Antibacterial Nanofibers of Self-quaternized Block Copolymers of 4-Vinyl Pyridine and Pentachlorophenyl Acrylate

Abstract

Well-defined antibacterial block copolymers of 4-vinyl pyridine (4VP) and pentachlorophenyl acrylate (PCPA) (P(4VP-b-PCPA)) were prepared via reversible addition—fragmentation chain transfer (RAFT) polymerization. Electrospinning of the P(4VP-b-PCPA) from a solution in mixed tetrahydrofuran and dimethylformamide gave rise to fibers with diameters in the range of 0.5—4.0 µm. The quaternary ammonium salts (QASs) were generated by N-alkylation of pyridine groups of P4VP block and chloro-aromatic compounds of PPCPA block (or self-quaternization of P(4VP-b-PCPA)). The self-quaternization of P(4VP-b-PCPA) nanofibers was studied by X-ray photoelectron spectroscopy. Attributable to the hydrophobicity of the PPCPA blocks and the electrostatic interaction of QASs generated from the self-quaternization of P(4VP-b-PCPA), the resulting nanofibers exhibit a high antibacterial efficiency. The antibacterial effect of the P(4VP-b-PCPA) nanofibers was assayed using Escherichia coli and Staphylococcus aureus cultures. It was found that 99.6% of E. coli and 99.1% S. aureus were killed after being in contact with 50 mg nanofibers in 10 min. The permanence of antibacterial activity of the self-quaternized P(4VP-b-PCPA) nanofibers was also demonstrated in repeat application.

Keywords

Antibacterial reversible addition—fragmentation chain transfer (RAFT) polymerization block copolymer nanofiber electrospinning self-quaternized

Get full access to this article

View all access options for this article.

References

McKee, M.G. , Layman, J.M. , Cashion, M.P. and Long, T.E. (2006). Phospholipid Nonwoven Electrospun Membranes, Science, 311: 353-355.

Matthews, J.A. , Wnek, G.E. , Simpson, D.G. and Bowlin, GL (2002). Electrospinning of Collagen Nanofibers, Biomacromolecules , 3: 232-238.

Sun, X.Y. , Shankar, R. , Borner , H.G. , Ghosh, and Spontak , T.K. , ( 2007). Field-driven Biofunctionalization of Polymer Fiber Surfaces during Electrospinning , Adv. Mater., 19: 87-91.

Burger, C. , Hsiao, B.S. and Chu, B. ( 2006). Nanofibrous Materials and their Applications, Annu. Rev. Mater. Res., 36: 333-368.

Perez, M.A. , Swan, M.D. and Louks, J.W. Nanofibers and Method of Making, US Patent, 6,110,588, 2000.

Pike, R.D. Superfine Nanofiber Nonwoven web, US. Patent 2,935,883, 1999.

Wouters, D. and Schubert, U.S. (2004) Nanolithography and Nanochemistry: Probe-related Patterning Techniques and Chemical Modification for Nanometer-sized Devices, Angew. Chem. Inter. Ed.; 43: 2480- 2482.

Faul, C.F.J. and Antonietti, M. (2003) Ionic Self-assembly: Facile Synthesis of Supramolecular Materials, Adv. Mater. , 15: 673-675.

Fridrick, S.V. , Yu, J.H. , Brenner, M.P. and Rutledge, G.C. (2003) Controlling the Fiber Diameter during Electrospinning, Phys. Rev. Lett., 90: 144502-1-4.

10.

Ramakrishna, S. , Fujihara, K. , Teo , W.E. , Yong, T. and Ramaseshan, R. (2006) Electrospun Nanofibers: Solving Global Issues, Materials Today , 9: 40-50.

11.

Klibanov, A.M. (2007) Permanently Microbicidal Materials Coatings, J. Mater. Chem., 17: 2479-2482.

12.

Chen, L. , Brmberg, L. , Hatton, T.A. and Rutledge, GC , (2008). Electrospun Cellulose Acetate Fibers Containing Chlorhexidine as a Bactericide, Polymer, 49: 1266-1275.

13.

Jin, M. , Zhang, Z. , Nishimoto , S. , Liu , Z. , Tryk, D.A. , Emline, A.V.T.M. and Fujishima , A. ( 2007). Light-stimulated Composition Conversion in TiO2-based Nanofibers, J. Phys. Chem. C, 111: 658-665.

14.

Melaiye, A. , Sun, Z. , Hindi , K. , Milsted, A. , Ely , D. , Reneker, D.H. , Tesssier, C.A. and Youngs, W.J. (2005). Silver(I)-imidazole Cyclophane Gem-diol Complexes Encapsulated by Electrospun Tecophilic Nanofibers: Formation of Nanosilver Particles and Antimicrobial Activity, J. Am. Chem. Soc., 127: 2285- 2291.

