基于γ-聚谷氨酸复合组装体系的传感涂层及其性能研宄

发布时间：2018-03-22 11:05

本文选题：γ-聚谷氨酸　切入点：复合组装　出处：《江南大学》2015年博士论文　论文类型：学位论文

【摘要】：20世纪以来,高分子科学家们对大分子自组装过程的本质和规律进行了深入、系统的研究,取得了令人瞩目的成果。随着大分子自组装研究的发展,组装基元及组装过程逐渐丰富,开拓了许多新型组装基元,同时也发展了多组分复合组装;对组装过程的控制也日趋多元化,尝试多层次外场诱导可控组装,获得了一些具有特殊结构和功能的多层次组装体系。大分子自组装以分子或分子聚集体为基本单元,拓展了构造新物质、新材料的新方法。人们期待在化学合成之后,自组装给人类制造出更丰富多彩的多尺度新物质、新功能材料以及新功能器件。我们课题组以双亲性无规共聚物为组装基元,经溶液组装得到纳米粒子,开展了自组装纳米粒子在液-液界面的多级组装及应用研究。是否可以将双亲性无规共聚物自组装纳米粒子的多级组装拓展至液-固界面、开拓制备功能涂层的新方法?我们曾尝试以光敏性无规共聚物与模板分子复合组装制备荷电的纳米粒子,经外电场诱导在液-固界面进行多级组装,成功制备得到传感功能涂层。但是,对双亲性生物大分子组装体系在液-固界面的多级组装及应用尚未进行相关研究。生物发酵法合成的γ-聚谷氨酸(γ-PGA)是由L-谷氨酸/D-谷氨酸通过α-酰胺键结合形成的一种多肽分子。由于γ-PGA具有良好的生物相容性、生物降解性、保湿性和环境友好等特点,在食品、医药、农业、环保、化妆品等领域具有广泛的应用。通过自组装法制备的γ-PGA纳米粒子目前的应用研究主要集中在蛋白质、药物负载以及免疫等生物医药领域。本论文以改性生物大分子γ-PGA与功能因子为组装基元,在溶液中经复合组装制备γ-PGA复合组装纳米粒子,利用电泳沉积将其二次组装在电极表面制备传感功能涂层。从不同层面对改性γ-PGA与功能因子的多级组装过程进行研究,建立改性γ-PGA多级组装及其功能化的普适性方法,拓展γ-PGA复合组装体系在传感功能涂层的实际应用。具体研究内容分为以下几个部分:1.基于血红蛋白/γ-聚谷氨酸组装体系的分子印迹传感涂层及其性能研究以7-氨基-4-甲基香豆素(AMC)对γ-PGA进行光敏改性制备γ-PGA聚合物(γ-PGA-AMC),与血红蛋白(Hb)在溶液中经复合组装制备Hb/γ-PGA-AMC分子印迹纳米粒子(MINPs),通过电泳沉积技术将MINPs组装在电极表面;光交联后洗脱除去模板分子,得到Hb分子印迹传感涂层,考察了涂层的传感性能。结果表明:利用光敏性双亲生物大分子γ-PGA-AMC与Hb经多级组装成功制备得到分子印迹纳米粒子传感涂层,在水溶液中实现了对Hb的直接检测。将结合大分子自组装技术和电泳沉积技术制备分子印迹纳米粒子传感涂层的应用拓展至生物大分子领域。2.基于金/γ-聚谷氨酸组装体系的传感涂层及其性能研究以多巴胺为功能单体对γ-PGA进行功能改性,制备多巴胺改性γ-PGA聚合物(γ-PGA-DA),在水溶液中以γ-PGA-DA为还原剂和稳定剂,以HAu Cl4为前驱体,一步原位合成Au/γ-PGA-DA纳米粒子;对Au/γ-PGA-DA在溶液中的复合组装及其在电极表面的传感性能开展研究。结果表明:组装基元比例及溶液的p H值是影响Au/γ-PGA-DA纳米粒子形貌和性能的重要因素;在γ-PGA-DA纳米粒子中Au纳米粒子的存在可以显著改善其电性能,从而有效提高复合纳米粒子的导电性和灵敏性;Au/γ-PGA-DA纳米粒子中Au纳米粒子分散越好、粒径越小,制备的复合纳米粒子涂层的导电性和灵敏性越好。3.基于外电场诱导金/γ-聚谷氨酸组装体系的传感涂层及其性能研究在对Au/γ-PGA-DA在溶液中的复合组装及在电极表面的传感性能研究的基础上,利用电泳沉积技术将Au/γ-PGA-DA纳米粒子二次组装在电极表面制备传感功能涂层,系统研究了电泳沉积条件(沉积电压及沉积时间)及沉积液性质(沉积液p H值及沉积液盐浓度)对复合纳米粒子在电极表面组装涂层形貌及传感性能的影响。结果表明:通过改变电泳沉积条件及沉积液性质可以有效调控Au/γ-PGA-DA纳米粒子在电极表面涂层的形貌和性能;随着电压的增加,涂层更易保持良好的粒子形貌,但沉积电压过大,涂层均匀度降低;通过改变Au/γ-PGA-DA纳米粒子分散液的p H值和盐浓度使复合纳米粒子粒径较小时,制备的涂层更易保持良好的粒子形貌;当电极表面形成均匀的粒子膜、且厚度较小时,得到的涂层具有较佳的传感性能。4.基于银/三聚氰胺/γ-聚谷氨酸组装体系的分子印迹传感涂层及其性能研究以γ-PGA-DA聚合物、三聚氰胺(MEL)及Ag NO3为三组分组装基元制备Ag/MEL/γ-PGA-DA MINPs,考察组装基元比例对Ag/MEL/γ-PGA-DA MINPs结构及其涂层传感性能的影响。结果表明:印迹纳米粒子中引入Ag纳米粒子可有效提高印迹传感涂层的导电性和检测灵敏性;三元组装体系中各组分比例是影响到复合组装体系的结构及其涂层传感性能的重要因素;制备得到的三元印迹纳米粒子传感涂层对三聚氰胺的检测具有高灵敏性和高选择性,可应用于实际样品的检测。本论文将大分子自组装体系在液-固界面的多级组装及应用拓展至双亲性生物大分子领域,开拓了生物大分子γ-PGA复合组装体系在传感功能涂层的应用;系统研究了组装环境对基于γ-PGA复合组装体系的传感功能涂层制备及性能的影响,为传感功能涂层的规模化生产奠定基础。
[Abstract]:Since twentieth Century, the essence and laws of polymer scientists to the macromolecular self-assembly process in-depth, systematic research, has made remarkable achievements. With the development of molecular self-assembly, assembly element and the assembly process gradually, open up a lot of new assembly unit, but also the development of multi-component composite assembly; diversified control of assembly process, try multi-level field induced controllable assembly, obtained with special structure and function of the multi-level assembly system. The self-assembly of macromolecules with molecular or molecular aggregates as the basic unit, expand the construction of new material, new methods and new materials. Expected in chemical synthesis after self-assembly to humans produce more plentiful and colorful multi scale new material, new functional materials and new functional devices. Our research group using amphiphilic random copolymer for assembling element, The solution assembly of nanoparticles, the self-assembly of nanoparticles in multistage assembly and application of liquid-liquid interface. It can be of amphiphilic copolymer self-assembled