【作者】 林琳；

【导师】 何勇；

【作者基本信息】 北京化工大学 ， 材料科学与工程， 2012， 硕士

【摘要】 偶氮苯类化合物由于其具有良好的光化学性质，可应用于制备特殊性质的光响应水凝胶材料。水凝胶成胶条件温和、易于制备且生物相容性好。相比于其它响应性的水凝胶，光响应水凝胶具有对光刺激响应速度快和定域响应的特点，是一种在生物、光开关和信息记录领域有着广阔应用前景的材料。我们设计并合成了十种新型的偶氮苯类衍生物，这些偶氮苯含有邻位的取代基，可以形成分子内氢键。通过红外图谱和核磁图谱表征，证明所合成的物质与设计是一致的。我们对合成产物进行紫外收光谱及荧光发射光谱的测定，研究在光照条件下异构化的动力学性质，并将实验数据与量子计算结果相互比较。实验结果表明含有丙烯酰氧基的偶氮苯光异构化速率较快，磺酸基与羟基的氢键作用对于偶氮苯顺式的稳定起到了一定的作用，其中2-((4-(丙烯酰氧基)苯基)偶氮)苯磺酸可以在1分钟内实现可逆的顺反异构化。含有邻位硝基和羟基的偶氮苯衍生物在紫外光照射后，其荧光发射增强。我们将聚乙二醇二丙烯酸酯600、N,N-亚甲基双丙烯酰胺与所合成的丙烯酸酯偶氮苯共聚，制备了光响应的水凝胶，水凝胶的平衡溶胀度在紫外光光照条件下会降低。我们选用利巴韦林作为释放对象，利巴韦林是一种含有大量氨基和羟基的药物作，而所制备的水凝胶是用含有硝基、羟基和磺酸基的偶氮苯单体共聚而成，这些基团与利巴韦林之间存在氢键作用。偶氮苯异构化的时候，分子构型的改变将导致药物与偶氮苯基团之间氢键的改变，从而释放行为改变。实验的数据表明含磺酸基的水凝胶和利巴韦林的相互作用较强，导致在光照条件下的释放快于无光照的释放。本文研究了偶氮苯光异构化速度的影响因素，得通过合理的分子的设计和水凝胶组分的调节，得到了可实现光控的药物释放体系。其实验结果对于光响应材料的制备有着指导意义。更多还原

【Abstract】 Azobenzene compounds have good photochemical properties whichcan be used in the preparation of light responsive hydrogel. Hydrogel isof easy preparation under mild conditions and good biocompatibility.Compared with other responsive hydrogel, light responsive hydrogel is offast and localized response characteristics, so it would have broadapplication prospects in optical switch, information recording andbiological materials.We designed and synthesized ten new azobenzene derivatives withortho substituents which have potential to form intermolecular hydrogenbond. Their structures were determined by FT-IR and NMR. Toinvestigate the photochemical properties of these products, UV-Visspectra, fluorescence emission spectra and the isomerization kinetic weremeasured, and the optimized molecular structures of the trans isomers and HOMO-LUMO gaps were calculated in the gas-phase at the DFTlevel with the Gaussian09package, B3LYP/3-21G basis set. The relativeisomerization rate of the azobenzene with acrylate group was muchbigger than that without acrylate group. The photostationary state of2-((4-(acryloyloxy)phenyl) diazenyl) benzenesulfonic acid was achievedin no more than1minute. Fluorescence emission of azobenzene withnitro and hydroxyl were enhanced after UV irradiation.The acrylate azobenzene and polyethylene glycol diacrylate600were copolymerized to make the light responsive hydrogel. The resultsshowed that UV light irradiation can reduce swelling ratio of the hydrogel.Ribavirin was used for drug release as it has many OH and NH2. Drugreleased quantity of hydrogel could be improved by UV light irradiationdue to the strong hydrogen bonding between SO3H and ribavirin.This paper designed and synthesized a series of new azobenzeneacrylate and investigted some factors affecting their photoisomerizationbehavior, at which base; a kind of light-responsible drug delivery systemwas developed by regulation of the hydrogel component.更多还原