R 6a , R 3b , R 6b , R 3c , and R 6c are each independently aryl. For example, R 3a , R 6a , R 3b , R 6b , R 3c , and R 6c can each independently be phenyl. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), R 7a , R 10a , R 11a , R 14a , R 7b , R 10b , R 11b , R 14b , R 7c , R 10c , R 11c , and R 14c are each independently alkyl. For example, R 7a , R 10a , R 11a , R 14a , R 7b , R 10b , R 11b , R 14b , R 7c , R 10c , R 11c , and R 14c can each independently be methyl or ethyl. For example, R 7a , R 10a , R 11a , R 14a , R 7b , R 10b , R 11b , R 14b , R 7c , R 10c , R 11c , and R 14c can each independently be methyl. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), R 8a , R 12a , R 8b , R 12b , R 8c , and R 12c are each independently alkyl. For example, R 8a , R 12a , R 8b , R 12b , R 8c , and R 12c can each be independently methyl or ethyl. For example, R 8a , R 12a , R 8b , R 12b , R 8c , and R 12c can each be independently methyl. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), n and p are each more than 0 percent. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), the polymer includes one or more counterions selected from the group consisting of iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, tosylate, bisulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate. In some embodiments, for any of the above-described random polymers including (or consisting essentially of, or consisting of) repeating units of Formula (XIII-A), (XIII-B), and (XIII-C), the polymer includes one or more anions X- selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, cyanide, acetate, nitrate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. For example, the one or more anions X- can be selected from iodide, bromide, chloride, fluoride, hydroxide, carbonate, bicarbonate, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. For example, one or more anions X- can be selected from iodide, bromide, chloride, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. As another example, one or more anions X- can be selected from iodide, hydroxide, and any combination thereof, where the one or more anions X- counterbalance one or more positive charges in the polymer. In some embodiments, for any of the above-mentioned random copolymers including repeating units of Formula (IV-A), (IV-B), and (IV-C), the polymer includes one or more hydroxide anions, where the one or more hydroxide anions counterbalance one or more positive charges in the polymer. In some embodiments, the polymer includes a repeating unit including a moiety of Formula (XIV): ^ N N N N ^ (XIV). In some embodiments, the polymer includes a repeating unit including a moiety of Formula (XV): (XV). In some embodiments, the polymer includes a repeating unit including a moiety of Formula (XVI): (XVI). Antimicrobial polymer coatings are described in the Examples below. EXAMPLES EXAMPLE 1. ANTIMICROBIAL ACTIVITY ASSESSMENT The overall antimicrobial test procedure is shown in FIGURE 5. The present Example was conducted based on two different lots of polymers with different degrees of methylation (dm). The structures of the polymers are shown in Schemes 1 and 2 below. These are hereafter noted as high (91%) and low (57%) dm. Polymers in the iodide form were dissolved at 2 wt% in 50:50 (v/v) methanol:acetone by heating at 40 ºC with stirring and then precipitated respectively in a 1 M aqueous solution of the desired anion: i.e., sodium chloride, sodium nitrate and ammonium acetate. The precipitated, anion-exchanged polymers were filtered, washed with water and dried (80 ºC, 12 h). Solutions for casting were done by dissolving with stirring at 40 ºC. The high dm polymer was dissolved in pure methanol at 0.7 wt% while the low dm polymer was dissolved in 88:12 (v/v) methanol:acetone. Untreated microscope slides (AmScope BS-50P, clear glass, ground edge, 1"x3") were cleaned prior to use by ultrasonication in methanol at room temperature for 30 min. A 1 mL aliquot of a given polymer solution was drop-cast onto the glass slide and dried at room temperature in the fume hood overnight. Referring to FIGURES 2 (micrograph), 3A (transmission), and 3B (TGA), the polymer-coated samples (high dm) were smooth, clear, and transparent. The polymer film properties are also shown in FIGURE 4. dm = 57% Solvent: Methanol/Acetone (88%:12%) Concentration: 0.5 weight %
