【摘要】 用开环聚合法合成了端基分别为巯基和马来酰亚胺基团的聚己内酯,利用马来酰亚胺与巯基的迈克尔加成反应和巯基之间的偶联反应,合成了两种端基为谷胱甘肽的聚己内酯(GS-PCL和GSS-PCL),利用核磁共振氢谱和凝胶渗透色谱表征了两亲性聚己内酯的结构.研究了这两种聚己内酯在水中的聚集行为,发现这两种聚已内酯都可在一定pH值下聚集形成球形胶束,胶束的形态、大小等受pH影响;同时,由GSS-PCL形成的聚集体还表现出氧化还原敏感性.更多还原

【Abstract】 Two kinds of end-functionalized poly（ε-caprolactone）s,maleimido-PCL and HS-PCL,were synthesized by the ring-opening polymerization of ε-caprolactone （ε-CL） with N-hydroxyl ethyl maleimide （HEME） and 2-mercaptoethanol （ME） as initiators,respectively.Polymerizations were catalyzed by tin （Ⅱ） trifluoromethane （Sn（OTf）₂） in bulk under mild conditions.These polymers showed low polydispersities and have functional groups at both ends.Two glutathione-terminated poly（ε-caprolactone） （GS-PCL and GSS-PCL） were then synthesized by Michael addition reaction of the maleimido-PCL with glutathione,or the coupling reaction of HS-PCL with glutathione,respectively.The structures of the two amphiphilic polyesters were confirmed by ¹H-NMR and GPC measurements.Glutathione groups on the chain end increased the hydrophilicity of PCL,therefore,the polyesters can self-assemble in aqueous buffer solutions.Transmission electron microscopy （TEM） measurements confirmed the formation of spherical aggregates with the diameter range from 20～80 nm,and the size of the aggregates was found to increase with the decease of the pH of the buffer.In addition,aggregates from GSS-PCL showed redox-sensitive properties.更多还原