Antimicrobial coatings and methods of making and using thereof
Disclosed are antimicrobial articles and surfaces, as well as methods of making such articles and surfaces.
1. A process for rendering a polyvinyl chloride surface antimicrobial, the process comprising:
(a) contacting the polyvinyl chloride surface with a cyanation reagent in the presence of a phase transfer catalyst to form a cyano-substituted polyvinyl chloride surface; and
(b) covalently bonding an antimicrobial agent to the cyano-substituted polyvinyl chloride surface.
2. The process of claim 1 , wherein the antimicrobial agent comprises a hydrazone moiety or an azide moiety, and wherein step (b) comprises contacting the cyano-substituted polyvinyl chloride surface with the antimicrobial agent under conditions effective to covalently bond the antimicrobial agent to the polyvinyl chloride surface.
3. The process of claim 1 , wherein step (b) comprises: (i) converting cyano groups in the cyano-substituted polyvinyl chloride surface to 1H-tetrazole moieties, thereby forming a 1H-tetrazole-substituted polyvinyl chloride surface; and (ii) contacting the 1H-tetrazole-substituted polyvinyl chloride surface with an antimicrobial agent comprising an electrophilic moiety under conditions effective to covalently bond the antimicrobial agent to the polyvinyl chloride surface.
4. The process of claim 3 , wherein step (i) comprises contacting the cyano-substituted polyvinyl chloride surface with an azide salt in the presence of a catalyst.
5. The process of claim 1 , wherein step (b) comprises: (i) converting cyano groups in the cyano-substituted polyvinyl chloride surface to 1H-tetrazole moieties, thereby forming a 1H-tetrazole-substituted polyvinyl chloride surface; (ii) contacting the 1H-tetrazole-substituted polyvinyl chloride surface with an electrophile comprising an azide group to form an azide-substituted polyvinyl chloride surface; and (iii) contacting the azide-substituted polyvinyl chloride with an antimicrobial agent comprising an alkyne moiety under conditions effective to covalently bond the antimicrobial agent to the polyvinyl chloride surface.
6. The process of claim 5 , wherein the electrophile comprising the azide group is chosen from a benzylic halide comprising an azide group, an allylic halide comprising an azide group, and a propargylic halide comprising an azide group.
7. The process of claim 5 , wherein the alkyne moiety is activated by ring strain, electron withdrawing groups, or a combination thereof.
8. The process of claim 5 , wherein step (iii) comprises contacting the azide-substituted polyvinyl chloride surface with the antimicrobial agent comprising the alkyne moiety in the presence of a Cu(I) catalyst.
9. The process of claim 1 , wherein step (b) comprises: (i) converting cyano groups in the cyano-substituted polyvinyl chloride surface to 1H-tetrazole moieties, thereby forming a 1H-tetrazole-substituted polyvinyl chloride surface; (ii) contacting the 1H-tetrazole-substituted polyvinyl chloride surface with an electrophile comprising an alkynyl group to form an alkyne-substituted polyvinyl chloride surface; and (iii) contacting the alkyne-substituted polyvinyl chloride surface with an antimicrobial agent comprising an azide moiety under conditions effective to covalently bond the antimicrobial agent to the polyvinyl chloride surface.
10. The process of claim 9 , wherein the electrophile comprising the alkynyl group is chosen from a benzylic halide comprising an alkynyl group, an allylic halide comprising an alkynyl group, and a propargylic halide comprising an alkynyl group.
11. The process of claim 9 , wherein the alkynyl group is activated by ring strain, electron withdrawing groups, or a combination thereof.
12. The process of claim 9 , wherein step (iii) comprises contacting the alkyne-substituted polyvinyl chloride with the antimicrobial agent comprising the azide moiety in the presence of a Cu(I) catalyst.
13. The process of claim 1 , wherein step (a) comprises flowing an aqueous solution comprising the cyanation reagent and the phase transfer catalyst across the polyvinyl chloride surface.