nanoparticles assembled multi-stage expansion to the liquid-solid interface, develop a new method for preparation of functional coatings? I have tried to non photosensitive copolymer nanoparticles with the template composite preparation charge, the electric field induced by multistage assembly at the liquid-solid interface, successfully prepared sensing function coating. However, the amphiphilic macromolecular assembly system has not carried out related research on multi-stage assembly and application of the liquid-solid interface. Biological fermentation synthesis of gamma poly (gamma -PGA) is a polypeptide molecules formed by L- glutamate /D- glutamic acid by the alpha amide bond. Because gamma -PGA has good biocompatibility, biodegradability, moisture and environment Friendly, in food, medicine, agriculture, environmental protection, has been widely applied to cosmetics and other fields. Mainly concentrated in the protein through the research and application of gamma self-assembled -PGA nanoparticles prepared by the drug loading and the immune and other biomedical fields. In this paper, the modified biological macromolecules gamma -PGA and functional factors for assembly base yuan, in the solution preparation of -PGA composite nanoparticles by gamma composite assembly system, assembly prepared by electrophoretic deposition coating on the surface of the electrode for sensing the second. From different aspects, multi-level group modified gamma -PGA and functional factor loading process was studied. The establishment of modified gamma -PGA hierarchical assembly and functionalization of universal method, expand the gamma -PGA assembly system in the practical application of composite sensing function of coating. The concrete research content is divided into the following parts: 1. based on molecular hemoglobin / gamma polyglutamic acid assemble system of India Study on coating and properties of trace sensor with 7- amino -4- methyl coumarin (AMC) of gamma -PGA photosensitive preparation of modified -PGA polymer gamma (gamma -PGA-AMC), hemoglobin (Hb) in the solution preparation of molecularly imprinted nanoparticles by Hb/ gamma -PGA-AMC composite system (MINPs), by electrophoretic deposition technique in MINPs assembly the surface of the electrode; crosslinking after washing and removing the template molecule, Hb molecular imprinting coating, sensing properties of the coatings were investigated. The results show that the amphiphilic macromolecules and the Hb gamma -PGA-AMC photosensitive hierarchical assembly have been successfully synthesized by molecular imprinted nanoparticles sensing coating in aqueous solution to achieve a direct detection of Hb. Combining the application of expansion to the field of biological macromolecules.2. molecular self-assembly technique and electrophoretic deposition technology for the preparation of molecularly imprinted nanoparticles sensing coating sensitive coating gold / glutamic acid assembly system based on And the performance of using dopamine as functional modification of gamma -PGA functional monomer, preparation of dopamine modified gamma (gamma -PGA-DA), -PGA polymer in aqueous solution using gamma -PGA-DA as reducing agent and stabilizer, with HAu Cl4 as the precursor, step in situ synthesis of Au/ -PGA-DA nanoparticles on gamma gamma -PGA-DA Au/; in the solution of complex assembly and its development in the sensing performance of the electrode surface. The results show