【作者】 胡建新；

【导师】 李巍； 吴静波；

【作者基本信息】 天津大学 ， 化学工程（专业学位）， 2017， 硕士

【摘要】 卟啉-多肽超分子的组装以及应用在最近几年内得到了快速发展,是一个新兴的前沿领域。相关研究表明,卟啉-多肽超分子组装结构的形成与其分子内和分子间相互作用力紧密相关,可通过分子组装技术构筑具有特定结构和功能的超分子体系。而对卟啉-多肽类分子组装进行调控,开发卟啉-多肽类纳米材料,在生物传感、药物治疗等方面展示出巨大的应用潜力。因此,设计合成具有生物活性的卟啉-多肽化合物,通过不同手段调控其微观形貌,制备具有生物活性的纳米材料具有重要意义。本文采用液相合成的方法在卟啉环上引入氨基酸序列,合成了新型的卟啉-六肽化合物TPP-Ala-Ala-MV。通过HPLC进行了分离提纯,采用MALDI-TOF和~1H NMR对其进行了表征和分析,确认了其结构,并且对相关反应进行了优化。本文通过不同的手段(pH、溶剂、结合方式和磁力搅拌),研究了卟啉-六肽化合物在DMSO/水、HFIP/水和TMG/水体系中的自组装行为,达到形貌调控的目的。并且通过SEM、TEM、UV-vis、CD和XRD的表征对不同形貌变化进行了分析。研究结果表明,p H在1-12范围内,内部离子形式的不同改变了其静电相互作用,影响卟啉的聚集方式和多肽的β-折叠,使其在DMSO/水体系中形貌从纳米蜂窝向纳米花瓣和纳米纤维结构变化。有机溶剂具有不同的提供/接受氢键能力,进而影响多肽间的氢键相互作用,形成α-螺旋和β-折叠的自组装体。共价结合自组装体现出卟啉和多肽协同作用,非共价结合更多的体现出多肽间相互作用;磁力搅拌产生的剪切力更有利于形成均一稳定的自组装形貌。更多还原

【Abstract】 In recent years,the assembly and application of porphyrin-peptide supramolecule have got the fast development,which is a rising front field.Many related studies show that the formation of supramolecular structure of porphyrin-polypeptide is closely related to its interaction force,which can construct the specific structure and functional meterials.It is of great application potential in the field of biosensors and drug therapy to develop porphyrin-polypeptide nanomaterials by controlling the porphyrin-polypeptide assembly.Therefore,it has great significance to design and synthesize biologically active porphyrin-polypeptide compounds which can be used to control the morphology.In this paper,we synthesized and characterized the porphyrin-hexapeptide compound which the amino acid sequence was attached to the porphyrin ring by liquid-phase synthesis.We finally got the porphyrin-hexapeptide by the test of HPLC,MALDI-TOF and ~1H NMR,meanwhile we had optimized the related reactions.In order to achieve the purpose of shape control,we through co-solution self-assembly analyzed the effects of different conditions(pH,solvent,binding and stirring)to morphology of porphyrin-hexapeptide compound in DMSO/water,HFIP/water and TMG/water system.In addition,we analyzed the reasons for the change of morphology by SEM,TEM,UV-vis,CD and XRD.Under the different pH situations,the internal ion changes the electrostatic interaction in order to effect the aggregation of porphrin and secondary structure of polypeptides,which the morphology changes from honeycomb to nanoflower and nanofiber structure in DMSO/water system.Organic solvents have different ability to provide/accept hydrogen bonds,affect the hydrogen bonding interactions between peptides,which we can obtained different morphologies because of different secondary structure.The covalent binding self-assembly reflects the cooperation of porphyrin-polypeptide,and the non covalent binding is more likely to reflect the template of the polypeptide.The shear force produced by magnetic stirring is beneficial to form stable and well-distributed self-assembled morphologies.更多还原