Anions: Chloride, Nitrate and Acetate Solvent: Methanol Concentration: 0.7 weight % Referring to FIGURE 6 and Table 1 below, Samples 1, 2, 3, 4, 5, indicate polymer anions nitrate, acetate, chloride (cast thinly), chloride, chloride (low degree of methylation) respectively for the polymers. Two controls were also included; sample C comprised of uncoated glass and SBSC was the untreated internal control provided by Situ-Bioscience. Samples were provided in triplicate. Anti-Bacterial testing ISO-22196 test method is designed to measure the antimicrobial properties of solid or hard surface treated test samples incubated with selected microorganisms. The basis of the test method is the incubation of the bacterial inoculum in contact with the test sample for a duration of 24 hours without drying of the inoculum. Following this exposure, the inoculated bacteria are recovered and the concentration of the organisms is determined. The antimicrobial performance is determined by comparison of the recovered organisms from the untreated material and treated material after the 24-hour incubation. The antimicrobial performance is reported as both the Log10 and % Reduction relative to the untreated control sample. Three timepoints were tested: 30 min, 6 hrs and 24 hrs. Results Samples were all tested in triplicate to JIS Z 2801 and inoculated with S. aureus (6538) and E. coli (8739). All samples were plated twice and tested for activity at 0.5, 6 and 24 hours. Referring to FIGURES 1B, 1D, and 7, Sample 1 showed a reduction in activity of 75.07% (0.6 Log10 reduction), 98.42% (1.8 Log10 reduction) and 99.80% (2.7 Log10 reduction) to S. aureus and 56.59% (0.4 Log10 reduction), 99.95% (3.3 Log10 reduction) and 99.68% (2.5 Log10 reduction) to E. coli. Sample 2 showed a reduction in activity of 99.00% (4.3 Log10 reduction), 99.99% (4.3 Log10 reduction) and 99.99% (2.74.6 Log10 reduction) to S. aureus and 82.46% (0.8 Log10 reduction), >99.99% (5 Log10 reduction) and >99.99% (5.5 Log10 reduction) to E. coli. Sample 3 showed a reduction in activity of 77.26% (0.6 Log10 reduction), 99.92% (3.1 Log10 reduction) and >99.99% (4.6 Log10 reduction) to S. aureus and 40.50% (0.2 Log10 reduction), >99.99% (5.3 Log10 reduction) and >99.99% (5 Log10 reduction) to E. coli. Sample 4 showed a reduction in activity of 98.72% (1.9 Log10 reduction), 99.99% (4.5 Log10 reduction) and >99.99% (4.6 Log10 reduction) to S. aureus and >99.99% (4.3 Log10 reduction), >99.99% (5.3 Log10 reduction) and >99.99% (5.5 Log10 reduction) for E. coli. Sample 5 showed a reduction in activity of 50.53% (0.3 Log10 reduction), 99.83% (2.8 Log10 reduction) and >99.99% (4.6 Log10 reduction) to S. aureus and 23.42% (0.1 Log10 reduction), 97.03% (1.5 Log10 reduction) and 98.93% (2 Log10 reduction) to E. coli. Sample C showed a reduction in activity of 25.28% (0.1 Log10 reduction), 46.68% (0.3Log10 reduction) and 69.24% (0.5 Log10 reduction) to S. aureus and 9.58% (0 Log10 reduction), 0% (0 Log10 reduction) and 0% (0 Log10 reduction) for E. coli. The internal control sample SBSC Untreated Control showed bacterial concentration of 7.1E5 CFU/mL, 1.0E6 CFU/mL, at 0 and 0.5 hours, respectively, and 7.7E5 CFU/mL, 1.4E6 CFU/mL, and 2.0E6 CFU/mL at 0, 0.5 and 24 hours, respectively, for S. aureus. The SBSC Untreated Control showed bacterial concentration of 9.3E5 CFU/mL, 1.0E6 CFU/mL for 0 and 0.5 hours, respectively, and 7.0E5 CFU/mL, 1.1E7 CFU/mL, and 1.4E7 CFU/mL at 0, 6 and 24 hours, respectively, for E. coli. Anti-Viral Testing ISO 21702 provides a test method for the quantitative evaluation of virucidal activity on plastics and other non-porous surfaces. Products tested are intended to be treated antiviral products, that are tested against the specified virus. The basis of the test method is the incubation of the viral inoculum in contact with the test sample for a duration of 24 hours without drying of the inoculum. Following this exposure, the inoculated virus is recovered, and the concentration of the infective virus is determined. The antiviral performance is determined by a comparison of the recovered virus from the untreated material and treated material after the 24-hour incubation. The antimicrobial performance is reported as both the Log10 and % Reduction relative to the untreated control sample. Testing was conducted with soiling by incorporation of 5% serum to the viral inoculation solution. Results and Discussion Result: Log Reduction rounded to nearest tenths (ex 3.1) Samples were all tested to ISO 21702 and inoculated with Feline Calicivirus (F-9) and Human Coronavirus (229E). All samples were tested for activity at 0.5 and 24 hours. Cytotoxicity optimization was performed for sample 4 only Referring to FIGURES 1A, 1C, and 7, Sample 4 showed a reduction in activity of 0% (0 Log10 reduction), and 90% (1 Log10 reduction) to Feline Calicivirus (F-9) and >=99.99% (4.2 Log10 reduction), and 99.99% (4 Log10 reduction) to Human Coronavirus (229E) at 0.5 and 24 hours respectively. Sample 5 showed a reduction in activity of 78.5% (0.7 Log10 reduction), and 95.4% (1.3 Log10 reduction) to Feline Calicivirus (F-9) and 99.7% (2.5 Log10 reduction), and 99% (2 Log10 reduction) to Human Coronavirus (229E) at 0.5 and 24 hours respectively. Sample C showed a reduction in activity of 0% (0 Log10 reduction), and 85.3% (0.8 Log10 reduction) to Feline Calicivirus (F-9) and 93.2% (1.2 Log10 reduction), and 95.4% (1.3 Log10 reduction) to Human Coronavirus (229E) at 0.5 and 24 hours respectively. The internal control sample SBSC Untreated Control showed Virus concentration of 2.9E6 log10 TCID50/sq cm, 2.9E6 log10 TCID50/sq cm, and 6.1E6 log10 TCID50/sq cm at 0, 0.5 and 24 hours, respectively, for Feline Calicivirus (F-9) and 6.1E5 log 10 TCID50/sq cm, 9.0E5 TCID50/sq cm and 6.2E5 Log10 TCID50/sq cm at 0, 0.5 and 24 hours, respectively, for Human Coronavirus (229E). ISO 21702 Inherent Cytotoxicity Optimization for sample 4 was negative. Kinetic analysis and half-life data was also obtained. The results are shown in FIGURE 8. DETAILED ANTIBACTERIAL AND ANTIVIRAL TESTS AND RESULTS. ISO 22196: Antibacterial test A method of evaluating the antibacterial activity of antibacterial-treated plastic products including intermediate products). It is not intended to be used to evaluate the effects and propagation of bacteria on plastics without antibacterial treatments. Antimicrobial activity is determined in the following manner: R = (Ut -U0) - (At-U0) = Ut - At Where R is the antibacterial activity; U0 is the average of the common logarithm of the number of viable bacteria, in cells/cm2, recovered from the untreated test specimens immediately after inoculation; Ut is the average of the common logarithm of the number of viable bacteria, in cells/cm2, recovered from the untreated test specimens after 24 h At is the average of the common logarithm of the number of viable bacteria, in cells/cm2, recovered from the treated test specimens after 24 h. For purposes of common reference, the % reduction is also reported in the notes section for each sample result. Legend CFU = colony forming unit (typically cited per unit volume or surface area). CFU is determined by bacterial plating of the test samples according to the specified method, followed by counting of the resultant colonies. Untreated Control (UTC) - untreated control sample material used to demonstrate normal test performance, showing robust microorganism growth. Interval - represents the point or time point from which the result value was determine; T0 indicates that the result is from the soonest possible time from inoculation to recovery of the inoculated sample (typically < 5 min). Result - the result is the measure of change or abundance. Result units indicate the actual measurements, frequently relative to a control value depending on the method or test requirements. Notation of changes to the published test method: Several references are made to 'Plate count agar' for the test method plating following neutralization and recovery of the bacterial from the test samples. As standard practice, counts are performed on appropriate plate media such as Nutrient agar, tryptic soy agar, or as required by the specific organism tested. The published standard refers to incubation conditions of 35 ± 1 °C. Standard microbiological practice with other international methods is for incubations to occur at 37 ± 1 °C. The test conditions performed will be conducted at 37 ± 1 °C unless specified for other temperature conditions. Expanded Uncertainty for the test method of k=2 is for a 95% confidence of Log10 (0.136). Uncertainty Values in CFU are obtained by converting CFU counts (C1) to Log10 values (Log10 C1); multiply this result by the Expanded Uncertainty (Log10 C1*EU), then add and subtract from the Log10 value (Log C1 ± (Log10 C1*EU)); convert back by taking the anti-log (lx10^ (Log C1 ± Log10 C1*EU)) which provides the upper and lower limits of 95% confidence in CFU. Stated Method Standard For ISO 22196, an interlaboratory test demonstrated a results with Standard deviation of Log10(0.45) or ~ 1/2 log. This equates to a - mean value ± 50 % reduction. Conditions for a valid test When the three conditions are satisfied, the test is deemed valid. If all conditions are not met, the test is not considered valid and the specimens shall be retested. The logarithmic value of the number of viable bacteria recovered immediately after inoculation from the untreated test specimens shall satisfy the following requirement: (Lmax-Lmin)/(Lmean)<= 0.2 Where: Lmax is the common logarithm (i.e., base 10 logarithm) of the maximum number of viable bacteria found on a specimen Lmin is the common logarithm of the minimum number of viable bacteria found on a specimen; Lmean is the common logarithm of the mean number of viable bacteria found on the specimens. Abstract The