Abstract
A poly(methyl methacrylate) (PMMA) surface was fluorinated by immersion in 3-(perfluoro-7-methyloctyl)-1,2-epoxypropene and subsequent heat treatment at 120 °C. The water contact angle on PMMA increased from 67° to 111° after the fluorination treatment with no loss of optical transparency. This high contact angle corresponds to a surface free energy of 10 mJ m−2, which is much lower than that of poly(tetrafluoroethylene) (22 mJ m−2). X-ray photoelectron spectroscopy analysis revealed that the surface was almost completely covered by fluoroalkyl groups, which imparted high hydrophobicity. This simple fluorination method effectively lowers the surface free energy of PMMA. The fluorinated PMMA also demonstrated low albumin adsorption, low blood clotting and antifouling properties against fingerprints. These characteristics reveal that fluorinated PMMA generated by a simple immersion treatment could serve as an antithrombogenic or antifingerprint fouling material.
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References
Sogiv, J. Organized monolayers by adsorption I. formation and structure of oleophobic mixed monolayers on solid surfaces. J. Am. Chem. Soc. 102, 92–98 (1980).
Tillman, N ., Ulman, A. & Penner, T. L. Formation of multilayers by self-assembly. Langmuir 5, 101–111 (1989).
Wasserman, S. R ., Tao, Y. T. & Whitesides, G. M. Structure and reactivity of alkylsiloxane monolayers formed by reaction of alkyltrichlorosilanes on silicon substrates. Langmuir 5, 1074–1087 (1989).
Terlingen, J. G. A ., Takens, G. A. J, Van Dei Gaag, F. J ., Hoffman, A. S. & Feijen, J. On the effect of treating poly(acrylic acid) with argon and tetrafluoromethane plasmas: kinetics and degradation mechanism. J. Appl. Polym. Sci. 52, 39–53 (1992).
Terlingen, J. G. A ., Hoffman, A. S. & Feijen, J. Effect of glow discharge treatment of poly(acrylic acid) preadsorbed onto poly(ethylene). J. Appl. Polym. Sci. 50, 1529–1539 (1994).
Park, D ., Weinman, C. J ., Finlay, J. A ., Fletcher, B. R ., Paik, M. Y ., Sundaram, H. S ., Dimitriou, M. D ., Sohn, K. E ., Callow, M. E ., Callow, J. A ., Handlin, D. L ., Willis, C. L ., Fischer, D. A ., Kramer, E. J. & Ober, C. K. Amphiphilic surface active triblock copolymers with mixed hydrophobic and hydrophilic side chains for tuned marine fouling-release properties. Langmuir 26, 9772–9781 (2010).
Kessman, A. J. & Cairns, D. R. Microtribological study of internal surfaces of fluorinated mesoporous silica films. Langmuir 27, 5968–5975 (2011).
Booth, B. D ., Vilt, S. G ., Lewis, J. B ., Rivera, J. L ., Buehler, E. A ., McCabe, C. & Jennings, G. K. Tribological durability of silane monolayers on silicon. Langmuir 27, 5090–5917 (2011).
Klein, R. J ., Fischer, D. A. & Lenhart, J. L. Thermal and mechanical aging of self-assembled monolayers as studied by near edge X-ray absorption fine structure. Langmuir 27, 12423–12433 (2011).
Zisman, W. A. Relation of the equilibrium contact angle to liquid and solid constitution. Adv. Chem 43, 1–51 (1964).
Guo, Y ., Di, C ., Liu, H ., Zheng, J ., Zhang, L ., Yu, G. & Liu, Y. General route toward Patterning of graphene oxide by a combination of wettability modulation and spin-coating. ACS NANO 4, 5749–5754 (2010).
Nishino, T ., Meguro, M. & Nakamae, K. Poly(vinyl alcohol) with low surface free energy by fluorination. Int. J. Adhes. 19, 399–403 (1999).
