表面氧化是一种常用的高分子生物材料表面改性方法，可提升表面的亲水性和生物相容性，并为材料的后续功能化修饰提供活化位点。以TEMPO为代表的氮氧自由基作为电子传递剂可介导水相中的催化氧化反应，通过将TEMPO固定于水溶性高分子载体，并使用漆酶作为催化剂，可实现对含伯醇生物材料表面的选择性氧化，所生成的醛基或羧基可作为后续表面功能化修饰的起点。本项目基于申请人前期工作基础，将TEMPO以不同比例接枝于不同带电性、分子量的水溶性高分子上，拟利用“漆酶/高分子接枝TEMPO/氧气”体系对聚甲基丙烯酸羟乙酯和聚(聚乙二醇甲基丙烯酸酯)等含伯醇生物材料进行表面氧化，探索该反应电子传递机理，明确反应速率的控制步骤，寻找反应条件与氧化产物间的规律，并考察催化体系循环利用的可行性。此类新型表面氧化反应的机理、规律与方法，可为高分子生物材料的表面修饰、活化与功能拓展提供新途径。

Surface oxidation is a commonly used surface modification method for macromolecular biomaterials, which can increase the surface hydrophilicity and biocompatibility, and provide active sites for subsequent functional modifications. The nitroxyl radical, as represented by TEMPO, could act as an electron transfer mediator in the catalytic oxidation reaction in the aqueous phase. By immobilizing TEMPO on a water-soluble polymer carrier and using laccase as a catalyst, the surface of biomaterials containing primary alcohol can be selectively oxidized. The resulting aldehyde or carboxyl groups can be used as a starting point for subsequent functional modifications of the surface. Based on the previous work of the applicant, this project plans to graft TEMPO onto differently charged water soluble polymers with different molecular weight and different degrees of substitution. The laccase/TEMPO-grafted polymer/oxygen system is employed for the surface oxidation of poly(2-hydroxyethyl methacrylate) and poly[poly(ethylene glycol) methacrylate]. We will explore the electron transfer mechanism of the reaction, clarify the control step of reaction rate, find the laws between reaction conditions and oxidation products, and investigate the feasibility of recycling the catalytic system. The mechanism, rules and methods found in this novel surface oxidation reaction can provide new ways for the modification, activation and function expansion for the surface of polymeric biomaterials.