本文選題：偶氮苯　切入點：界面材料　出處：《北京科技大學》2018年博士論文　論文類型：學位論文

【摘要】：刺激響應界面是生物界面化學研究中的前沿熱點之一,它不僅有助于我們了解生命的奧秘、還對構(gòu)建新型功能多尺度界面材料及實現(xiàn)高靈敏度檢測有著重要意義。在眾多的刺激響應中,光作為一種清潔能源,不會對環(huán)境造成污染和破壞,并且能夠?qū)崿F(xiàn)遠程調(diào)控,是目前研究的熱點之一。偶氮苯類化合物被認為是最理想的光響應材料之一,其高效的順反異構(gòu)化率使其廣泛應用在功能界面、信息存儲和藥物控釋等領域。本論文研究了光響應偶氮苯自組裝界面對細胞和細菌的粘附與釋放行為;及其對客體分子的控制釋放,主要內(nèi)容如下:(1)通過化學吸附技術與靜電自組裝技術設計合成了兩種偶氮苯膜材料。分別研究了兩種膜材料在紫外光照前后的分子異構(gòu)化率、浸潤性的變化情況。我們采用光刻蝕技術將微納結(jié)構(gòu)引入體系中,來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細胞吸附能力的變化情況。紫外光照后靜電自組裝膜的細胞粘附力顯著下降,而化學吸附膜中由于偶氮苯生色團的高密度排列,其在光照前后膜的粘附性能未發(fā)生明顯變化。(2)通過硅烷偶聯(lián)化反應將小分子環(huán)糊精連接到基底表面,設計合成了可以特異性識別細胞的界面材料(Si-CD/Azo-apt)。研究該特異性界面材料Si-CD/Azo-apt在紫外/可見光交替照射下對目標細胞的捕獲與釋放性能,實現(xiàn)Si-CD/Azo-apt對特異性細胞的捕獲與釋放。此外,利用偶氮苯與環(huán)糊精的主客體相互作用,實現(xiàn)Si-CD/Azo-apt的再生和可重復利用,為光響應智能界面材料在腫瘤細胞的分離和提取技術領域的潛在應用提供了重要的依據(jù)。(3)利用偶氮苯與環(huán)糊精的主客體相互作用,將聚陽離子(Azo-PDMAEMA)、聚陰離子(Azo-PAA)的偶氮苯聚合物修飾到基底材料表面,制備具有不同粘附性能的界面材料。研究聚陽離子表面與聚陰離子表面的細菌吸附能力。同時,研究可見光(綠光/藍光)照射前后,上述兩個表面的細菌粘附能力的變化情況。利用偶氮苯與環(huán)糊精的主客體可逆的相互作用,在可見光交替照射下,可以實現(xiàn)界面材料Si-CD/Azo-PDMAEMA、Si-CD/Azo-PAA的再生和可重復利用。(4)通過季銨化反應合成了一種可見光響應的偶氮苯聚陽離子化合物;利用偶氮苯與環(huán)糊精之間的主客體相互作用,將修飾有藥物模板分子的環(huán)糊精與可見光偶氮苯制成主客體絡合物(Azo-PDMAEMA/β-CD-RhB)。Azo-PDMAEMA/β-CD-RhB作為聚陽離子,PAA作為聚陰離子,通過靜電作用制備層層自組裝多層膜系統(tǒng),用于完成藥物模板分子的裝載。研究藥物模板分子的裝載量與自組裝膜層數(shù)的關系。綠光(520 nm)可以誘導偶氮苯從反式結(jié)構(gòu)異構(gòu)化為順式結(jié)構(gòu),導致主客體絡合物的解離,從而使藥物模板分子從多層膜中釋放出來。隨后藍光的照射(450 nm),可使順式偶氮苯重新變?yōu)榉词脚嫉?使藥物分子重新裝載到界面材料上,實現(xiàn)可見光調(diào)控的模板分子的裝載與釋放。
[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.
【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2018
【分類號】：TQ460.1;O625.65

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