Random copolymers (P(M100-m/T m )) composed of 2-methacryloyloxyethyl phosphorylcholine (MPC), which suppresses protein adsorption, and 3-(triethoxysilyl)propyl methacrylate (MTEOS), which can be covalently fixed on a glass surface, were prepared via photoinitiated radical polymerization. When P(M100-m/T m ) was coated on a glass surface, a protein antifouling effect could be observed because of the presence of MPC units on the glass surface. To confirm the coating of the glass surface with P(M100-m/T m ) by fluorescence microscopy, pyrene-labeled P(M100-m/T m ) was also prepared. An ethanol solution of P(M100-m/T m ) was spin-coated on the glass, which was exposed to NH3 vapor to promote the reaction of the pendant triethoxysilyl groups in P(M100-m/T m ) with silanol groups on the glass. The coating of the glass with MPC was confirmed by fluorescence microscopy. The protein antifouling effects of the P(M100-m/T m )-coated glass were confirmed using fluorescence-labeled proteins. It is expected that P(M100-m/T m ) can be applied as a surface-coating agent on glass containers for protein formulations.
Subscribe to Journal
Get full journal access for 1 year
only $27.58 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Mathes J. Protein adsorption to vial surfaces - quantification, structural and mechanistic studies. Göttingen, Germany: Cuvillier Verlag; 2010.
Xu Y, Takai M, Konno T, Ishihara K. Microfluidic flow control on charged phospholipid polymer interface. Lab Chip. 2007;7:199–206.
Kihara T, Yoshida N, Mieda S, Fukazawa K, Nakamura C, Ishihara K, Miyake J. Nanoneedle surface modification with 2-methacryloyloxyethyl phosphorylcholine polymer to reduce nanospecific protein adsorption in a living cell. Nanobiotechnol. 2007;3:127–34.
Yang Z, Galloway JA, Yu H. Protein interactions with poly(ethylene glycol) self-assembled monolayers on glass substrates: diffusion and adsorption. Langmuir. 1999;15:8405–11.
Wazawa T, Kasturan YI, Nishikawa S, Iwane AH, Aoyama S. Grafting of poly(ethylene glycol) onto poly(acrylic acid)-coated glass for a protein-resistant surface. Anal Chem. 2006;78:2549–56.
Li M, Neoh KG, Xu LQ, Wang R, Kang ET, Lau T, Olszyna DP, Chiong E. Surface modification of silicone for biomedical applications requiring long-term antibacterial, antifouling, and hemocompatible properties. Langmuir. 2012;28:16408–22.
Ishihara K & Fukazawa K. In Phosphorus-based polymers: from synthesis to applications. (eds) Monge S & David G, Ch. 5, London: RSC; 2014. p. 68–96.
Ishihara K, Mu M, Konno T, Inoue Y, Fukazawa K. The unique hydration state of poly(2-methacryloyloxyethyl phosphorylcholine). J Biomat Sci Polym Ed. 2017;28:884–99.
Ishihara K, Mu M & Konno T. Water-soluble and amphiphilic phospholipid copolymers having 2-methacryloyloxyethyl phosphorylcholine units for the solubilization of bioactive compounds. J. Biomat. Sci. Polym. Ed. 1–19. https://doi.org/10.1080/09205063.2017.1377023).
Ueda T, Oshida H, Kurita K, Ishihara K, Nakabayashi N. Preparation of 2-methacryloyloxyethyl phosphorylcholine copolymers with alkyl methacrylates and their blood compatibility. Polym J. 1992;24:1259–69.
Iwata R, Suk-In P, Hoven VP, Takahara A, Akiyoshi K, Iwasaki Y. Control of nanobiointerfaces generated from well-defined biomimetic polymer brushes for protein and cell manipulations. Biomacromolecules. 2004;5:2308–14.
Feng W, Brash J, Zhu S. Atom-transfer radical grafting polymerization of 2-methacryloyloxyethyl phosphorylcholine from silicon wafer surfaces. J Polym Sci, Part A: Polym Chem. 2004;42:2931–42.
Feng W, Zhu S, Ishihara K, Brash JL. Adsorption of fibrinogen and lysozyme on silicon grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom transfer radical polymerization. Langmuir. 2005;21:5980–7.
Inoue Y, Onodera Y, Ishihara K. Preparation of a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine) by surface-initiated atom transfer radical polymerization and analysis of protein adsorption resistance. Colloid Surf B. 2016;141:507–12.
Sakata S, Inoue Y, Ishihara K. Molecular interaction forces generated during the protein adsorption to well-defined polymer brush surfaces. Langmuir. 2015;31:3108–14.
Pereira AS, Sheikh S, Blaszykowski C, Pop-Georgievski O, Fedorov K, Thompson M, Rodriguez-Emmenegger C. Antifouling polymer brushes displaying antithrombogenic surface properties. Biomacromolecules. 2016;17:1179–85.
