Abstract
Plasma-based technology is an alternative to produce universal polymer coatings with the appropriate requirements of robustness and stability for antibacterial applications. Here, we proposed a sequential two-step alternative to synthesize antibacterial polymer coatings. A non-isothermal plasma reactor, operated at atmospheric pressure (Patm) and room temperature (Troom), was used to induce free radical polymerization of 4-vinyl pyridine (4VP) on high-density polyethylene (PE). In a subsequent step, the poly-4VP (P4VP) films were treated with a bromoethane/He gas stream to produce quaternized P4VP (P4VPQ) films. Chemical structure of polymer films was validated by infrared and UV–visible spectroscopy, and morphology was evaluated by optical and atomic force microscopy; scanning electron microscopy was used to determine films thickness, which was then used to estimate the surface charge density. The bactericidal capacity was determined with a standard test by using Escherichia coli. Both types of films had an estimated charge density in the order of 1016 positive charges per cm2; P4VP films removed about 95–99% of bacteria, whereas 4PVPQ films eliminated 100%. The methodology proposed for the synthesis of antibacterial polymer coatings is simpler, faster, and more environmentally friendly than other plasma-based methods; operation at Troom and Patm may also have a significant effect on the economics and the ease of implementation of the process at commercial scale. The suggested approach may facilitate the development of new universal coatings, and operating plasma conditions could be extrapolated for engineering antibacterial coatings in industrial areas where bacterial attachment is of concern.
Similar content being viewed by others
References
Sardella E, Palumbo F, Camporeale G, Favia P (2016) Non-equilibrium plasma processing for the preparation of antibacterial surfaces. Materials 9:515–538
Jacobs T, Morent R, De Geyter N, Dubruel P, Leys C (2012) Plasma surface modification of biomedical polymers: influence of cell-material interaction. Plasma Chem Plasma Process 32:1039–1073
Cloutier M, Mantovani D, Rosei F (2015) Antibacterial coatings: challenges, perspectives, and opportunities. Trends Biotechnol 33(11):637–652
Wei Q, Haag R (2015) Universal polymer coatings and their representative biomedical applications. Mater Horiz 2:567–577
Desmet T, Morent R, Geyter N, Leys C, Schacht E, Dubruel P (2009) Nonthermal plasma technology as a versatile polymeric biomaterials strategy for surface modification: a review. Biomacromol 10(9):2351–2378
Nikiforov A, Deng X, Xiong Q, Cvelbar U, De Geyter N, Morent R, Leys C (2016) Non-thermal plasma technology for the development of antimicrobial surfaces: a review. J Phys D Appl Phys 49:2004002
Vasilev K (2014) Nanoengineered plasma polymer films for biomaterial applications. Plasma Chem Plasma Process 334:538–545
Siedenbiedel F, Tiller JC (2012) Antimicrobial polymers in solution and on surfaces: overview and functional principles. Polymers 4:46–71
Tiller JC, Liao CJ, Lewis K, Klibanov AM (2001) Designing that kill bacteria on surface contact. PNAS 98(11):5981–5985
Kugler R, Bouloussa O, Rondelez F (2005) Evidence of a charge-density threshold for optimum efficiency of cationic biocidal surface. Microbiology 151:1341–1348
Jampala SN, Sarmadi M, Somers EB, Wong ACL, Denes FS (2008) Plasma enhanced synthesis of bactericidal quaternary ammonium thin layers on stainless steel and cellulose surfaces. Langmuir 24(16):8583–8591
Schofield WCE, Badyal JPS (2009) A substrate-independent approach for bactericidal surfaces. ACS Appl Mater Interfaces 1(12):2763–2767
Jiang J, Winther-Jensen B, Kjær MS (2006) Characterization of plasma-polymerized 4-vinyl pyridine on poly (ethylene terephthalate) film for anti-microbial properties. Macromol Symp 239:84–90
Wade LG (2013) Organic chemistry, 8th edn. Pearson Education, London
Skoog DA, Holler FJ, Crouch SR (2007) Principles of instrumental analysis, 6th edn. Thomson Brooks/Cole, Belmont
Chen Y, Zheng X, Xie Y, Ding Ch, Ruan H, Fan C (2008) Anti-bacterial and cytotoxic properties of plasma sprayed silver-container containing HA coatings. J Mater Sci Mater Med 19:3603–3609
JIS Z 2801 (2000) Test for antimicrobial products-antimicrobial activity and efficacy. Jpn Stand Assoc, Japan
D’Agostino R, Favia P, Oehr C, Wertheimer MR (2005) Low temperature plasma processing of materials: past, present and future. Plasma Process Polym 2:7–15
Smith BC (1999) Infrared spectral interpretation: a systematic approach, 1st edn. CRC Press, Boca Ratón
Harnish B, Robinson JT, Pei Z, Ramström O, Yan M (2005) UV-cross-linked poly (vinylpyridine) thin films as reversibly responsive surfaces. Chem Mater 17:4092–4096
Mistry BD (2009) A handbook of chemistry data spectroscopic (UV, IR, PMR, 13C NMR and mass spectroscopy), 2009th edn. Oxford Book Company, Jaipur
Derrick MR, Stulik D, Landry JM (1999) Infrared spectroscopy in conservation science. J. Paul Getty Trust, Los Angeles
Billmeyer FW (1984) Polymer science, 3rd edn. Wiley, New York
Friedbacher G, Bubert H (2011) Surface and thin film analysis: a compendium of principles, instrumentation, and applications, 2nd edn. Wiley, New York
Hong Y, Brown DG (2009) Alteration of bacterial surface electrostatic potential and pH upon adherence to a solid surface and impacts to cell bionergetics. Biotechnol Bioeng 105(5):965–972
Terada A, Yuasa A, Kushimoto T, Satoshi T, Katakai A, Tamada M (2006) Bacterial adhesion to and viability on surfaces positively charged polymer. Microbiology 152:3575–3583
Murata H, Koepsel RR, Matyjaszewski K, Russell AJ (2007) Permanent, non-leaching antimicrobial surfaces 2: how high density cationic kill bacterial cells surfaces. Biomaterials 28:4870–4879
Sambhy V, Eves D, Ewing A, Sen A (2007) Direct visualization of lipid membrane disruption by antibacterial pyridinium polymers in GUV model systems. Polym Prepr Am Chem Soc Div Polym Chem 48(1):676
Cen L, Neoh KG, Kang ET (2003) Surface functionalization technique for conferring antibacterial properties to polymeric and cellulosic surfaces. Langmuir 19:10295–10303
Acknowledgements
MHO thanks Consejo Nacional de Ciencia y Tecnología (CONACyT) scholarship 228888. The financial support of CONACYT (Grants 162651 and 252320) and UASLP (Grant C13-FRC-01-04-04) for the development of the project is greatly appreciated The authors thank Rosa E. Delgado-Portales for supplying the E. coli 11775 strain, and Claudia Arellano del Rio, Maria de Lourdes González-González, Claudia Guadalupe Elías, Gladis Judith Labrada-Delgado and Maria Estela Nunez-Pastrana for technical support.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
Authors declare no conflict of interest.
Rights and permissions
About this article
Cite this article
Hernández-Orta, M., Pérez, E., Cruz-Barba, L.E. et al. Synthesis of bactericidal polymer coatings by sequential plasma-induced polymerization of 4-vinyl pyridine and gas-phase quaternization of poly-4-vinyl pyridine. J Mater Sci 53, 8766–8785 (2018). https://doi.org/10.1007/s10853-018-2183-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-018-2183-x