ISO-22196 test method is designed to measure the antimicrobial properties of solid or hard surface treated test samples incubated with selected microorganisms. The basis of the test method is the incubation of the bacterial inoculum in contact with the test sample for a duration of 24 hours without drying of the inoculum. Following this exposure, the inoculated bacteria are recovered and the concentration of the organisms is determined. The antimicrobial performance is determined by comparison of the recovered organisms from the untreated material and treated material after the 24 hour incubation. The antimicrobial performance is reported as both the Log10 and % Reduction relative to the untreated control sample. Three timepoints were tested: 30 min, 6 hrs and 24 hrs. Results and Discussion Results are provided in the Result Data Tables Test Sample Result Timepoint of the result: (typically T0 or other time in test) Timepoint Units: typically "hr" hours Result: Log Reduction rounded to nearest tenths (ex 3.1) UNITS: Log Reduction Limit of detection (LOD): LOD is entered in the result note for each sample where no bacteria were recovered. JIS Z 2801 - Antibacterial products - Test for antimicrobial activity and efficacy JIS Z 2801 specifies a method of evaluating the antibacterial activity of plastic products. It is a method commonly used for evaluating the antimicrobial properties of many material types that can range from coated surfaces or those of monolithic composition. The basis of the test method is the incubation of the microorganism inoculum in intimate contact with the test substance on a flat horizontal surface for 24 hours. Following this exposure, a sample of the inoculum is recovered and the concentration of the organisms is determined. The antimicrobial performance is determined by comparison of the recovered organisms from the untreated inoculum-only test substances after the selected time points and treated test substance after the selected time points. It is not intended to be used to evaluate the effects and propagation of bacteria on plastics without antibacterial treatments. Testing Inoculum Preparation Following an overnight incubation of the test bacteria, a transfer to the inoculation solution is performed. Using a sterile inoculating loop, transfer one loop of the test bacteria into a small amount of 1/500 NB prepared. A dilution of this suspension with 1/500 NB is created as appropriate to establish an estimated bacterial concentration, to obtain a bacterial concentration that is between SES CFU / mL and 2E6 CFU / mL, with a target concentration of 1E6 CFU /mL. Inoculation of test specimens • The surface to be tested is the exposed outer surface of the product. • Pipette 0.2 mL of the test inoculum prepared onto the test surface. • Cover the test inoculum with a piece of film that measures 40 mm x 40 mm and gently press down. on the film so that the test inoculum spreads to the edges. • Make sure that the test inoculum does not leak beyond the edges of the film. • After the specimen has been inoculated and the cover film applied, replace the lid of the Petri dish. Incubation of the inoculated test specimens The standard procedure for incubation of the inoculated specimens is to incubate the Petri dishes containing the inoculated test specimens (including half of the untreated test specimens) at a temperature of (37 ± 1) °C and a relative humidity of not less than 90 % for (24 ± 1) h, unless otherwise noted. Recovery of bacteria from test specimens. Immediately after inoculation, process half of the untreated test specimens by adding 5 mL of a suitable neutralizer to the Petri dish containing the test specimen. Test specimens after incubation After the incubation, process the remaining test specimens. Proceed immediately to count the viable bacteria recovered from the test specimen. Reagents Nutrient Broth 2 (NB2) D/E Neutralizing Broth (D/E) Phosphate Buffered Saline (PBS) Tryptic Soy Agar Laboratory RO water, deionized Equipment List Thermo Orbital Shaker Incubator Scales (Mettler H80, Mettler PM-11K, Mettler MS104S/03) Autoplater Spiral Biotech 4000 National Water Incubator Shimadzu Spectrophotometer MarketForge Autoclave Hach pH Meter/ 02 measure / conductivity meter Dwyer Hygrometer Gilson Pipetters Test Organisms Staphylococcus aureus Escherichia coli Sample Preparations Each test substance was prepared according to the analytic method requirements. Each test sample is prepared in triplicate unless otherwise specified. As available, flat samples are procured, and cut into a piece SOxSO mm. Sample variability are accommodated at needed for the standard test, notes regarding differences in the sample characteristic are recorded in the report summary.
