单链-Gemini结构变化对多肽表面活性剂自组装行为的影响
首发时间:2012-01-18
摘要:通过Cys残基在阴离子型多肽表面活性剂分子V3C中引入巯基,然后巯基之间氧化连接形成二硫键,成功制备了完全氨基酸构成的Gemini型多肽表面活性剂V3C-CV3。进一步运用电导测定、红外光谱、原子力显微镜、pH滴定等多种技术手段研究了分子结构改变前后分子基本性质和自组装行为的变化。V3C单体分子含有巯基和羧基两个pH敏感可带电基团,其临界聚集浓度为0.16 mM,在云母片上组装为膜状结构,二级结构中β折叠含量达61.2%。分子转变为Gemini结构V3C-CV3之后,临界聚集浓度极大降低,约为0.02 mM,自组装体则变得更为规整,为细小的纤维状结构,同时,组装体中β折叠含量也大大提高,约为76.9%。因为结构变化前后分子pKa值变化很小,推测各基团空间构象的变化而不是分子带电情况的变化是引起分子基本性质和自组装行为明显改变的根本原因。
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Effect of Monomer-to-Gemini Structural Change on the Self-Assembly of Peptide Surfactant
Abstract:The anionic peptide surfactant V3C that bearing hydrosulfide group was produced by introducing Cys residue into the molecule. Then by oxidation of hydrosulfide groups to form disulfide bond, a Gemini peptide surfactant V3C-CV3 was successfully synthesized. The self-assembly behaviors before and after structural change were investigated by techniques of electric conductivity measurement, fourirer transformed infrared spectroscopy, atomic force microscopy, and pH titration. V3C monomers contains pH-sensitive hydrosulfide and carboxyl groups, which can be charged via protonation/deprotonation. It shows critical aggregation concentration (CAC) of 0.16 mM and self-assembles to form membrane on the mica surface. The secondary structures contain 61.2 percent of beta-sheet. When the molecule transformed to Gemini structure of V3C-CV3, the CAC decreases greatly to be only 0.02 mM. The molecular self-assembly turns to be more orderd to form tiny fibers. Simutaneously beta-sheet content in the secondary structure increases to be about 76.9 percent. Since the pKa shows almost no variation before and after the molecular structural change, it is believed that the different self-assembly behaviors are resulted from change in configuration of each functional group while not change in charge of the molecule.
Keywords: Peptide surfactants Self-assembly Monomer Gemini
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