Abstract
We studied the effect of polymer design on the interfacial structure and physical properties of polymer films in water based on a poly(vinyl ether) platform with hydrophilic side-chains to construct bioinert interfaces. Initially, we explored how to prepare hydrophilic surfaces using poly(vinyl ether)s, utilizing the preferential segregation of a rubbery component in a diblock copolymer film with a glassy component, crosslinking a hydrophilic polymer, and designing an interfacial modifier with a special architecture. Characterizing the interfacial structure and physical properties of the obtained polymer films in water revealed that a small difference in the side-chain structure significantly impacts the resultant interfacial properties of the polymers, leading to excellent blood compatibility. Furthermore, we demonstrate that swelling behaviors, which are related to chain dynamics, at the water interface play a key role in determining bioinert properties.
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References
Cabral H, Miyata K, Osada K, Kataoka K. Block copolymer micelles in nanomedicine applications. Chem Rev. 2018;118:6844–92.
Zhang J, Liu K, Müllen K, Yin M. Self-assemblies of amphiphilic homopolymers: synthesis, morphology studies and biomedical applications. Chem Commun. 2015;51:11541–55.
Wei Q, Becherer T, Angioletti-Uberti S, Dzubiella J, Wischke C, Neffe AT, et al. Protein interactions with polymer coatings and biomaterials. Angew Chem Int Ed. 2014;53:8004–31.
Hasegawa H, Hashimoto T. Morphology of block polymers near a free surface. Macromolecules. 1985;18:589–90.
Russel TP, Coulon G, Deline VR, Miller DC. Characteristics of the surface-induced orientation for symmetric diblock PS/PMMA copolymers. Macromolecules. 1989;22:4600–6.
Tanaka K, Takahara A, Kajiyama T. Surface molecular motion in thin films of poly(styrene-block-methyl methacrylate) diblock copolymer. Acta Polym. 1995;46:476–82.
Mori H, Hirao A, Nakahama S. Synthesis and surface characterization of hydrophilic-hydrophobic block copolymers containing poly(2,3-dihydroxypropyl methacrylate). Macromolecules. 1994;27:4093–100.
Hariharan A, Kumar SK, Russell TP. Reversal of the isotopic effect in the surface behavior of binary polymer blends. J Chem Phys. 1993;98:4163–73.
Tanaka K, Takahara A, Kajiyama T. Effect of polydispersity on surface molecular motion of polystyrene films. Macromolecules. 1997;30:6626–32.
Yethiraj A. Entropic and enthalpic surface segregation from blends of branched and linear polymers. Phys Rev Lett. 1995;74:2018–21.
Walton DG, Soo PP, Mayes AM, Sofia Allgor SJ, Fujii JT, Griffith LG, et al. Creation of stable poly(ethylene oxide) surfaces on poly(methyl methacrylate) using blends of branched and linear polymers. Macromolecules. 1997;30:6947–56.
Tateishi Y, Kai N, Noguchi H, Uosaki K, Nagamura T, Tanaka K. Local conformation of poly(methyl methacrylate) at nitrogen and water interfaces. Polym Chem. 2010;1:303–11.
Horinouchi A, Atarashi H, Fujii Y, Tanaka K. Dynamics of water-induced surface reorganization in poly(methyl methacrylate) films. Macromolecules. 2012;45:4638–42.
Oda Y, Horinouchi A, Kawaguchi D, Matsuno H, Kanaoka S, Aoshima S, et al. Effect of side-chain carbonyl groups on the interface of vinyl polymers with water. Langmuir. 2014;30:1215–19.
Dhopatkar N, Anim-Danso E, Peng C, Singla S, Liu X, Joy A, et al. Reorganization of an amphiphilic glassy polymer surface in contact with water probed by contact angle and sum frequency generation spectroscopy. Macromolecules. 2018;51:5114–20.