ISO 21702: antiviral test The ISO 21702 provides a test method for the quantitative evaluation of virucidal activity on plastics and other non-porous surfaces. Products tested are intended to be treated antiviral products, that are tested against the specified virus. The basis of the test method is the incubation of the viral inoculum in contact with the test sample for a duration of 24 hours without drying of the inoculum. Following this exposure, the inoculated virus is recovered, and the concentration of the infective virus is determined. The antiviral performance is determined by a comparison of the recovered virus from the untreated material and treated material after the 24-hour incubation. The antimicrobial performance is reported as both the Log10 and % Reduction relative to the untreated control sample. Results and Discussion Results are provided in the Result Data Tables Testing was conducted with soiling by incorporation of 5% serum to the viral inoculation solution. ISO 21702 specifies a method of evaluating virucidal activity of non-porous surfaces. Each product was tested using clean test condition (no additional soil). Unless otherwise specified, secondary effects of antibacterial treatments, the measured antimicrobial performance, or the durability of a measured activity are not covered by the standard. The standard is not intended to be used or referenced as a method to document or claim antimicrobial performance unless indicated by the test report. The determinations of product performance within a given environment can vary dramatically, and must be specifically documented and then determined within the context of a specific project plan. Methods Project- Specialized Organism Culturing- Virus Cell culturing for non-standard virus used in a given test method. For each virus, the necessary media, and culture conditions are employed according to standard requirements established by the lab. ISO 21702 - Measurement of antiviral activity on plastics and other non-porous surfaces The ISO 21702 method is used to evaluate the virucidal efficacy of a non-porous product. Testing can incorporate different exposure times, soiling, and virus types and other variables according to the test standard or specific needs of a product. The most common test conditions employ the standard method protocol requiring a 24-hour exposure to the test material depending on the intended use of the product. Test virus are prepared in advance of the testing followed by a determination of viral titer. The inocula created is then utilized as the inocula for the exposure of the test material to the virus. ISO 21702 Inherent Cytotoxicity Optimization Antiviral testing requires the use of host cells for propagation and enumeration of the viral concentration. The host cells must be viable and biologically intact to allow viral infection. Successful infection by the virus results in the replication and ultimate lysis and loss of the host cell. This process provides the means by which viruses are measured. Cytotoxicity of the host cell as a result of any chemical carry-over from the test sample can affect the biological viability of the host cell and interfere with needed processes subsequent to the exposure of the cells to the virus. This interference is generally considered as the inherent cytotoxicity of the test sample. The test is conducted by incubating the test sample for 30 seconds with the neutralizing recovery solution, followed by exposure of the host cells to eight concentrations of the recovered solution. Inherent cytotoxicity is identified by the loss of the cell culture viability. Testing Inoculum Preparation A known viral titer suspension is prepared to a concentration of at least 1E6 TCID5O / mL. Passaged of the virus are not used beyond ten passes from the original seed culture. Experimental Conditions Following inoculation, the samples are incubated at 25 C ± 1 °C (unless otherwise specified). The incubation is conducted to prevent the inoculum from drying while in contact with the test surface. Following the incubation period, the virus is recovered in neutralizing media and then diluted for culturing. Recovery of virus from test specimens. Two time points are created for each test item, a washout of the inoculated sample is collected immediately after inoculation by addition of the selected neutralizer solution by placing the sample into a vial and adding 10 mL of the neutralizer, followed by vortexing. A second recovery is created following the intended incubation time (24 hr), after which the sample is placed into a vial with 10 mL of the neutralizing solution and vortexed. Following the test sample neutralization, aliquots of the sample are recovered and used to determine the infective titer following the respective incubation periods. Reagents Dulbecco's Modified Eagle Medium (DMEM; EM-1) Soybean Casein Lecithin Polysorbate 80 Medium (SCDLP) Phosphate Buffered Saline (PBS) Formaldehyde solution (3.7%) Crystal Violet (0.5%) Fetal bovine serum Viral Maintenance medium Trypsin Ethylenediaminetetraacetic acid solution (EDTA) Laboratory RO water, deionized Equipment List Thermo Orbital Shaker Incubator Scales (Mettler H80, Mettler PM-11K, Mettler MS104S/03) Nuaire BSL 2 cabinet Nuaire water-jacketed incubator Nikon inverted microscope Vortex mixer Centrifuge Liquid Nitrogen Dewar MarketForge Autoclave Hach pH Meter/ 02 measure / conductivity meter Dwyer Hygrometer Gilson Pipettes ISO 21702 - Measurement of antiviral activity on plastics and other non-porous surfaces Feline Calicivirus (F-9) {CCL-94 Eu cell Host) Human Coronavirus (229E} Human lung fibroblast MRC-5 (CCL-171} Sample Preparations Each test substance was prepared according to the analytic method requirements. Each test sample is prepared in triplicate for each time point. As available, the samples are cut into a piece approximately 50 mm x 50 mm. Sample variability is accommodated as needed for the standard test; notes regarding differences in the sample characteristic are recorded in the report summary. Ideally, the test sample is flat and non-hydrophobic and allow layering of the inoculum over the sample surface. Calculations End-point dilutions are conducted with the recovered virus inocula using serial log10 dilution factors. TCIDSO (Spearman-Karber; modified by M.A. Ramakrishnan) is used to determine the concentration of the inoculated virus based on the outcome of the end-point dilution resulting in the CTE of the host cells. It represents the end-point dilution (average) of the host cell monolayers exhibiting the CTE. Log10 50% end-point Dilution= - [(total number of CTE wells/ total number of dilution replicates) + 0.5] x log dilution factor R = - [Total CTE / replicate count per dilution)+ 0.5] x Log dilution factor R = The log 50% end-point dilution Total CTE - is the average of the common logarithm of the number of viable virus, in cells/cm2, recovered from the untreated test specimens immediately after inoculation; Replicate count per dilution - the numbers of well replicates inoculated at each dilution Log dilution factor - is the dilution factor used for each serial dilution (typically 10x or log10(10) = 1) Antiviral Activity Value R= U(t24)-C(t24)R = the antiviral activity value C(t24) = the common logarithm average of 3 infectivity titer values after 24 hours from the untreated material U(t24) = the common logarithm average of 3 infectivity titer values after the contact time (24 hr) with the treated (test) sample Statistical Methods Replicate data are utilized in the calculation by the Spearman-Karber method, no additional statistical analysis is conducted.
EXAMPLE 2. ANTIMICROBIAL ACTIVITY AGAINST ESCHERICHIA COLI
The polymer used was HMT-PMBI having 89% degree of methylation, as described, for example in PCT publication No WO2015/157848 incorporated herein by reference in
JIS Z 2801:2010, Japanese Industrial Standard Test for Antimicrobial Activity and Efficacy in Antimicrobial Products, was followed. Specifics of the test method applied to this project are described below.
This test method was designed to evaluate (quantitatively) the antimicrobial effectiveness of agent(s) incorporated or bound into or onto mainly flat (two dimensional) hydrophobic or polymeric surfaces.
The test organism was Escherichia coli ATCC# 8739.
Submitted samples were inoculated with 0.4 mL of a 0.2% nutrient broth seeded with a standardized culture of the test organism in triplicate. The inoculated samples were covered with an inert film and incubated at 36 ± 2 °C in a humidity chamber for 24 hours. Surviving microorganisms were recovered via elution of the broth inoculum from the test sample into neutralizing broth. Microbial counts of the samples were determined and the percent reduction of microorganisms (treated versus untreated samples at timepoint) was calculated.
A 1.2 mil polymeric membrane showed antimicrobial activity against Escherichia coli after 24 hours incubation in the JIS Z 2801 test method with 99.99% reduction and an antimicrobial activity value of 4 04 Percent reduction and antimicrobial activity were
EXAMPLE 3. ANTIMICROBIAL ACTIVITY AGAINST STAPH. AUREUS
The polymer used was HMT-PMBI having 89% degree of methylation, as described, for example, in PCT publication No. WO2015/157848, incorporated herein by reference in its entirety. uni A unit s unite
JIS Z 2801:2010, Japanese Industrial Standard Test for Antimicrobial Activity and Efficacy in Antimicrobial Products, was followed. Specifics of the test method applied to this project are described below.
This test method was designed to evaluate (quantitatively) the antimicrobial effectiveness of agent(s) incorporated or bound into or onto mainly flat (two dimensional) hydrophobic or polymeric surfaces.
The test organism was Staphylococcus aureus ATCC #6538.
Submitted samples were inoculated with 0.4 mL of a 0.2% nutrient broth seeded with a standardized culture of the test organism in triplicate. The inoculated samples were covered with an inert film and incubated at 36 ± 2 °C in a humidity chamber for 24 hours. Surviving microorganisms were recovered via elution of the broth inoculum from the test sample into neutralizing broth. Microbial counts of the samples were determined and the percent reduction of microorganisms (treated versus untreated samples at timepoint) was calculated.
