刺激响应性聚合物的制备与表征及其固定化酶的研究

发布时间：2017-12-31 08:24

本文关键词：刺激响应性聚合物的制备与表征及其固定化酶的研究　出处：《陕西师范大学》2016年硕士论文　论文类型：学位论文

【摘要】：当今的聚合物己向智能材料发展,经过多年的对于刺激响应聚合物的深入研究,刺激响应聚合物已获得了越来越多的关注,刺激响应是能使外部物理变化致使其产生智能的变化。由于它们有非常多的应用,因此聚合有响应基团的聚合物丰富了智能材料的世界。多种响应性的基团整合到聚合物中,从而表现出多响应的性质,这些刺激响应性聚合物的响应行为能够缩小或扩大来改变它们的光学性质或根据环境的变化来改变它们的电性能。由于对于材料科学的发展是社会的发展的需求,因此我们需调整自己的方向为社会发展做贡献。显然,近些年产生了许多智能聚合物,并且事实说明刺激响应性聚合物在我们生活中不可缺少的。智能聚合物其刺激响应行为基本上是由聚合物链上存在的官能团决定的。不同的功能基团可产生不同的刺激。最常用的刺激有温度、pH、光、离子强度、电子转移(氧化还原)和主客体相互作用。在刺激响应性聚合物中一种新颖的聚合物是多刺激响应性高分子,双响应性或多响应性聚合物是可以根据不同的刺激作出反应产生叠加效果,这种智能高分子材料可以被用到更为精细的过程。基于此,本论文主要设计制备了三种新型的多刺激响应性的聚合物,并研究了其响应性质,为刺激响应型材料的应用奠定了基础。本论文的研究内容如下所示：(1) 基于主客体化学构建Janus型超分子聚合物通过原子转移自由基聚合、叠氮化反应、点击反应和酯水解反应合成pH响应的客体高分子Ad-(PMAA)7,通过原子转移自由基聚合的方法合成了温度响应的主体高分子β-CD-(PNIPAAm)4。通过红外光谱、核磁和GPC对所涉及到的聚合物进行了确认,通过测试数据证明了客体高分子己成功制得。在水溶液中,主客体高分子可自组装具有Janus型超分子聚合物,通过紫外吸收光谱仪证实了设计合成的超分子具有温度和pH双响应的性质,通过透射电镜图观测其自组装的胶束形态。在pH=5.4时,形成了以主体分子为壳,客体分子为核的球状胶束,其粒径尺寸为100nm；在温度为35℃时,自组装成以主体分子为核,客体分子为壳的球状胶束,其粒径尺寸为200nm, DLS测试了自组装的粒径分布。(2) 基于光和pH响应客体高分子和温度响应的主体高分子构建超分子聚合物通过原子转移自由基聚合,点击反应和酯水解反应成功的制备了一种具有温度和pH双响应的超分子聚合物β-CD-(PNIPAAm)4-Azo-(PMAA)7,并用FTIR、NMR和GPC分析进行了确认,证实了主客体高分子材料已被成功制备。通过紫外可见分光光度计研究结果可以推断：超分子体系具有温度、pH和光多响应的特点,并验证其存在主客体的相互作用。通过透射电镜图观测其自组装的胶束形态。在pH=5.4时,形成了以主体分子为壳,客体分子为核的球状胶束,其粒径尺寸为100nm；在温度为35℃时,自组装成以主体分子为核,客体分子为壳的球状胶束,其粒径尺寸为20Onm, DLS的测试表明形成的胶束具有较高的稳定性,通过透射电镜证实了超分子聚合物β-CD-(PNIPAAm)4-Azo-(PMAA)7的组装和重组。(3)pH/光双响应高分子的制备及其固定化酶的研究通过原子转移自由基聚合,点击反应和酯水解反应成功的制备了一种具有光和pH双响应的聚合物mPEG-hv-PNB-PMAA-b-PS,并用FTIR, NMR和GPC分析进行了确认。通过紫外可见吸收光谱、GPC确定了此高分子具有光响应的性质。通过紫外-可见分光光度计确定其临界胶束浓度。通过透射电镜图可观测其自组装的胶束形态,合成的嵌段聚合物在水溶液条件下自组装成具有核壳结构的球状胶柬,通过在不同pH条件下测试其粒径尺寸,证明其具有pH响应的性质,可通过改变pH值,从而调节胶束尺寸的大小。通过固定α-淀粉酶于此刺激响应性高分子胶束,研究了此高分子胶束固定化酶的应用,通过一系列测试,得出了最佳的条件,固定化酶温度为45℃,给酶量为10U/mL,最大固定化酶的量为240mg/g,最适反应温度为65℃,最佳反应pH为5.6,酶储存日期为40天左右。
[Abstract]:The polymer has to intelligent material development, after years of in-depth research on stimuli responsive polymer, stimuli responsive polymers have gained more and more attention, stimulus response can make external physical changes cause a smart change. Because they have a lot of applications, so the polymerization of polymers enriched the intelligent response the material in the world. Many responsive groups into the polymer, which exhibit properties of multi response, the stimulus response response behavior of polymer to shrink or expand to change their optical properties or according to changes in the environment to change their electrical properties. Due to the development of material science is the social development needs therefore, we need to adjust their direction to make a contribution to the social development. Obviously, in recent years has produced many intelligent polymers, and the fact that. Response of polymer is indispensable in our life. The intelligent polymer responsive behavior basically is decided by the functional groups present on the polymer chain. Different functional groups can produce different stimuli. The most commonly used stimulus light, temperature, pH, ionic strength, electron transfer (redox) and host guest in response to stimulus interaction. A novel polymer polymer is more responsive polymer stimulation, dual responsive or more responsive polymers can make reaction superposition effect according to different stimuli, this intelligent high molecular materials can be used for more elaborate process. Based on this, this paper mainly design preparation three kinds of new polymer prickly response, and to study the response properties, which laid the foundation for the application of stimulus response materials. The research contents of this thesis are as follows: (1) base In the main object of chemical building Janus type supramolecular polymers via