Tamada Y, Ikada Y. Effect of preadsorbed proteins on cell adhesion to polymer surfaces. J Colloid Interface Sci. 1993;155:334–9.
Arima Y, Iwata H. Effect of wettability and surface functional groups on protein adsorption and cell adhesion using well-defined mixed self-assembled monolayers. Biomaterials. 2007;28:3047–82.
Tanaka M, Motomura T, Kawada M, Anzai T, Kasori Y, Shiroya T, et al. Blood compatible aspects of poly(2-methoxyethylacrylate) (PMEA) relationship between protein adsorption and platelet adhesion on PMEA surface. Biomaterials. 2000;21:1471–81.
Hayashi T, Tanaka Y, Koide Y, Tanaka M, Hara M. Mechanism underlying bioinertness of self-assembled monolayers of oligo(ethyleneglycol)-terminated alkanethiols on gold: protein adsorption, platelet adhesion, and surface forces. Phys Chem Chem Phys. 2012;14:10196–206.
Seo JH, Kakinoki S, Inoue Y, Nama K, Yamaoka T, Ishihara K, et al. The significance of hydrated surface molecular mobility in the control of the morphology of adhering fibroblasts. Biomaterials. 2013;34:3206–14.
Hirata T, Matsuno H, Kawaguchi D, Hirai T, Yamada NL, Tanaka M, et al. Effect of local chain dynamics on a bioinert interface. Langmuir. 2015;31:3661–7.
Hirata T, Matsuno H, Kawaguchi D, Inutsuka M, Hirai T, Tanaka M, et al. Dynamics of a bioinert polymer in hydrated states by dielectric relaxation spectroscopy. Phys Chem Chem Phys. 2017;19:1389–94.
Fujii Y, Akabori K, Tanaka K, Nagamura T. Chain conformation effects on molecular motions at the surface of poly(methyl methacrylate) films. Polym J. 2007;39:928–34.
Aoshima S, Oda H, Kobayashi E. Synthesis of thermally-induced phase separating polymer with well-defined polymer structure by living cationic polymerization. I. Synthesis of poly(vinyl ether)s with oxyethylene units in the pendant and its phase separation behavior in aqueous solution. J Polym Sci, Part A: Polym Chem. 1992;30:2407–13.
Takishita H, Kanazawa A, Kanaoka S, Aoshima S. Design and synthesis of thermo- responsive films with high sensitivity: effects of primary architectures of diblock copolymers and conditions for film formation. Kobunshi Ronbunshu. 2012;69:305–8.
Aoshima S, Kanaoka S. A renaissance in living cationic polymerization. Chem Rev. 2009;109:5245–87.
Jones RAL, Richards RW. Polymers at surfaces and interfaces. Cambridge: Cambridge University Press; 1999.
Zhang C, Oda Y, Kawaguchi D, Kanaoka S, Aoshima S, Tanaka K. Dynamic-driven surface segregation of a hydrophilic component in diblock copolymer films. Chem Lett. 2015;44:166–8.
Oda Y, Zhang C, Kawaguchi D, Matsuno H, Kanaoka S, Aoshima S, et al. Design of blood-compatible interfaces with poly(vinyl ether)s. Adv Mater Interfaces. 2016;3:1600034.
Hirata T, Matsuno H, Tanaka M, Tanaka K. Surface segregation of poly(2-methoxyethyl acrylate) in a mixture with poly(methyl methacrylate). Phys Chem Chem Phys. 2011;13:4928–34.
Knoll A, Horvat A, Lyakhova KS, Krausch G, Sevink GJA, Zvelindovsky AV, et al. Phase behavior in thin films of cylinder-forming block copolymers. Phys Rev Lett. 2002;89:035501.
Stoykovich MP, Müller M, Kim SO, Solak HH, Edwards EW, de Pablo JJ, et al. Directed assembly of block copolymer blends into nonregular device-oriented structures. Science. 2005;308:1442–6.
