光响应螺吡喃基聚合物纳米粒子的制备与性能研究

发布时间：2018-04-24 14:51

本文选题：光响应 + 螺吡喃　；参考：《北京科技大学》2018年博士论文

【摘要】：螺吡喃类衍生物是典型的光响应分子,具有光致异构化性能,并且在不同光照下螺吡喃基团会呈现不同的亲/疏结构。螺吡喃分子有两种状态:闭环状态(SP,螺吡喃结构)与开环状态(MC,部花菁结构)。在黑暗或者可见光(Vis)照射下,螺吡喃分子以疏水的SP结构存在。而在紫外光(UV)照射下,螺吡喃分子又以亲水的MC结构存在。除了光刺激,pH刺激也能使螺吡喃分子发生质子化或去质子化过程,产生结构变化。利用螺吡喃光照前后分子结构转变和光化学性质的变化,可将其广泛应用于光记录材料,光学器件,化学传感,药物控制释放等领域。本文合成了螺吡喃激光响应聚合物纳米粒子,并研究其在不同外界刺激下的释放性能与规律。研究内容分为四部分:第一部分是紫外光、pH、温度三重响应螺吡喃基聚合物胶束纳米粒子的制备及性能研究。利用无规共聚的方法结合光响应基团螺吡喃和温度响应基团异丙基丙烯酰胺,成功制备了聚(异丙基丙烯酰胺-共-螺吡喃酯)两亲性聚合物。在水溶液中该两亲性聚合物可以通过自组装过程形成外壳亲水内核疏水的胶束型纳米粒子。本部分系统研究了温度、pH以及协同刺激对该纳米粒子形貌与性能的影响,揭示了不同刺激与客体分子释放速率之间的规律,实现了对模型分子香豆素102高效快速的可控释放。并在温和的外场协同刺激下,实现了纳米粒子对客体分子的有效控制释放。实验结果表明该纳米粒子可作为性能优良的智能释放体系。第二部分是近红外光和pH双重响应螺吡喃基聚合物-UCNPs复合纳米粒子的制备及性能研究。在水溶液中,两亲性螺吡喃基聚合物(异丙基丙烯酰胺-共-螺吡喃酯)通过自组装的过程形成胶束型纳米粒子,其中螺吡喃基疏水部分组成该纳米粒子的核,聚异丙基丙烯酰胺亲水部分组成该纳米粒子的壳。伴随该聚合物自组装的过程,疏水的上转换纳米粒子(UCNPs)和客体分子可以被包载到纳米自组装体的核中,并形成聚合物-UCNPs(UCNPs@Polymer)复合纳米粒子。在近红外光照射时,UCNPs可以同时发射出紫外光和可见光,并且发出的紫外光能够引起疏水分子螺吡喃(SP)异构化为亲水分子部花菁(MC)。本部分系统研究了近红外光、pH以及协同刺激对该纳米复合物形貌与性能的影响,揭示了不同刺激与客体分子释放速率之间的规律,实现了对模型分子高效快速的可控释放。并在温和的外场协同刺激下,实现了纳米粒子对客体分子有效的控制释放。体外细胞活性实验的结果表明:在外场协同刺激下,纳米复合物能有效的控制释放包载的药物并成功的杀死癌细胞,表明该纳米复合物可作为性能优良的智能药物释放体系。第三部分是光、pH以及还原物质三重响应螺吡喃基聚合物纳米凝胶的制备及性能研究。利用乳液聚合的方法结合光响应分子螺吡喃、酸响应分子丙烯酸和还原物质响应交联剂成功制备了一种新型的光、pH以及还原物质三重刺激响应的纳米凝胶。本部分系统研究了不同刺激对纳米凝胶形貌与性能的影响:在紫外光照射下,纳米凝胶上SP异构化为MC使其内部的亲-疏水平衡被打破,使纳米凝胶略有膨胀;在酸性环境刺激下,纳米凝胶上的丙烯酸发生质子化,使纳米凝胶快速膨胀;在还原物质刺激下,纳米凝胶上的交联剂被切断,使纳米凝胶迅速解散。进一步研究外场协同刺激对纳米凝胶形貌与性能的影响,探究了客体分子可控释放的内在原理,实现了温和条件下纳米凝胶对客体分子有效的控制释放。体外细胞活性实验的结果表明:在外场协同刺激时,纳米凝胶能有效的控制释放包载药物并成功的杀死癌细胞,表明该纳米凝胶可作为性能优良的智能药物释放体系。第四部分是近红外光、pH、氧化还原三重响应螺吡喃基聚合物-UCNPs复合纳米凝胶的制备及性能研究。通过乳液聚合法成功制备了一种新型的近红外光、pH以及还原物质三重刺激响应的聚合物-UCNPs复合纳米凝胶。利用包载的UCNPs吸收近红外光转换为紫外光,使复合纳米凝胶上的SP基团可以在近红外光照刺激下可逆的异构化为MC基团。本部分系统研究了近红外光、pH、氧化还原物质以及协同刺激对该复合纳米凝胶形貌与性能的影响,揭示了不同刺激与客体分子释放速率之间的规律,实现了对装载药物高效快速的可控释放。并在协同刺激时,实现了温和条件下复合纳米凝胶对药物有效的控制释放。结果表明该复合纳米凝胶可作为性能优良的智能释放体系。
[Abstract]:Spiroparan derivatives are typical photoresponsive molecules with photoisomerization properties, and the spiroparan groups present different parent / sparse structures under different illumination. Spiroparan molecules have two states: closed loop state (SP, spiropran structure) and open loop state (MC, cyanine structure). Spiroparan under dark or visible light (Vis) irradiation. Under the ultraviolet (UV) irradiation, the spiroparan molecule is in the presence of a hydrophilic MC structure. In addition to the light stimulation, the pH stimulates the protonalization or deprotonation process of the spiroparan molecules, resulting in structural changes. The changes in the molecular structure transition and photochemical properties of the spiroparan before and after illumination can be widely used. For light recording materials, optical devices, chemical sensing, drug control release and other fields. This paper syntheses the spiroparan laser response polymer nanoparticles and studies its release properties and laws under different external stimuli. The research content is divided into four parts: the first part is ultraviolet light, pH, and temperature three heavy response of spiroparan polymer micelles. Preparation and properties of rice particles. The two amphiphilic polymer of poly (isopropylacrylamide - Co spironyl) was prepared by using the method of random copolymerization combining light response group spirono and temperature response group isopropyl acrylamide. In aqueous solution, the two amphiphilic polymer can form the hydrophilic core of the shell through the self-assembly process. The effect of temperature, pH and synergistic stimulation on the morphology and properties of the nanoparticles was systematically investigated, and the regularity between the different stimuli and the release rate of the guest molecules was revealed. The effective and rapid release of the model molecule coumarin 102 was realized. The nanoparticles can be effectively controlled and released on the guest molecules. The experimental results show that the nanoparticles can be used as a good intelligent release system. The second part is the preparation and performance study of the dual response spiran based polymer -UCNPs composite