光响应偶氮苯自组装界面材料的制备及性能研究

发布时间：2018-03-11 21:20

本文选题：偶氮苯　切入点：界面材料　出处：《北京科技大学》2018年博士论文　论文类型：学位论文

【摘要】：刺激响应界面是生物界面化学研究中的前沿热点之一,它不仅有助于我们了解生命的奥秘、还对构建新型功能多尺度界面材料及实现高灵敏度检测有着重要意义。在众多的刺激响应中,光作为一种清洁能源,不会对环境造成污染和破坏,并且能够实现远程调控,是目前研究的热点之一。偶氮苯类化合物被认为是最理想的光响应材料之一,其高效的顺反异构化率使其广泛应用在功能界面、信息存储和药物控释等领域。本论文研究了光响应偶氮苯自组装界面对细胞和细菌的粘附与释放行为;及其对客体分子的控制释放,主要内容如下:(1)通过化学吸附技术与静电自组装技术设计合成了两种偶氮苯膜材料。分别研究了两种膜材料在紫外光照前后的分子异构化率、浸润性的变化情况。我们采用光刻蚀技术将微纳结构引入体系中,来增加表面材料的粗糙程度,并研究紫外光照前后粗糙界面上细胞吸附能力的变化情况。紫外光照后静电自组装膜的细胞粘附力显著下降,而化学吸附膜中由于偶氮苯生色团的高密度排列,其在光照前后膜的粘附性能未发生明显变化。(2)通过硅烷偶联化反应将小分子环糊精连接到基底表面,设计合成了可以特异性识别细胞的界面材料(Si-CD/Azo-apt)。研究该特异性界面材料Si-CD/Azo-apt在紫外/可见光交替照射下对目标细胞的捕获与释放性能,实现Si-CD/Azo-apt对特异性细胞的捕获与释放。此外,利用偶氮苯与环糊精的主客体相互作用,实现Si-CD/Azo-apt的再生和可重复利用,为光响应智能界面材料在肿瘤细胞的分离和提取技术领域的潜在应用提供了重要的依据。(3)利用偶氮苯与环糊精的主客体相互作用,将聚阳离子(Azo-PDMAEMA)、聚阴离子(Azo-PAA)的偶氮苯聚合物修饰到基底材料表面,制备具有不同粘附性能的界面材料。研究聚阳离子表面与聚阴离子表面的细菌吸附能力。同时,研究可见光(绿光/蓝光)照射前后,上述两个表面的细菌粘附能力的变化情况。利用偶氮苯与环糊精的主客体可逆的相互作用,在可见光交替照射下,可以实现界面材料Si-CD/Azo-PDMAEMA、Si-CD/Azo-PAA的再生和可重复利用。(4)通过季铵化反应合成了一种可见光响应的偶氮苯聚阳离子化合物;利用偶氮苯与环糊精之间的主客体相互作用,将修饰有药物模板分子的环糊精与可见光偶氮苯制成主客体络合物(Azo-PDMAEMA/β-CD-RhB)。Azo-PDMAEMA/β-CD-RhB作为聚阳离子,PAA作为聚阴离子,通过静电作用制备层层自组装多层膜系统,用于完成药物模板分子的装载。研究药物模板分子的装载量与自组装膜层数的关系。绿光(520 nm)可以诱导偶氮苯从反式结构异构化为顺式结构,导致主客体络合物的解离,从而使药物模板分子从多层膜中释放出来。随后蓝光的照射(450 nm),可使顺式偶氮苯重新变为反式偶氮苯,使药物分子重新装载到界面材料上,实现可见光调控的模板分子的装载与释放。
[Abstract]:The stimuli response interface is one of the frontier research hotspots in biointerface chemistry, which not only helps us understand the mystery of life, It is also of great significance for the construction of new functional multi-scale interface materials and the realization of high sensitivity detection. Among the numerous stimulus responses, light, as a clean energy source, does not pollute and damage the environment, and can achieve remote regulation and control. Azobenzene compounds are considered as one of the most ideal photoresponse materials, and their high cis / trans isomerization rate makes them widely used in functional interfaces. In the field of information storage and drug controlled release, we studied the adhesion and release behavior of photoresponsive azobenzene self-assembly interface to cells and bacteria, and the controlled release of guest molecules. The main contents are as follows: (1) two kinds of azobenzene membrane materials were designed and synthesized by chemisorption and electrostatic self-assembly techniques. The molecular isomerization rates of two kinds of membrane materials before and after UV irradiation were studied respectively. The change of wettability. We use photoetching technology to introduce micro-nano structure into the system to increase the roughness of surface materials. The cell adhesion of the electrostatic self-assembled membrane decreased significantly after UV irradiation, but the chemisorbent membrane was arranged in high density because of the chromophore of azobenzene. The adhesion of the membrane to the substrate was not changed significantly before and after irradiation. (2) the small molecule cyclodextrin was connected to the substrate surface by silane coupling reaction. An interface material, Si-CD / P / Azo-aptr, was designed and synthesized to specifically recognize cells. The capture and release properties of the specific interface material, Si-CD/Azo-apt, to target cells under alternating ultraviolet / visible light irradiation were studied to realize the capture and release of specific cells by Si-CD/Azo-apt. By the interaction of azobenzene with the host and guest of cyclodextrin, Si-CD/Azo-apt can be regenerated and reused. It provides an important basis for the potential application of photo-responsive intelligent interface materials in the field of tumor cell separation and extraction, using azobenzene and the host-guest interaction of cyclodextrin. The azobenzene polymer of polycationic Azo-PDMAEMAA (polyanionic azo-PAA) was modified on the surface of the substrate to prepare interfacial materials with different adhesion properties. The bacterial adsorption capacity between polycation surface and polyanionic surface was studied. To study the change of bacterial adhesion ability of the two surfaces before and after visible (green / blue) irradiation. Using the reversible interaction between azobenzene and the host and guest of cyclodextrin, under the alternating irradiation of visible light, A visible light-responsive azobenzene polycationic compound was synthesized by quaternary ammonium reaction, and the host and guest interaction between azobenzene and cyclodextrin was used to realize the regeneration and reusability of Si-CD / PDMAEMA-Si-CD / CD / Azo-PAA. The host and guest complex Azo-PDMAEMA / 尾 -ActivehBU. Azo-PDMAEMAEMA / 尾 -JAX-hB was prepared by electrostatic interaction of cyclodextrin modified with drug template molecule and visible light azobenzene as polyanions. Layers of self-assembled multilayer film system were prepared by electrostatic action. To complete the loading of drug template molecules. The relationship between the loading amount of drug template molecules and the number of self-assembled film layers is studied. The isomerization of azobenzene from trans-structure to cis-structure can be induced, which leads to the dissociation of host and guest complexes. Then the drug template molecule is released from the multilayer film. Then the blue light irradiation of 450nmg can change the cis-azobenzene back to trans-azobenzene and reload the drug molecule onto the interface material. The loading and releasing of template molecules controlled by visible light are realized.
【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】：TQ460.1;O625.65

【相似文献】