Chen Yangjun, Diaz-Dussan Diana, Wu Di, Wang Wenda, Peng Yi-Yang, Asha Anika Benozir, Hall Dennis G, Ishihara Kazuhiko, Narain Ravin
Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
ACS Macro Lett. 2018 Aug 21;7(8):904-908. doi: 10.1021/acsmacrolett.8b00434. Epub 2018 Jul 12.
Boronic ester, one typical example of dynamic covalent bonds, has presented great potential to prepare self-healing hydrogels. However, most of currently reported hydrogels based on boronic esters are formed at pH > 8, which impeded their further use in physiological conditions. In this study, we designed two kinds of zwitterionic copolymers with benzoxaborole and catechol pendant groups, respectively. Owing to the lower p value of benzoxaborole (7.2), gelation can happen easily at pH 7.4 PBS after mixing these two copolymers due to efficient formation of benzoxaborole-catechol complexations. The resulting hydrogels exhibited excellent self-healing property as well as dual pH/sugar responsiveness due to the dynamic nature of boronic ester. Moreover, benefiting from the cell membrane bioinspired 2-methacryloyloxyethyl phosphorylcholine (MPC)-based polymeric matrix, the hydrogel was further investigated for 3D cell encapsulation. The combination of biocompatible zwitterionic polymers with dynamic benzoxaborole-catechol complexation makes the hydrogels a promising platform for diverse potential bioapplications like drug delivery and tissue engineering.
硼酸酯作为动态共价键的一个典型例子,在制备自愈合水凝胶方面展现出了巨大潜力。然而,目前报道的大多数基于硼酸酯的水凝胶是在pH > 8的条件下形成的,这阻碍了它们在生理条件下的进一步应用。在本研究中,我们分别设计了两种带有苯并氧杂硼杂环戊二烯和儿茶酚侧基的两性离子共聚物。由于苯并氧杂硼杂环戊二烯的pKa值较低(7.2),在将这两种共聚物混合后,由于苯并氧杂硼杂环戊二烯 - 儿茶酚络合物的有效形成,在pH 7.4的磷酸盐缓冲盐溶液(PBS)中很容易发生凝胶化。由于硼酸酯的动态性质,所得水凝胶表现出优异的自愈合性能以及双重pH/糖响应性。此外,受益于受细胞膜启发的基于2-甲基丙烯酰氧基乙基磷酰胆碱(MPC)的聚合物基质,对该水凝胶进行了三维细胞封装的进一步研究。生物相容性两性离子聚合物与动态苯并氧杂硼杂环戊二烯 - 儿茶酚络合的结合,使水凝胶成为药物递送和组织工程等多种潜在生物应用的有前景的平台。