本文選題：γ-聚谷氨酸　切入點(diǎn)：復(fù)合組裝　出處：《江南大學(xué)》2015年博士論文　論文類型：學(xué)位論文

【摘要】：20世紀(jì)以來,高分子科學(xué)家們對大分子自組裝過程的本質(zhì)和規(guī)律進(jìn)行了深入、系統(tǒng)的研究,取得了令人矚目的成果。隨著大分子自組裝研究的發(fā)展,組裝基元及組裝過程逐漸豐富,開拓了許多新型組裝基元,同時(shí)也發(fā)展了多組分復(fù)合組裝;對組裝過程的控制也日趨多元化,嘗試多層次外場誘導(dǎo)可控組裝,獲得了一些具有特殊結(jié)構(gòu)和功能的多層次組裝體系。大分子自組裝以分子或分子聚集體為基本單元,拓展了構(gòu)造新物質(zhì)、新材料的新方法。人們期待在化學(xué)合成之后,自組裝給人類制造出更豐富多彩的多尺度新物質(zhì)、新功能材料以及新功能器件。我們課題組以雙親性無規(guī)共聚物為組裝基元,經(jīng)溶液組裝得到納米粒子,開展了自組裝納米粒子在液-液界面的多級組裝及應(yīng)用研究。是否可以將雙親性無規(guī)共聚物自組裝納米粒子的多級組裝拓展至液-固界面、開拓制備功能涂層的新方法?我們曾嘗試以光敏性無規(guī)共聚物與模板分子復(fù)合組裝制備荷電的納米粒子,經(jīng)外電場誘導(dǎo)在液-固界面進(jìn)行多級組裝,成功制備得到傳感功能涂層。但是,對雙親性生物大分子組裝體系在液-固界面的多級組裝及應(yīng)用尚未進(jìn)行相關(guān)研究。生物發(fā)酵法合成的γ-聚谷氨酸(γ-PGA)是由L-谷氨酸/D-谷氨酸通過α-酰胺鍵結(jié)合形成的一種多肽分子。由于γ-PGA具有良好的生物相容性、生物降解性、保濕性和環(huán)境友好等特點(diǎn),在食品、醫(yī)藥、農(nóng)業(yè)、環(huán)保、化妝品等領(lǐng)域具有廣泛的應(yīng)用。通過自組裝法制備的γ-PGA納米粒子目前的應(yīng)用研究主要集中在蛋白質(zhì)、藥物負(fù)載以及免疫等生物醫(yī)藥領(lǐng)域。本論文以改性生物大分子γ-PGA與功能因子為組裝基元,在溶液中經(jīng)復(fù)合組裝制備γ-PGA復(fù)合組裝納米粒子,利用電泳沉積將其二次組裝在電極表面制備傳感功能涂層。從不同層面對改性γ-PGA與功能因子的多級組裝過程進(jìn)行研究,建立改性γ-PGA多級組裝及其功能化的普適性方法,拓展γ-PGA復(fù)合組裝體系在傳感功能涂層的實(shí)際應(yīng)用。具體研究內(nèi)容分為以下幾個(gè)部分:1.基于血紅蛋白/γ-聚谷氨酸組裝體系的分子印跡傳感涂層及其性能研究以7-氨基-4-甲基香豆素(AMC)對γ-PGA進(jìn)行光敏改性制備γ-PGA聚合物(γ-PGA-AMC),與血紅蛋白(Hb)在溶液中經(jīng)復(fù)合組裝制備Hb/γ-PGA-AMC分子印跡納米粒子(MINPs),通過電泳沉積技術(shù)將MINPs組裝在電極表面;光交聯(lián)后洗脫除去模板分子,得到Hb分子印跡傳感涂層,考察了涂層的傳感性能。結(jié)果表明:利用光敏性雙親生物大分子γ-PGA-AMC與Hb經(jīng)多級組裝成功制備得到分子印跡納米粒子傳感涂層,在水溶液中實(shí)現(xiàn)了對Hb的直接檢測。將結(jié)合大分子自組裝技術(shù)和電泳沉積技術(shù)制備分子印跡納米粒子傳感涂層的應(yīng)用拓展至生物大分子領(lǐng)域。