Yuan B, Chen Q, Ding WQ, Liu PS, Wu SS, Lin SC, Shen J, Gai Y. Copolymer coatings consisting of 2-methacryloyloxyethyl phosphorylcholine and 3-methacryloxypropyl trimethoxysilane via ATRP to improve cellulose biocompatibility. ACS Appl Mater Interfaces. 2012;4:4031–9.
Futamura K, Matsumoto R, Konno T, Takai M, Ishihara K. Rapid development of hydrophilicity and protein adsorption resistance by polymer surfaces bearing phosphorylcholine and naphthalene groups. Langmuir. 2008;24:10340–4.
Iwasaki Y, Takami U, Shinohara Y, Kurita K, Akiyoshi K. Selective biorecognition and preservation of cell function on carbohydrate-immobilized phosphorylcholine polymers. Biomacromolecules. 2007;8:2788–94.
Bi H, Zhong W, Meng S, Kong J, Yang P, Liu B. Construction of a biomimetic surface on microfluidic chips for biofouling resistance. Anal Chem. 2006;78:3399–405.
Razunguzwa TT, Warrier M, Timperman AT. ESI-MS compatible permanent coating of glass surfaces using poly (ethylene glycol)-terminated alkoxysilanes for capillary zone electrophoretic protein separations. Anal Chem. 2006;78:4326–33.
Sung D, Park S, Jon S. Facile immobilization of biomolecules onto various surfaces using epoxide-containing antibiofouling polymers. Langmuir. 2012;28:4507–14.
Gong M, Dang Y, Wang YB, Yang S, Winnik FM, Gong YK. Cell membrane mimetic films immobilized by synergistic grafting and crosslinking. Soft Matter. 2013;9:4501–8.
Brinker CJ, Scherer GW. Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing. San Diego, USA: Academic Press; 1990.
Jiang H, Zheng Z, Li Z, Wang X. Effects of temperature and solvent on the hydrolysis of alkoxysilane under alkaline conditions. Ind Eng Chem Res. 2006;45:8617–22.
Yagci Y, Jockusch S, Turro NJ. Photoinitiated polymerization: advances, challenges, and opportunities. Macromolecules. 2010;43:6245–60.
Ishihara K, Ueda T, Nakabayashi N. Preparation of phospholipid polylners and their properties as polymer hydrogel membranes. Polym J. 1990;22:355–60.
Yusa S, Sakakibara A, Yamamoto T, Morishima Y. Fluorescence studies of pH-responsive unimolecular micelles formed from amphiphilic polysulfonates possessing long-chain alkyl carboxyl pendants. Macromolecules. 2002;35:10182–8.
Yip J, Duhamel J, Qiu XP, Winnik FM. Long-range polymer chain dynamics of pyrene-labeled poly(N-isopropylacrylamide)s studied by fluorescence. Macromolecules. 2011;44:5363–72.
Fukazawa K, Ishihara K. Synthesis of photoreactive phospholipid polymers for use in versatile surface modification of various materials to obtain extreme wettability. Acs Appl Mater Interfaces. 2013;5:6832–6.
Xu Y, Takai M, Ishihara K. Protein adsorption and cell adhesion on cationic, neutral, and anionic 2-methacryloyloxyethyl phosphorylcholine copolymer surfaces. Biomaterials. 2009;30:4930–8.
Kobayashi M, Terayama Y, Kikuchi M, Takahara A. Chain dimensions and surface characterization of superhydrophilic polymer brushes with zwitterion side groups. Soft Matter. 2013;9:5138–48.
Krasowska M, Zawala J, Malysa K. Air at hydrophobic surfaces and kinetics of three phase contact formation. Adv Colloid Interface Sci. 2009;147-148:155–69.
Wang JH, Bartlett JD, Dunn AC, Small S, Willis SL, Driver MJ, Lewis AL. The use of rhodamine 6G and fluorescence microscopy in the evaluation of phospholipid‐based polymeric biomaterials. J Microsc. 2005;217:216–24.
This work was financially supported by a Grant-in-Aid for Scientific Research (17H03071 and 16K14008) from the Japan Society for the Promotion of Science (JSPS), JSPS Bilateral Joint Research Projects, and the Cooperative Research Program of “Network Joint Research Center for Materials and Devices (20174031).”
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
About this article
Cite this article
Honda, T., Nakao, A., Ishihara, K. et al. Polymer coating glass to improve the protein antifouling effect. Polym J 50, 381–388 (2018). https://doi.org/10.1038/s41428-018-0026-x
ACS Applied Bio Materials (2020)
Fluorinated vs. Zwitterionic-Polymer Grafted Surfaces for Adhesion Prevention of the Fungal Pathogen Candida albicans
Novel Fe3O4 based superhydrophilic core-shell microspheres for breaking asphaltenes-stabilized water-in-oil emulsion
Chemical Engineering Journal (2019)
Journal of Materials Chemistry B (2019)
Chemistry Letters (2018)