含有锂皂土/聚多巴胺复合纳米微粒的再生丝蛋白水凝胶  

Regenerated Silk Fibroin Hydrogel with Laponite/Polydopamine Composite Nanoparticles

作　　者：达高欢 马易群[2] 林沁睿 邵正中[1] Gao-huan Da;Yi-qun Ma;Qin-rui Lin;Zheng-zhong Shao(State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science,Laboratory of Advanced Materials,Fudan University,Shanghai 200433;Zhongshan Hospital,Fudan University,Shanghai 200032)

机构地区：[1]聚合物分子工程国家重点实验室复旦大学先进材料实验室高分子科学系,上海200433 [2]复旦大学附属中山医院,上海200032

出　　处：《高分子学报》2023年第1期95-105,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21935002)资助项目.

摘　　要：在辣根过氧化物酶/过氧化氢酶促交联(化学交联)制备再生丝蛋白化学交联凝胶的过程中,通过引入锂皂土/聚多巴胺复合纳米材料作为第二组分,以调节反应并提高化学交联效率;再经乙醇熟化后,再生丝蛋白化学交联凝胶中可进一步形成物理网络,进而得到双交联凝胶.结果表明,第二组分的引入不仅能够提高再生丝蛋白化学交联水凝胶的力学性能,并有利于后续均匀物理交联网络的形成,致使最终所得双交联水凝胶具有更好的力学性能.同时,由此制备的双交联水凝胶传承了再生丝蛋白良好的生物相容性以及与交联结构密切相关的生物降解性,并具备了诱导干细胞成骨分化的能力,因而在软骨修复等领域具有潜在的应用价值.Regenerated silk fibroin(RSF)hydrogel has been widely used in the field of tissue engineering due to its good biocompatibility,degradability and low immunogenicity.It shows a good application prospect in the field of cartilage repair.However,as a natural polymer hydrogel,the strength of RSF hydrogel is difficult to match with cartilage.In this study,during the preparation of RSF chemical crosslinked hydrogel by horseradish peroxidase(HRP)/hydrogen peroxide(H2O2)enzymatic crosslinking,laponite(LAP)/polydopamine(PDA)composite nanomaterials were introduced as a second component to adjust the reaction and improve the chemical crosslinking efficiency.Compared with the pure RSF chemically crosslinked hydrogel,the mechanical properties of the composite hydrogel were significantly improved after the addition of LAP/PDA composite nanomaterials,and the compression modulus was improved by about 70%.This is mainly because the LAP/PDA composite nanomaterials inhibited the“curling”of silk protein molecular chains in the crosslinking process by participating in the enzymatic crosslinking reaction,and increased the chemical crosslinking points in the crosslinked network.After soaking in ethanol,physical crosslinked network can be further formed in RSF chemical crosslinked hydrogel to obtain a double crosslinked hydrogel.The increase of chemical crosslinking points in the RSF-LAP/PDA chemical crosslinked hydrogel was beneficial to decreasing the dimensions and improving the distribution uniformity of theβ-sheet domains formed during ethanol ripening,such that the mechanical properties of the final double crosslinked hydrogel were greatly improved.This double crosslinked method can effectively solve the problem of mechanical properties degradation caused by inhomogeneous crosslinked network when preparing RSF hydrogel with high solid content,and improve the stability of regenerated silk fibroin based hydrogel as implant repair materials in vivo.In vitro study showed that the RSF-LAP/PDA double crosslinked hydrogel had excelle

关 键 词：丝蛋白 水凝胶 酶交联 物理交联 双交联 

分 类 号：TQ427.26[化学工程] R318.08[医药卫生—生物医学工程]