nanoparticles with near infrared light and pH. In aqueous solution, the two Pro propyl propyl polymer (isopropyl C) A micelle type nanoparticle is formed through the process of self-assembly, in which the hydrophobic part of the spironyl group consists of the core of the nanoparticle, and the hydrophilic part of the polyisopropylacrylamide consists of the shell of the nanoparticles. With the self-assembly process of the polymer, the hydrophobic upconversion nanoparticles (UCNPs) and the guest molecules can be used. The polymer -UCNPs (UCNPs@Polymer) composite nanoparticles are loaded into the core of the nano self assembled body. The ultraviolet and visible light can be emitted by UCNPs at the same time in the near infrared light, and the ultraviolet light can cause the hydrophobicity of the spiran (SP) isomerization to the hydrophilic molecular part of the cyanine (MC). This part studies the near red system. The effect of external light, pH and synergistic stimulation on the morphology and properties of the nanocomposites reveals the laws between the different stimuli and the release rates of the guest molecules, realizing the efficient and rapid controlled release of the model molecules. And under the mild synergistic stimulation of the external field, the effective release of nanoparticles to the guest molecules is realized. The experimental results show that nanocomposites can effectively control the release of encapsulated drugs and kill cancer cells successfully under the synergistic stimulation of external field, indicating that the nanocomposite can be used as an intelligent drug release system with excellent performance. The third part is the preparation of light, pH and reductive substances in the preparation of spirono based polymer nanosels with three heavy responses. A new type of nanosels of light, pH and reductive substances were successfully prepared by the method of emulsion polymerization in combination with light response molecular spiroparan, acid response molecular acrylic acid and reductive substance response crosslinking agent. The effects of different spines on the morphology and properties of nanosels were studied in this part. Under the light of external light, the SP isomerization of the nanosels to MC makes the hydrophobic equilibrium inside the gel broken and the nano gel expands slightly. Under the acid environment, the acrylic acid on the nanosels is protonated and the nano gel expands rapidly. Under the stimulation of the reductive substance, the crosslinking agent on the nanosels is cut off and the nanosels can be solved quickly. The effect of the synergistic stimulation on the morphology and performance of nanosels was further studied, and the intrinsic principle of controlled release of the guest molecules was explored. The effective control release of nanosels to the guest molecules under mild conditions was realized. The results of cell activity experiments in vitro showed that the nanorels could be effectively controlled and released when the external field was stimulated. The fourth part is the preparation and performance study of the near infrared light, pH, redox three heavy response spiran based polymer -UCNPs composite nanosels. A new type of near infrared (NIR) is successfully prepared by emulsion polymerization. The polymer -UCNPs composite nanosels of light, pH and reductive substances with three heavy stimulus response are used to convert the SP group on the composite nanosels to the MC group in a reversible isomerization under the near infrared light stimulation. This part systematically studies the near infrared light, pH, redox material and the compound nanosels. The effect of synergistic stimulation on the morphology and properties of the composite nanosels revealed the regularity between the different stimuli and the release rates of the guest molecules and realized the efficient and rapid controlled release of the loaded drugs. The gel can be used as an intelligent release system with excellent performance.

【学位授予单位】：北京科技大学
【学位级别】：博士
【学位授予年份】：2018
【分类号】：O633.5;TB383.1

【参考文献】