A 1.2 mil polymer membrane showed antimicrobial activity against Staphylococcus aureus after 24 hours incubation in the JIS Z 2801 test method with >99.94% reduction and an antimicrobial activity value of >3.19. Percent reduction and antimicrobial activity were
EXAMPLE 4. ANTIFOULING TESTS
Test polymeric coupons are prepared by spraying a 5 wt% methanolic solution of a partially demethylated polymer material of the present disclosure, in mixed chloride/iodide form, onto glass slides, to afford continuous films of a given thickness and a given mass loading. Coupons were then subjected to biofilm growth conditions and cell enumeration as per ASTM E2647-13, a standard test method for quantification of Pseudomonas aeruginosa biofilm grown using drip flow biofilm reactor with low shear and continuous flow, incorporated herein by reference in its entirety.
Specifically, ASTM E2647-13 specifies the operational parameters required to grow a repeatable Pseudomonas aeruginosa biofilm close to the air/liquid interface in a reactor with a continuous flow of nutrients under low fluid shear conditions. The resulting biofilm is representative of generalized situations where biofilm exists at the air/liquid interface under low fluid shear rather than representative of one particular environment.
The test method uses the drip flow reactor. The drip flow reactor (DFR) is a plug flow reactor with laminar flow resulting in low fluid shear. The reactor is versatile and can also be used for growing and/or characterizing biofilms of different species.
This test method describes how to sample and analyze biofilm for viable cells. Biofilm population density is recorded as log colony forming units per surface area.
The test method is used for growing a repeatable P. aeruginosa biofilm in a drip flow reactor. The biofilm is established by operating the reactor in batch mode (no flow of nutrients) for 6 h. A mature biofilm forms while the reactor operates for an additional 48 h with a continuous flow of nutrients. During continuous flow, the biofilm experiences very low shear caused by the gravity flow of media dripping onto a surface set at a 10° angle. At the end of the 54 h, biofilm accumulation is quantified by removing coupons from the reactor channels, rinsing the coupons to remove the planktonic cells, scraping the biofilm from the coupon surface, disaggregating the clumps, then diluting and plating for viable cell enumeration. The experimental setup is as illustrated in FIGURES 9 and 10. Purity of Water—All reference to water as diluent or reagent shall mean distilled water or water of equal purity. Culture Media: Bacterial Liquid Growth Broth—Tryptic Soy Broth (TSB)7 is recommended. Two different TSB concentrations are used in the test method, 3000 mg/L for the inoculum and batch reactor operation and 270 mg/L for the continuous flow reactor operation. Bacterial Plating Medium—R2A agar7 is recommended. Buffered Water—0.0425 g/L KH2PO4 distilled water, filter sterilized and 0.405 g/L MgCl·6H2O distilled water, filter-sterilized (prepared according to Method 9050 C.1a). Pseudomonas aeruginosa (ATCC 700888) is the organism used in this test. Aseptically remove an isolated colony from an R2A plate and inoculate into 100 mL of sterile bacterial liquid growth broth (3000 mg TSB/L). Incubate bacterial suspension in an environmental shaker at 35 ± 2 °C for 20 to 24 h. Viable bacterial density should equal 108 CFU/mL and may be checked by serial dilution and plating. Procedure The Batch Phase: Place the cooled reactor in a level position on the bench top. Aseptically add 15 mL of sterile 3000 mg TSB/L and 1 mL of inoculum to each channel. Tighten each channel lid securely with nylon screws. Incubate the reactor system in batch mode at room temperature (2162°C) for 6 h, in the level position. Remove foil from the effluent tubing and attach end into a waste carboy. Do not unclamp until continuous flow phase. Preparation for Continuous Flow Phase: Prepare continuous flow nutrient broth by adding sterilized bacterial liquid growth medium to 20 L sterile reagent grade water so that final concentration is equal to 270 mg TSB/L (see 7.2.1). That is, dissolve and sterilize a broth concentrate in a smaller volume of water to prevent caramelization that can occur under the lengthy sterilization times required for large volumes. Aseptically pour the concentrated medium into the carboy of sterile water to make a total of 20 L. Adjust Reactor Angle (FIGURE.11): Measure a, the length of the reactor base, in cm. Angle (x) is 10°. Calculate y using the following equation: y – a[sin (x)]) where: a = measured length of reactor base in cm, x = angle (10°), and y = difference between length of b and length of c in cm. Decide upon the lengths of b and c to obtain the required difference (y). Use the following equation: Y = b-c where: b = measured length (cm) from bottom corner of influent end of reactor base to laboratory surface, c = measured