14. The process of claim 1 , wherein step (a) comprises contacting the polyvinyl chloride surface with the cyanation reagent and the phase transfer catalyst for 3 hours or less.
15. The process of claim 1 , wherein the polyvinyl chloride surface comprises a surface of a medical article.
16. The process of claim 15 , wherein the medical article comprises tubing.
17. The process of claim 16 , wherein the surface of the medical article comprises an interior surface of the tubing, an exterior surface of the tubing, or both an interior surface of the tubing and an exterior surface of the tubing.
18. The process of claim 1 , wherein the antimicrobial agent comprises a polycationic polymer.
19. The process of claim 18 , wherein the polycationic polymer comprises a polymer defined by Formula I below
wherein
Z represents, individually for each occurrence, S, Se, or NR 3 ;
A represents, individually for each occurrence, a heterocyclic ring comprising a cationic nitrogen center;
X represents, individually for each occurrence, an anion;
Y is absent, or represents, individually for each occurrence, a linking group;
R 1 is absent, or represents, individually for each occurrence, halogen, hydroxy, amino, cyano, azido, hydrazone, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, alkylaryl, alkylheteroaryl, cycloalkyl alkylcycloalkyl, heterocycloalkyl, alkylheterocycloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, peptidyl, polyamino, or polyalkyleneoxy;
R 2 is absent, or represents, individually for each occurrence, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, alkylaryl, alkylheteroaryl, cycloalkyl alkylcycloalkyl, heterocycloalkyl, alkylheterocycloalkyl, peptidyl, polyamino, or polyalkyleneoxy;
R 3 represents, individually for each occurrence, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, alkylaryl, alkylheteroaryl, cycloalkyl alkylcycloalkyl, heterocycloalkyl, alkylheterocycloalkyl, peptidyl, polyamino, or polyalkyleneoxy; and
n is an integer from 2 to 400.
20. The process of claim 19 , A is chosen from pyridine, imidazole, pyrazole, triazole, tetrazole, oxazole, isoxazole, furazan, isothioazole, and thiazole.
21. The process of claim 19 , wherein Z is S.
22. The process of claim 19 , wherein Z is NR 3 .
23. The process of claim 19 , wherein R 1 , R 2 , R 3 , or a combination thereof comprise a cationic moiety.
24. The process of claim 19 , wherein Y is chosen from one of the following:
where m is an integer from 1 to 12.
25. The process of claim 19 , where X is chosen from chloride, bromide, iodide, nitrate, sulfate, triflate, borate, and phosphate.
26. The process of claim 19 , wherein n is from 10 to 50.
27. The process of claim 19 , wherein the polycationic polymer comprises a polymer defined by Formula IA below
wherein Z, X, Y, R 1 , R 2 , R 3 , and n are as defined above with respect to Formula I.
28. The process of claim 18 , wherein the polycationic polymer comprises a recurring unit defined by Formula V below
wherein
R 4 represents H or methyl;
L is absent or represents a linking group;
A represents, individually for each occurrence, a heterocyclic ring comprising a cationic nitrogen center;
R 5 is absent, or represents, individually for each occurrence, halogen, hydroxy, amino, cyano, azido, hydrazone, alkyl, alkenyl, alkynyl, alkoxy, aryl, heteroaryl, alkylaryl, alkylheteroaryl, cycloalkyl alkylcycloalkyl, heterocycloalkyl, alkylheterocycloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, peptidyl, polyamino, or polyalkyleneoxy; and
m is an integer from 0 to 5.
29. The process of claim 28 , wherein the polycationic polymer further comprises a recurring unit derived from the polymerization of one or more ethylenically-unsaturated monomers.
30. The process of claim 29 , wherein the one or more ethylenically-unsaturated monomers are chosen from the group consisting of styrene, butadiene, meth(acrylate) monomers, vinyl acetate, vinyl ester monomers and combinations thereof.
31. The process of claim 1 , wherein the phase transfer catalyst comprises a quaternary ammonium salt.
32. The process of claim 1 , wherein the cyanation reagent comprises NaCN, KCN, or a combination thereof.