atom transfer radical polymerization, azidation reaction and hydrolysis of esters, click on the Ad- pH response object polymer synthesis (PMAA) of 7, the main polymer beta -CD- temperature response was synthesized via atom transfer radical polymerization (PNIPAAm) of the 4. polymer by infrared spectra. NMR and GPC of the involved was confirmed through the test data to prove the object of polymer has been successfully prepared. In aqueous solution, the main object of polymer self-assembly with Janus type supramolecular polymers, confirmed the properties with temperature and pH dual responsive supramolecular synthesis by UV absorption spectroscopy, the micellar morphology TEM observation of the self-assembly. In pH=5.4, formed the main molecular shell, spherical micelles of guest molecules, the particle size of 100nm in temperature; 35 degrees, to the main molecular self-assembled into spherical micelles as the core, the guest molecules as shell, the particle size is 200nm, DLS tested the self-assembly of particle size distribution. (2) the main polymer light and pH response object construction and temperature response of polymer supramolecular polymer polymerized by atom transfer radical based on, click on the reaction and the hydrolysis of esters was successfully prepared with a temperature and pH dual responsive supramolecular polymer beta -CD- (PNIPAAm) 4-Azo- (PMAA) 7, and FTIR, NMR and GPC analysis confirmed, confirmed that the subject and object of polymer materials has been successfully prepared by UV Vis. The spectrophotometer results can be inferred: supramolecular system with temperature, characteristics of pH and optical multi response, and verify the interaction of its existence. The main object of the micellar morphology by transmission electron microscopy observation its self-assembly. In pH=5.4, formed the main molecular shell The object, molecule as spherical micelle core, the particle size is 100nm; the temperature is 35 degrees centigrade to the main molecular self assemble into spherical micelles as the core, the guest molecules as shell, the particle size is 20Onm, the DLS test showed that the micelles has high stability, supramolecular polymer beta -CD- confirmed by transmission electron microscopy (PNIPAAm) and 4-Azo- (PMAA) assembly and reorganization of 7. (3) pH/ light responsive polymer preparation and immobilized enzyme by atom transfer radical polymerization, click on the reaction and hydrolysis of esters was successfully prepared with a polymer with mPEG-hv-PNB-PMAA-b-PS and pH double light response. And with FTIR, NMR and GPC analysis confirmed by UV Vis absorption spectra, GPC determines the polymer has the property of light response. By UV VIS spectrophotometer to determine the critical micelle concentration can be observed by TEM. The micellar morphology of self-assembly, synthesis of block copolymer in aqueous solution under the condition of self assemble into spherical core-shell micelles, through the test under conditions of different pH particle size, prove its properties of the pH response, by changing the pH value, so as to adjust the size of the micelles by fixing. Alpha amylase in the stimuli responsive polymeric micelles, the application of the polymer micelle immobilized enzyme, through a series of tests, the optimum conditions of immobilized enzyme, the temperature is 45 DEG C, the amount of enzyme is 10U/mL, the maximum of the immobilized enzyme was 240mg/g, the optimal reaction temperature is 65 DEG C, the optimum pH is 5.6, the enzyme storage date for 40 days.

【学位授予单位】：陕西师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631;Q814.2

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