基于氢键自组装作用的PEA和PEO-g-P4VP纳米胶束的制备

发布时间：2018-03-19 00:21

本文选题：非共价键键合胶束　切入点：自组装　出处：《郑州大学》2015年硕士论文　论文类型：学位论文

【摘要】：在高分子学领域,我们采用自组装法可以获得形态和结构各异的两亲性高分子胶束,同时赋予它们优良的生物相容性、亲水性等特点。当这种两亲性胶束呈现空心结构时,它的内腔可以包覆大量的药物、疏水性聚合物等,在药物传输、材料改性等方面应用广泛。目前,基于非共价键键合胶束法(NCCM)制备聚合物纳米胶束的方法简单易操作,且可通过改变交联剂用量、聚合物摩尔比等得到不同尺寸的胶束。而在诸多的非共价键键合体系中,相较于其他驱动力,氢键的作用力强,方向性好,有利于形成稳定胶束;且通过氢键连接的聚合物胶束,其核-壳结构无需特殊溶剂降解内核,改变溶剂状态即可。因此基于氢键的自组装体系在化学和生物体系中都占据非常重要的位置。本论文研究的主要内容是制备基于氢键作用的聚合物纳米胶束,并探究交联剂用量、溶剂等对胶束制备的影响。论文的具体工作可分为如下两个部分:1、首先合成了端羧基化的聚苯乙烯(PS-COOH)和线性多嵌段聚醚胺(PEA),然后基于此构建NCCM体系,在水相中成功制备PS/PEA核-壳胶束,经甲醛交联固定核-壳结构后,切换溶剂至二甲基甲酰胺(DMF)获得PEA纳米胶束。并进一步探究PS和PEA的滴加顺序,PS和PEA的摩尔比,甲醛用量,DMF用量对胶束结构和尺寸的影响。经动态光散射(DLS)测试,交联后的胶粒尺寸由98.40nm减小至75.85nm,证明胶束的壳结构被成功锁住;经空穴化处理后,胶粒尺寸又增加至113.70nm。探究实验结果分析可知,反向滴加制备的胶束尺寸为93.46nm,明显减小;其他条件下,用量适当增有利于得到尺寸更大的胶束,但超过一定的范围后,胶束尺寸反而减小。证明制备条件及体系各组份用量的改变会影响聚合物胶束的形状和尺寸。2、首先合成了接枝共聚物PEO-g-P4VP,同种条件下在硝基甲烷(CH3NO2)溶液中制备PS/PEO-g-P4VP胶束,经二溴丁烷交联固定后切换溶剂至DMF空穴化得到PEO-g-P4VP纳米胶束。并进一步探究PS和PEO-g-P4VP的滴加顺序,不同摩尔比的PS和PEO-g-P4VP,二溴丁烷用量,DMF用量对胶束形成或空穴化的影响。经DLS测试,我们得到尺寸为143.21nm的PEO-g-P4VP纳米胶束,分散指数(PDI)为0.226,说明其具有较好的分散性。反向滴加得到117.40nm的胶束,其他条件如摩尔比、二溴丁烷及DMF用量的改变等均进一步验证了第一个体系的结论。
[Abstract]:In the field of macromolecule science, we can obtain amphiphilic micelles with different morphology and structure by self-assembly method, and give them excellent biocompatibility and hydrophilicity, etc. When the amphiphilic micelles show hollow structure, Its inner cavity can be coated with a large number of drugs, hydrophobic polymers, etc. It is widely used in drug transport, material modification, etc. At present, the method of preparing polymer nano-micelles based on non-covalent bonding micelles is simple and easy to operate. Different sizes of micelles can be obtained by changing the amount of crosslinking agent and the molar ratio of polymer. In many non-covalent bonding systems, the hydrogen bonding force is stronger and the direction is good than other driving forces, which is conducive to the formation of stable micelles. The core-shell structure of the polymer micelles connected by hydrogen bond does not require special solvent to degrade the core. Therefore, the self-assembly system based on hydrogen bond occupies a very important position in both chemical and biological systems. The effects of crosslinking agent and solvent on the preparation of micelles were investigated. The specific work of this paper can be divided into two parts: 1. The carboxyl terminated polystyrene (PS-COOH) and linear multiblock polyether amine (PEAA) were synthesized, and then the NCCM system was constructed. PS/PEA core-shell micelles were successfully prepared in water phase. After crosslinking and fixing the core-shell structure by formaldehyde, the PEA nanomeres were obtained by switching solvent to dimethylformamide. The molar ratio of PS and PEA was further investigated. The effect of the amount of formaldehyde and DMF on the structure and size of the micelles was studied by DLSs. The size of the crosslinked micelles was reduced from 98.40 nm to 75.85 nm, which proved that the shell structure of the micelles was successfully locked up, and the structure of the micelles was treated by hole treatment. The size of micelle was increased to 113.70 nm. The results of the experiment showed that the size of micelle prepared by reverse dropping was 93.46 nm, which was obviously reduced. Under other conditions, the micelle with larger size was obtained by proper increase of dosage, but beyond a certain range. It was proved that the shape and size of polymer micelles would be affected by the changes of the preparation conditions and the amount of each component in the system. Firstly, the graft copolymer PEO-g-P4VPwas synthesized, and the PS/PEO-g-P4VP micelles were prepared in nitromethane Ch _ 3NO _ 2 solution under the same conditions. The PEO-g-P4VP nanomicelles were prepared by dibromobutane crosslinking immobilization by switching solvents to DMF cavitation. The dropping order of PS and PEO-g-P4VP was further investigated. The effects of PS, PEO-g-P4VPand dibromobutane on the micelle formation or cavitation of PS and PEO-g-P4VP at different molar ratios. By DLS, we obtained the PEO-g-P4VP nanomicelles with the size of 143.21 nm. The dispersion index (PDI) is 0.226, which indicates that it has good dispersion. The micelle of 117.40 nm is obtained by reverse dropping. The conclusion of the first system is further verified by the other conditions, such as molar ratio, dibromobutane and the change of the amount of DMF.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1;O648.1

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