Aoshima S, Hasegawa O, Higashimura T. Living cationic polymerization of vinyl ethers with a functional group. 2. Polymerization of vinyl ethers with an unsaturated ester pendant. Polym Bull. 1985;13:229–35.
Sugihara S, Ohashi M, Ikeda I. Synthesis of fine hydrogel microspheres and capsules from thermoresponsive coacervate. Macromolecules. 2007;40:3394–401.
Sakaguchi T, Ohashi M, Shimada K, Hashimoto T. Synthesis and gas permeability of membranes of poly(vinyl ether)s bearing oxyethylene segments. Polym (Guildf). 2012;53:1659–64.
Itagaki N, Oda Y, Hirata T, Nguyen HK, Kawaguchi D, Matsuno H, et al. Surface characterization and platelet adhesion on thin hydrogel films of poly(vinyl ether). Langmuir. 2017;33:14332–39.
Sneddon IN. The relation between load and penetration in the axisymmetric boussinesq problem for a punch of arbitrary profile. Int J Eng Sci. 1965;3:47–57.
Johnson KL, Greenwood JA. An adhesion map for the contact of elastic spheres. J Colloid Interface Sci. 1997;192:326–33.
Nakajima K, Ito M, Wang D, Liu H, Nguyen HK, Liang X, et al. Nano-palpation AFM and its quantitative mechanical property mapping. Microscopy. 2014;63:193–208.
Atarashi H, Ariura F, Akabori K, Tanaka A, Ozawa M, Tanaka K, et al. Interfacial segregation of hyper-branched polystyrene in mixtures of linear component. Trans Mater Res Soc Jpn. 2007;32:231–4.
Matyjaszewski K, Tsarevsky NV. Macromolecular engineering by atom transfer radical polymerization. J Am Chem Soc. 2014;136:6513–33.
Aoshima S, Sugihara S. Syntheses of stimuli-responsive block copolymers of vinyl ethers with side oxyethylene groups by living cationic polymerization and their thermosensitive physical gelation. J Polym Sci Part A: Polym Chem. 2000;38:3962–5.
Sugimoto S, Oda Y, Hirata T, Matsuyama R, Matsuno H, Tanaka K. Surface segregation of a branched polymer with hydrophilic poly[2-(2-ethoxy)ethoxyethyl vinyl ether] side chains. Polym Chem. 2017;8:505–10.
Grimaud T, Matyjaszewski K. Controlled/“living” radical polymerization of methyl methacrylate by atom transfer radical polymerization. Macromolecules. 1997;30:2216–8.
Hasegawa M, Kitano H. Adsorption kinetics of proteins onto polymer surfaces as studied by the multiple internal reflection fluorescence method. Langmuir. 1992;8:1582–6.
Acknowledgements
The author would like to express sincere gratitude to Prof. Keiji Tanaka, Prof. Hisao Matsuno, and Prof. Daisuke Kawaguchi (Kyushu University) for their continuous encouragement and constructive discussions throughout this work. The author also deeply appreciates great contributions to this work from Dr. Ayanobu Horinouchi, Dr. Cui Zhang, Dr. Shin Sugimoto, Ms. Nozomi Itagaki, and Dr. Hung Kim Nguyen (Kyushu University) and would like to thank Prof. Sadahito Aoshima (Osaka University) and Prof. Shokyoku Kanaoka (The University of Shiga Prefecture) for collaborations. Special thanks to the Asylum Research, Oxford Instruments Company for support. This research was partly supported by JSPS KAKENHI, Grant-in-Aid for Young Scientists (B), Grant Number JP16K17917 and The Mazda Foundation.
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Oda, Y. Construction of hydrophilic surfaces with poly(vinyl ether)s and their interfacial properties in water. Polym J 51, 955–962 (2019). https://doi.org/10.1038/s41428-019-0215-2
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DOI: https://doi.org/10.1038/s41428-019-0215-2
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