2.基于金/γ-聚谷氨酸組裝體系的傳感涂層及其性能研究以多巴胺為功能單體對γ-PGA進(jìn)行功能改性,制備多巴胺改性γ-PGA聚合物(γ-PGA-DA),在水溶液中以γ-PGA-DA為還原劑和穩(wěn)定劑,以HAu Cl4為前驅(qū)體,一步原位合成Au/γ-PGA-DA納米粒子;對Au/γ-PGA-DA在溶液中的復(fù)合組裝及其在電極表面的傳感性能開展研究。結(jié)果表明:組裝基元比例及溶液的p H值是影響Au/γ-PGA-DA納米粒子形貌和性能的重要因素;在γ-PGA-DA納米粒子中Au納米粒子的存在可以顯著改善其電性能,從而有效提高復(fù)合納米粒子的導(dǎo)電性和靈敏性;Au/γ-PGA-DA納米粒子中Au納米粒子分散越好、粒徑越小,制備的復(fù)合納米粒子涂層的導(dǎo)電性和靈敏性越好。3.基于外電場誘導(dǎo)金/γ-聚谷氨酸組裝體系的傳感涂層及其性能研究在對Au/γ-PGA-DA在溶液中的復(fù)合組裝及在電極表面的傳感性能研究的基礎(chǔ)上,利用電泳沉積技術(shù)將Au/γ-PGA-DA納米粒子二次組裝在電極表面制備傳感功能涂層,系統(tǒng)研究了電泳沉積條件(沉積電壓及沉積時(shí)間)及沉積液性質(zhì)(沉積液p H值及沉積液鹽濃度)對復(fù)合納米粒子在電極表面組裝涂層形貌及傳感性能的影響。結(jié)果表明:通過改變電泳沉積條件及沉積液性質(zhì)可以有效調(diào)控Au/γ-PGA-DA納米粒子在電極表面涂層的形貌和性能;隨著電壓的增加,涂層更易保持良好的粒子形貌,但沉積電壓過大,涂層均勻度降低;通過改變Au/γ-PGA-DA納米粒子分散液的p H值和鹽濃度使復(fù)合納米粒子粒徑較小時(shí),制備的涂層更易保持良好的粒子形貌;當(dāng)電極表面形成均勻的粒子膜、且厚度較小時(shí),得到的涂層具有較佳的傳感性能。4.基于銀/三聚氰胺/γ-聚谷氨酸組裝體系的分子印跡傳感涂層及其性能研究以γ-PGA-DA聚合物、三聚氰胺(MEL)及Ag NO3為三組分組裝基元制備Ag/MEL/γ-PGA-DA MINPs,考察組裝基元比例對Ag/MEL/γ-PGA-DA MINPs結(jié)構(gòu)及其涂層傳感性能的影響。結(jié)果表明:印跡納米粒子中引入Ag納米粒子可有效提高印跡傳感涂層的導(dǎo)電性和檢測靈敏性;三元組裝體系中各組分比例是影響到復(fù)合組裝體系的結(jié)構(gòu)及其涂層傳感性能的重要因素;制備得到的三元印跡納米粒子傳感涂層對三聚氰胺的檢測具有高靈敏性和高選擇性,可應(yīng)用于實(shí)際樣品的檢測。本論文將大分子自組裝體系在液-固界面的多級組裝及應(yīng)用拓展至雙親性生物大分子領(lǐng)域,開拓了生物大分子γ-PGA復(fù)合組裝體系在傳感功能涂層的應(yīng)用;系統(tǒng)研究了組裝環(huán)境對基于γ-PGA復(fù)合組裝體系的傳感功能涂層制備及性能的影響,為傳感功能涂層的規(guī)�；a(chǎn)奠定基礎(chǔ)。
[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.

【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TB383.1;TQ630.1

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本文編號：1648372