that the assembled element ratio and P of the solution H value is an important factor affecting the morphology and properties of -PGA-DA nanoparticles in Au/ gamma; gamma -PGA-DA nanoparticles in Au nanoparticles can significantly improve the electrical performance, so as to improve the conductivity and the sensitivity of the composite nanoparticles; the better dispersion Au nanoparticles Au/ gamma -PGA-DA nanoparticles, smaller particle size, composite nanoparticles coating prepared by electrical conductivity and better sensitivity of.3. based on electric field induced Au / gamma poly Glutamate assemble system of sensing coatings and its properties on Au/ gamma -PGA-DA in the solution of complex assembly and based on the sensing performance of the electrode surface, the electrophoretic deposition of Au/ -PGA-DA two nanoparticles assembled by gamma functional coating on the surface of the electrode sensing system, the system of electrophoretic deposition (deposition voltage and deposition conditions time and liquid deposition (deposition) properties of liquid p and liquid H value of salt deposition concentration) influence on the composite nanoparticles coating morphology and sensing properties on the surface of the electrode. The results show that by changing the deposition conditions and properties of deposited liquid can effectively control Au/ gamma -PGA-DA nanoparticles on the morphology and properties of the coating on the surface of electrode with voltage; increase, more easy to maintain good coating particle morphology, but the deposition voltage is too large, uniform coating is reduced; by changing the Au/ gamma -PGA-DA nanoparticles dispersion p H and salt concentration of the composite particle size is small, coating preparation easier to keep good particle morphology; when forming uniform particle film electrode surface, and the thickness is small, the coating has better sensing properties of.4. Ag / melamine / gamma polyglutamic acid assembly system of molecular imprinting based on the properties of coating and gamma -PGA-DA polymer, melamine (MEL) and Ag NO3 as the three component assembly element preparation of Ag/MEL/ gamma -PGA-DA MINPs, the influence of assembling element ratio on Ag/MEL/ gamma -PGA-DA MINPs structure and its coating sensing performance. The results show that imprinted nanoparticles by introducing Ag nanoparticles can effectively improve the conductivity the detecting sensitivity and imprinting coating; each group of three yuan in the assembly system ratio is an important factor that affects the structure and properties of the composite coating sensing assembly system; the prepared three yuan India Detection of trace of melamine coating nanoparticles sensor with high sensitivity and high selectivity, can be used in the detection of real samples. The macromolecular self-assembly system in biological macromolecular assembly and application of multistage expansion to the parent field of liquid-solid interface, develop biological macromolecules gamma -PGA composite assembly system in the application of sensing function coating; system of assembly environment influence on the synthesis and properties of -PGA composite coating gamma sensor function assembly system based on, to lay the foundation for the large-scale production of sensing function of the coating.

【学位授予单位】：江南大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383.1;TQ630.1

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