Durand, N ., Gaveau, P ., Silly, G ., Améduri, B. & Boutevin, B. Radical grafting of tetrafluoroethylene and vinylidene fluoride telomers onto silica bearing vinyl groups. Macromolecules 44, 6249–6257 (2011).
Nyström, D ., Lindqvist, J ., Őstmark, E ., Antoni, P ., Carlmark, A ., Hult, A. & Malmström, E. Superhydrophobic and self-cleaning bio-fiber surfaces via ATRP and subsequent postfunctionalization. ACS Appl. Mater. Interfaces 1, 816–823 (2009).
Sumiya, K ., Taii, T ., Nakamae, K. & Matsumoto, T. Adhesion of the vacuum-deposited cobalt thin films to polymer films. J. Adhes. Soc. Jpn. 18, 345–351 (1982).
Nishino, T ., Meguro, M ., Nakamae, K ., Matsushita, M. & Ueda, Y. The lowest surface free energy based on -CF3 . Langmuir 15, 4321–4323 (1999).
Owens, D. K. & Wendt, R. C. Estimation of the surface free energy of polymers. J. Appl. Polym. Sci. 13, 1741–1747 (1969).
Fowkes, S. M. Additivity of intermolecular forces at interfaces. I. determination of the contribution to surface and interfacial tensions of dispersion forces in various liquids. J. Phys. Chem. 67, 2538–2541 (1963).
Smith, P. K ., Krohn, R. I ., Hermanson, G. T ., Mallia, A. K ., Gartner, F. H ., Provenzano, M. D ., Fujimoto, E. K ., Geoke, N. M ., Olson, B. J. & Klenk, D. C. Measurement of protein using bicinchoninic acid. Anal. Biochem. 150, 76–85 (1985).
McCarley, R. L ., Vaidya, B ., Wei, S ., Smith, A. F ., Patel, A. B. & Feng, J. Resist-free patterning of surface architectures in polymer-based microanalytical devices. J. Am. Chem. Soc. 127, 842–843 (2005).
Tsougeni, K ., Tserepi, A ., Constantoudis, V. & Gogolides, E. Plasma nanotextured PMMA surfaces for protein arrays: increased protein binding and enhanced detection sensitivity. Langumuir 26, 13883–13891 (2010).
Hare, E. F ., Shafrin, E. G. & Zisman, W. A. Properties of films of adsorbed fluorinated acids. J. Phys. Chem. 58, 236–239 (1954).
Nishino, T ., Urushihara, Y ., Meguro, M. & Nakamae, K. Surface properties and structures of diblock and random copolymers with perfluoroalkyl side chains. J. Colloid Interface Sci. 279, 364–369 (2004).
Urushihara, Y. & Nishino, T. Effects of film forming conditions on surface properties and structures of diblock copolymer with perfluoroalkyl side chains. Langmuir 21, 2614–2618 (2005).
Tamada, Y. & Ikada, Y. Effect of preadsorbed proteins on cell adhesion to polymer surface. J. Colloid Interface Sci. 155, 334–339 (1993).
Tanaka, M ., Motomura, T ., Kawada, M ., Anzai, T ., Kasori, Y ., Shiroya, T ., Shimura, K ., Onishi, M. & Mochizuku, A. Blood compatible aspects of poly(2-methoxyethyl acrylate) (PMEA)-relationship between protein adsorption and platelet adhesion on PMEA surface. Biomaterials 21, 1471–1481 (2000).
Vroman, L. & Adams, A. L. Identification of rapid changes at plasma-solid interfaces. J. Biomed. Mater. Res. 3, 43–67 (1969).
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Tokuda, K., Ogino, T., Kotera, M. et al. Simple method for lowering poly(methyl methacrylate) surface energy with fluorination. Polym J 47, 66–70 (2015). https://doi.org/10.1038/pj.2014.91
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DOI: https://doi.org/10.1038/pj.2014.91
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