多肽自组装材料的物理力学性质及其应用

发布时间：2018-03-24 15:36

本文选题：多肽自组装　切入点：超分子　出处：《南京大学》2017年博士论文

【摘要】：多肽分子自组装材料在近些年引起了越来越多研究者的关注,逐渐在生物材料,环境材料,医学材料等新材料领域成为热点,大放异彩。多肽分子处于特定的条件和环境中,可以在氢键,疏水相互作用,π-π堆积作用,离子互补相互作用等的驱动下形成高度有序的复杂的组装结构。通过设计自组装多肽的序列,控制组装条件和过程,能够得到各种表现形式的自组装多肽材料,例如多肽水凝胶,多肽纳米管,多肽纳米球,多肽晶体,多肽纤维等等。由于多肽材料极为优秀的生物相容性,可降解性和简单的合成制备步骤,自组装多肽材料在光吸收材料,3D打印材料,软材料致动器,可控药物释放,超分子水凝胶等方面具有巨大的应用前景。本论文研究了多肽自组装材料的物理和力学性质及其在光吸收催化体系,光致发光体系,超分子水凝胶和双网络水凝胶体系中的设计和应用,主要内容包括:第一,基于多肽自组装的光吸收体系和催化材料。主要研究了分别基于氨基酸序列为苯丙氨酸-苯丙氨酸(FF)和卟琳-苯丙氨酸-苯丙氨酸(MCpP-FF)的两种多肽自组装结构的光吸收体系,包括自组装结构的形成机理,微观结构,光学性质,结合了电子供体和受体的光吸收催化反应速率,效率和重复性等内容,建立了高效的光吸收催化体系和人工模拟光合作用的系统,这两种光吸收体系对于NAD+到NADH的催化反应效率均达到了 25%以上,并且其中MCpP-FF的五次循环使用效率保持在60%以上,相比于其他的光吸收体系具备高效,可重复使用,生物相容性高等优势。第二,基于多肽自组装的光吸收和光致发光水凝胶材料。主要研究了基于二联吡啶-苯丙氨酸-谷氨酸-苯丙氨酸-赖氨酸-苯丙氨酸-谷氨酸-苯丙氨酸-赖氨酸(Bpy-FEFKFEFK,简称EFK-Bpy)自组装和金属离子配位相互作用形成胶联的水凝胶,包括其制备方法,化学结构,力学特性,光学性质,微观结构等,给出了使用该种类水凝胶材料作为光致发光软物质光源的相关应用。使用该种多肽水凝胶作为光致发光平台,在可以进行各种颜色光致发光的同时还可以受激发射纯净白光光源,白光CIE值为(0.33,0.33),同时还有具备可自修复,水中可正常工作等特点,可打印等特性,展现了其用于可编辑的3D打印材料和光致发光软材料方面的巨大应用前景。第三,自组装多肽在二级结构与铝离子的直接结合研究及其组成水凝胶的应用。主要研究了分别基于EFK8(N-FEFEFKFK-C,简称EFK8-Ⅰ型,N-FEFKFEFK-C,简称 EFK8-Ⅱ 型,N-KFKFEFEF-C,简称 KFE-Ⅰ 型和N-KFEFKFEF-C,简称KFE-Ⅱ型)的自组装多肽水凝胶对于铝离子的特异性结合,包括离子结合对多肽自组装纤维结构,二级结构,自组装速率,水凝胶的物理力学性质的影响,证明了多肽二级结构选择性离子结合的现象,提出了一种可能的离子结合模型,最后展示了该种水凝胶在铝金属保护方面的应用设计和实例。第四,基于多肽自组装的超分子水凝胶致动器材料。主要研究了使用序列为2-萘乙酸-谷氨酸-苯丙氨酸-苯丙氨酸-多巴(NapGFFDopa)的多肽作为自组装单体,形成电操控的超分子多肽水凝胶,详细研究了水凝胶的力学性质,电操控变换性质,电化学变化和微观结构的变化以及生物相容性,展示了使用该种水凝胶制备的各种致动器器件和实际应用,包括能够实现电操控线性运动,线性放大,旋转运动,药物释放和微流系统操控的致动器器件。第五,基于多肽自组装和高分子共价胶联的双网络超强水凝胶材料。主要设计了一种新型的具备与自然软骨结构类似力学性质的高分子-超分子(多肽)双网络水凝胶。该种水凝胶稳定,结实并具有随时间变化的应力驰豫性质和快速恢复性质,如此独一无二的力学性质使其具备成为软骨修复水凝胶支架的潜力。同时我们也展示了这种水凝胶的可设计性,其力学性质可以通过改变不同组分比例来调节,展现了该种双网络水凝胶在软骨修复领域和组织再生领域有巨大的应用前景。
[Abstract]:Molecular self-assembly of peptide material in recent years has attracted more and more attentions, gradually in biological materials, environmental materials, medical materials and other new materials has become a hot spot, shine. Peptide specific conditions and in the environment, in the hydrophobic interaction, hydrogen bonding, stacking interaction, forming a complex assembly structure the highly ordered driver interaction. Through the design of complementary ion self assembling peptide sequence, assembly condition and process control, can be self assembling peptide materials of various forms, such as polypeptide hydrogel, peptide nanotubes, polypeptide nanospheres, peptide crystals, polypeptide fibers and so on. Due to this material extremely compatibility good biological degradability and simple preparation steps, self assembling peptide material in the light absorbing material, 3D printing materials, soft material actuator, controlled drug release, super It has great application prospect. Sub hydrogel were studied in this paper the physical and mechanical properties of peptide self assembled materials in optical absorption and photoluminescence catalytic system, system design and application of supramolecular hydrogels and double network hydrogel system. The main contents include: first, the absorption system and self assembly peptide light catalytic materials based on the main research respectively based on the amino acid sequence of phenylalanine phenylalanine (FF) and porphyrin - phenylalanine - phenylalanine (MCpP-FF) two peptide self-assembly structure of light absorption system, including the formation mechanism of the self-assembled structure microstructure, optical properties, combined with the electron donor and acceptor absorption catalytic reaction rate the efficiency and reproducibility, etc., to establish the efficient light absorption system and artificial photosynthesis