含硫正离子聚类肽水凝胶的合成与性能  

Synthesis and Properties of Polypeptoid Hydrogels Containing Sulfonium Groups

作　　者：颜舒婷 姚远[1] 陶鑫峰 林绍梁[1] YAN Shuting;YAO Yuan;TAO Xinfeng;LIN Shaoliang(Shanghai Key Laboratory of Advanced Polymeric Materials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学材料科学与工程学院,上海市先进聚合物材料重点实验室,上海200237

出　　处：《高等学校化学学报》2022年第11期212-220,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21901073,52073092);上海市自然科学基金(批准号:19ZR1412100);上海市晨光计划项目(批准号:18CG32)资助。

摘　　要：通过伯胺引发肌氨酸-N-硫代羧酸酐(Sar-NTA)和N-烯丙基甘氨酸-N-硫代羧酸酐(NGA-NTA)的开环聚合制备了一种三嵌段聚类肽,即聚(N-烯丙基甘氨酸)-b-聚肌氨酸-b-聚(N-烯丙基甘氨酸)(PNAG-b-PSar-b-PNAG,简称PASA);然后通过PASA侧链上的烯丙基与3,6-二氧杂-1,8-辛烷二硫醇之间的巯-烯“点击”化学反应合成了不同肌氨酸(Sar)摩尔分数的聚类肽水凝胶(HG).巯-烯“点击”反应生成的大量硫醚基团可进一步与环氧化合物反应,在水凝胶的网络骨架中生成硫正离子,从而获得具有固有抗菌能力的含硫正离子聚类肽水凝胶(S+HG).S+HG具有优异的吸水能力,能够在1 min内达到吸水平衡,饱和溶胀率高达2024%.S+HG内部由大量规则的连续海绵孔状结构组成,能够承受一定的剪切、摩擦及挤压等外界应力.S+HG具有强效的广谱抗菌能力,对革兰氏阴性的大肠杆菌(E.coli)和革兰氏阳性的金黄色葡萄球菌(S.aureus)的抗菌率都在99.99%以上.Triblock copolypeptoid poly(N-allylglycine)-b-polysarcosine-b-poly(N-allylglycine)(PASA)was prepared by primary amine-initiated controlled ring-opening polymerization of sarcosine N-thiocarboxyanhydride(Sar-NTA)and N-allylglycine N-thiocarboxyanhydride(NAG-NTA).Followed by cross-linking via thiol-ene click reaction between the allyl groups on the PASA side chains and thiols groups on 3,6-dioxa-1,8-octanedithiol,polypeptoid hydrogels(HG)with different molar fraction of sarcosine(Sar),HG-Sar49%and HG-Sar64%,were obtained.A large amount of thioether groups were formed through the thiol-ene click reaction,which could further react with epoxide compounds to generate sulfonium groups on the network of PASA hydrogels.Thus,sulfoniumcontaining polypeptoid hydrogels(S+HG)with intrinsic antibacterial properties were successfully prepared.S+HG showed fast and excellent water absorption ability,which reached the water absorption balance within 1 min and had a saturation swelling rate up to 2024%.S+HG was composed of regular continuous sponge-like structures,and could withstand certain external stresses such as shearing,friction and extrusion.S+HG exhibited strong broad-spectrum antibacterial ability,and the antibacterial rates against gram-negative Escherichia coli(E.coli)and gram-positive Staphylococcus aureus(S.aureus)were over 99.99%.

关 键 词：聚类肽 N-硫代羧酸酐 水凝胶 抗菌能力 硫正离子 

分 类 号：O631[理学—高分子化学]