Altering the bio-inert properties of surfaces by fluorinated copolymers of mPEGMA

Ryohei Koguchi; Katja Jankova; Yukiko Tanaka; Aki Yamamoto; Daiki Murakami; Qizhi Yang; Bruno Ameduri; Masaru Tanaka

doi:10.1016/j.bioadv.2023.213573

Altering the bio-inert properties of surfaces by fluorinated copolymers of mPEGMA

Biomater Adv. 2023 Oct:153:213573. doi: 10.1016/j.bioadv.2023.213573. Epub 2023 Jul 28.

Authors

Ryohei Koguchi¹, Katja Jankova², Yukiko Tanaka³, Aki Yamamoto³, Daiki Murakami³, Qizhi Yang⁴, Bruno Ameduri⁵, Masaru Tanaka⁶

Affiliations

¹ AGC Inc. Organic Materials Division, Materials Integration Laboratories, 1-1 Suehiro-cho, Tsurumi-ku, Yokohama, Kanagawa 230-0045, Japan.
² Soft Materials Chemistry, Institute for Materials Chemistry and Engineering, Kyushu University, Build. CE41, 744 Motooka Nishi-ku, Fukuoka 819-0395, Japan; Department of Energy Conversion and Storage, Technical University of Denmark, Elektrovej, Build. 375, 2800 Kongens Lyngby, Denmark.
³ Soft Materials Chemistry, Institute for Materials Chemistry and Engineering, Kyushu University, Build. CE41, 744 Motooka Nishi-ku, Fukuoka 819-0395, Japan.
⁴ University of Montpellier, ICGM, CNRS, ENSCM, 34000 Montpellier, France.
⁵ University of Montpellier, ICGM, CNRS, ENSCM, 34000 Montpellier, France. Electronic address: bruno.ameduri@enscm.fr.
⁶ Soft Materials Chemistry, Institute for Materials Chemistry and Engineering, Kyushu University, Build. CE41, 744 Motooka Nishi-ku, Fukuoka 819-0395, Japan. Electronic address: masaru_tanaka@ms.ifoc.kyushu-u.ac.jp.

PMID: 37562157
DOI: 10.1016/j.bioadv.2023.213573

Abstract

Hydrophilic materials display "bio-inert properties", meaning that they are less recognized as foreign substances by proteins and cells. Such materials are often water soluble; therefore, one general approach to enable the use of these materials in various applications deals with copolymerizing hydrophilic monomers with hydrophobic ones to facilitate such resulting copolymers water insoluble. However, reducing the hydrophilic monomer amount may reduce the bio-inert properties of the material. The decrease in bio-inert properties can be avoided when small amounts of fluorine are used in copolymers with hydrophilic monomers, as presented in this article. Even in small quantities (7.9 wt%), the fluorinated monomer, 1,1,1,3,3,3-hexafluoropropan-2-yl 2-fluoroacrylate (FAHFiP), contributed to the improved hydrophobicity of the polymers of the long side-chain poly(ethylene glycol) methyl ether methacrylate (mPEGMA) bearing nine ethylene glycol units turning them water insoluble. As evidenced by the AFM deformation image, a phase separation between the FAHFiP and mPEGMA domains was observed. The copolymer with the highest amount of the fluorinated monomer (66.2 wt%) displayed also high (82 %) FAHFiP amount at the polymer-water interface. In contrast, the hydrated sample with the lowest FAHFiP/highest mPEGMA amount was enriched of three times more hydrophilic domains at the polymer-water interface compared to that of the sample with the highest FAHFiP content. Thus, by adding a small FAHFiP amount to mPEGMA copolymers, water insoluble in the bulk too, could be turned highly hydrophilic at the water interface. The high content of intermediate water contributed to their excellent bio-inert properties. Platelet adhesion and fibrinogen adsorption on their surfaces were even more decreased as compared to those on poly(2-methoxyethyl acrylate), which is typically used in medical devices.

Keywords: Bio-inert properties; Fluorinated copolymers; Hydration structure; Intermediate water; Platelet adhesion; mPEGMA.

MeSH terms

Polyethylene Glycols* / chemistry
Polymers*
Surface Properties
Water / chemistry

Substances

Polymers
polyethylene glycol methacrylate
Polyethylene Glycols
Water