length (cm) from bottom corner of effluent end of reactor base to laboratory surface, and y = difference between length of b and length of c in cm. Unclamp the effluent tubing and attach the legs to the DFR. Adjust the legs of the reactor chamber until the required lengths (b and c) are achieved so that it slopes downward 10°. Continuous Flow Phase: Aseptically connect the influent nutrient tubing line to the carboy containing the continuous flow nutrient broth. Feed each line through a pump head and connect a sterile needle on the end of each line. Aseptically attach the influent tubing by inserting the sterile needle through the Mininert valves in the channel lids. Turn on the pump, allowing media to slowly drip onto the bacterial cells attached to the coupon. A continuousflow of nutrients is pumped into the reactor through a pump set at a flow rate equal to 200 mL/h (50 mL/h per channel). The media should flow downward from the influent port to the effluent port. Periodically check the reactor for proper drainage and leaks. If problems occur, visually inspect the influent port and the tubing for bacterial plugging. The reactor is operated in CF mode for 48 h. Sampling the Biofilm: Prepare sampling materials: vortex, homogenizer, sterile beakers, sterile centrifuge tubes, culture tubes, pipettes, empty sterile petri dish, sterile spatulas, and flame sterilized stainless steel hemostat or forceps. Loosen channel lid screws with gloved hands and lift channel lid up. Aseptically remove one of the coupons by gently lifting up the coupon with sterile hemostat. Hold coupon over a sterile petri dish while carrying to the sampling area. Hold the coupon with flame sterilized hemostat being careful not to disturb the attached biofilm. Rinse the coupon to remove planktonic cells: Gently immerse coupon into the centrifuge tube containing 45 mL sterile buffered water with a fluid motion until slide is completely covered. Immediately reverse motion to remove the slide, being careful not to agitate liquid and biofilm. Remove the biofilm from the coupon: Scrape biofilm-covered coupon surface in a downward direction for approximately 15 s, using the flat end of a sterile spatula or scraper, into the beaker containing 45 mL of sterile dilution buffer. Rinse the spatula or scraper by stirring it in the beaker. Repeat the scraping and rinsing process 3 to 4 times, ensuring full coverage of the coupon surface. Hold the coupon at a 60° angle over the sterile beaker and pipette 1 mL of sterile buffered water over the top surface of the coupon. Repeat for a total of 5 rinses. The final volume in the beaker is 50 mL. Analyze the Biofilm Sample: Homogenize the scraped biofilm sample in the beaker at 20,500 ± 5000 r/min for 30s. If more than one biofilm sample is taken, rinse the homogenizer probe between each new sample as follows: Homogenize a dilution blank for 30s at 20,500 ± 5000 r/min, homogenize a tube containing 70 % ethanol for 15 s, then remove the probe and let the probe sit in the ethanol tube for 1 min. Shake any remaining ethanol off the probe, reattach probe, and homogenize a dilution blank for 30s. Homogenize a third dilution blank and then homogenize the next sample beaker. Homogenizing the sample disaggregates the biofilm clumps to form a homogeneous cell suspension. Improper disaggregation could result in an underestimation of the viable cells present in the sample. Perform serial 10-fold dilutions on the sample using sterile culture tubes. Plate each dilution in duplicate for colony growth using an accepted plating technique such as spread or spiral plating (Practice D5465). Incubate the plates for 17 to 20 h at 35 ± 2 °C. Cell Enumeration: Count the appropriate number of colonies according to the plating method used. Calculate the arithmetic mean of the colonies counted on the duplicate plates. The log density for one coupon is calculated as follows: LOG 10 (CFU/cm 2 ) = LOG 10 [(X/B)(V/A)(D)] where: X = mean CFU, B = volume plated, V = volume scraped into, A = surface area scraped, and D = dilution. Calculate the overall biofilm accumulation by calculating the mean of the log densities. EXAMPLE 4. PERFORMANCE OF ADDITIONAL POLYMER Another exemplary polymer, having the form shown in Scheme 3, was tested. Scheme 3 This "methyl-butyl" polymer was tested under similar conditions as the "high dm" polymer from the previous Examples. In comparison, it showed improved aliphatic character for improved activity against non-enveloped viruses. Comparable function against Gram- bacteria, Gram+ bacteria, and enveloped viruses. Comparable ability to be cast as films from low-boiling and/or non-toxic solvents. Comparable optical clarity, clearness & transparence. Improved consistency of charge density lot to lot. Reduced water uptake (or 'water uptake to charge' ratio) for improved durability on surfaces exposed to water or frequently washed surfaces. While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.