15.

Tsukad, M. , Arai, T. , Colonna , G.M. , Boschi, A. and Freddi, G. (2003). Preparation of Metal-containing Protein Fibers and their Antimicrobial Properties , J. Appl. Polm. Sci., 89: 638-644.

16.

Freiter, E.R. (1980). Chlorophenols, In Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edn, John Wiley and Sons, New York, Vol. 5, pp. 864-872.

17.

Gavrilescu, M. (2005). Fate of Pesticides in the Environment and Its Bioremediation, Eng. Life Sci., 5: 497-526.

18.

de Arruda Alerda, K. , de Queiroz, AAA , Higa, O.Z. , Abraham, G.A. and Roman, J.S. (2004). Macroporous Poly(epsilon-caprolactone) with Antimicrobial Activity obtained by Iodine Polymerization, J. Biomed Mater. Res. A., 68: 473-478.

19.

Tashiro, T. (2001). Antibacterial and Bacterium Adsorbing Macromolecules, Macro. Mater. Eng., 286: 63-87.

20.

Hu, F.X. , Neoh, K.G. and Kang, E.T. (2005). Antibacterial and Antifungal Efficacy of Surface Functionalized Polymeric Beads in Repeated Applications, Biotech. Bioeng., 89: 474-484.

21.

Lowe, A.B. and McCormick, C.L. (2007). Reversible Addition-fragmentation Chain Transfer (RAFT) Radical Polymerization and the Synthesis of Water-soluble (co)polymers under Homogeneous Conditions in Organic and Aqueous Media, Prog . Polym. Sci., 32: 283-351.

22.

Le, T.P.T. , Moad, G. , Rizzardo , E. and Thang, S.H. (1998). Polymerization with Living Characteristics, WO Patent 9801478.

23.

Moad, G. , Rizzardo, E. and Thang, S.H. ( 2008). Radical Addition-fragmentation Chemistry in Polymer Synthesis , Polymer, 49: 1079-1131.

24.

Borner, L. , Davis, T.P. , Stenzel, M.H. and Barner-Kowollik , C. (2007 ). Complex Macromolecular Architectures by Reversible Addition Fragmentation Chain Transfer Chemistry: Theory and Practice, Macromol. Rapid Commun., 28: 539-559.

25.

Moad, G. , Rizzardo, E. and Thang, S.H. ( 2005). Living Radical Polymerization by the RAFT Process, Aust . J. Chem., 58: 379-410.

26.

Favier, A. and Charreyre, M.T. ( 2006). Experimental Requirements for an Efficient Control of Free-radical Polymerizations via the Reversible Addition-fragmentation Chain Transfer (RAFT) Process, Macromol. Rapid Commun., 27: 653-692.

27.

Fu, G.D. , Yao, F. , Li, Z.G. and Li, X.S. ( 2008). Solvent-resistant Antibacterial Microfibers of Self-quaternized Block Copolymers from Atom Transfer Radical Polymerization and Electrospinning , J. Mater. Chem. , 18: 859-867.

28.

Cunliffe, D. , Smart, C.A. , Alexander, C. and Vulfson, E.N. ( 1999). Bacterial Adhesion at Synthetic Surfaces, Appl. Environ Microbiol., 65: 4995-5002.

29.

Hogt, A.H. , Dankert, J. and Feijen, J. ( 1986). Adhesion of Coagulase-negative Staphylococci to Methacrylate Polymers and Copolymers, J Biomed Mater Res. , 20: 533-545.

30.

Zhu, J. , Zhu, X.L. , Cheng, Z.P. , Liu, F. and Lu, J. ( 2002). Study on Controlled Free-radical Polymerization in the Presence of 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN), Polymer, 43; 7037-7042.

31.

Convertine, A.J. , Sumerlin, B.S. , Thomas, D.B. , Lowe, A.B. and McCormick , C.L. (2003). Synthesis of Block Copolymers of 2-and 4-vinylpyridine by RAFT Polymerization , Macromolecules, 36: 4679-4681.

32.

Beamson, G. and Briggs, D. ( 1992). High Resolution XPS of Organic Polymers The scienta ESCA 300 Database. John Wiley & Son, Chichester, UK, p. 274.

33.

Muilenberg, G.E. (ed.) ( 1978 ). Handbook of X-ray Photoelectron Spectroscopy, Perkin- Elmer: Eden Prairie, MN, p. 94.

34.

Greiner, A. and Wendorff, J.H. (2007). Electrospinning: A Fascinating Method for the Preparation of Ultrathin Fibres, Angew. Chem. Int. Ed., 46: 5670-5703.

35.

Sikkema, J. , de Bont, J.A.M. and Poolman , B. (1994). Interactions of Cyclic Hydrocarbons with Biological Membranes, J. Biol. Chem., 269: 8022-8028.