catalytic system, the two kinds of optical absorption system for NAD+ to NADH Catalytic efficiency reached above 25%, and the MCpP-FF five cycle efficiency remained above 60%, compared to other light absorption system with high efficient, reusable, biocompatible advantages. Second, absorption of light and the self-assembled peptide hydrogel material based on photoluminescence. Main research two pyridine - phenylalanine - glutamate - phenylalanine - lysine - phenylalanine - glutamate - phenylalanine lysine (Bpy-FEFKFEFK, EFK-Bpy) based on self-assembly and metal coordination interactions to form hydrogel contact, including its preparation, chemical structure, mechanical properties, optical properties, microstructure and so on, are given the application of using the type of hydrogel material as light emitting material soft light source. The use of the polypeptide hydrogel as photoluminescence in the platform, can be a variety of colors with photoluminescence When can the stimulated emission of pure white light, white light CIE value (0.33,0.33), as well as with self repairing, water can work normally and other characteristics, can print properties, show for 3D printing materials can be edited and photoluminescent materials soft large applications. Third, self assembling peptide in the application of direct combination research of two stage structure and aluminum ion and composition of hydrogel. Mainly studies which are based on EFK8 (N-FEFEFKFK-C, referred to as EFK8- 1, N-FEFKFEFK-C, EFK8- II, N-KFKFEFEF-C, KFE- and N-KFEFKFEF-C type, KFE- type II) self-assembled peptide hydrogel specific for aluminum ion binding, including ion binding peptide self-assembly on the fiber structure, two stage structure, self-assembly rate, physical and mechanical properties of hydrogels, proved that the polypeptide secondary structure of two selective ion binding phenomenon,. A possible ion binding model, and finally show the kind of hydrogel in aluminum metal protection design and application example. Fourth, supramolecular hydrogel actuator materials based on peptide self-assembly are investigated. The use of sequences of DOPA as 2- NAA - glutamic acid - phenylalanine - phenylalanine (NapGFFDopa) polypeptide as self assembling single the body, the formation of supramolecular peptide hydrogel electric control, a detailed study of the mechanical properties of the hydrogel, electric control transform nature, change the electrochemical changes and microstructure and biocompatibility, which shows a variety of actuator device using such a hydrogel preparation and application, including electric control can realize linear movement, linear amplification, rotation exercise, drug release and actuator device for microfluidic system control. Fifth, peptide self-assembly and polymer glue dual network based on super water Rubber materials. The main design of a new type of polymer and natural cartilage have similar structure and mechanical properties of the supramolecular (polypeptide) double network hydrogel. The hydrogel is stable, and has strong time-varying stress relaxation properties and mechanical properties of fast recovery properties, so the one and only make it have become cartilage repair hydrogel scaffold potential. We also show the design of the hydrogel, its mechanical properties can be changed by different components to regulate the proportion, showing the double network hydrogel has wide application prospect in the field of cartilage repair and tissue regeneration.

【学位授予单位】：南京大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB34

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