【摘要】：作為近代化學(xué)、生命科學(xué)、材料科學(xué)等多學(xué)科交匯的學(xué)科,超分子化學(xué)的發(fā)展受到了越來越多的科研學(xué)者的關(guān)注。而新材料的發(fā)展是現(xiàn)代文明社會進步的標(biāo)志和發(fā)展的重要物質(zhì)基礎(chǔ)。隨著科學(xué)技術(shù)的突飛猛進及社會需求的日益增長,多功效、高性能的新材料的設(shè)計開發(fā)是人類需要不斷面對的挑戰(zhàn)。如今,科研人員通過將具有超分子識別能力的有機超分子大環(huán)主體與各類無機材料相結(jié)合,制備出了各組分協(xié)同且具更優(yōu)異性能的有機-無機雜化材料,并通過進一步的功能調(diào)控,使其能在傳感檢測、藥物傳輸、智能響應(yīng)等方面有所應(yīng)用,為其在更廣領(lǐng)域的研究和應(yīng)用提供實驗依據(jù),開啟雜化材料的新未來。基于此,本論文選用超分子大環(huán)主體與各類無機材料進行雜化,在保留大環(huán)主體原有的主客體識別性能的基礎(chǔ)上,制備出比原始無機材料性能更優(yōu)的雜化材料,并開發(fā)其在不同領(lǐng)域的應(yīng)用。文章中我們采用了第三代大環(huán)杯芳烴的衍生物,即水溶性磺化杯[4,6]芳烴(SC[4,6]A),和新興大環(huán)柱芳烴及其衍生物,即羥基柱[5,6]芳烴(P5,P6)和水溶性羧基柱[5]芳烴(CP5),分別與介孔硅納米粒子、二氧化硅和石墨烯三種無機材料進行復(fù)合,得到具有不同性質(zhì)和功能的新型有機-無機雜化材料。本論文的主要研究內(nèi)容如下:第一部分工作,我們將兩種具有不同空腔大小的磺化杯芳烴,即磺化杯[4,6]芳烴,分別與修飾在介孔硅表面的帶有動態(tài)二硫鍵的烷基氨分子鏈段通過非共價鍵主客體相互作用相結(jié)合,以封住介孔硅的孔道出口制備出了一類基于杯芳烴的納米閥門藥物控釋體系。該納米閥門通過在谷胱甘肽(GSH)的刺激下使介孔硅表面的二硫鍵斷鍵,從而打開閥門使所裝載的藥物實現(xiàn)釋放;或者是利用酸性p H條件下磺化杯芳烴與介孔硅表面小分子鏈段的主客體相互作用減弱而促使杯芳烴大環(huán)脫離介孔硅表面進而打開閥門使藥物釋放。這類具有雙重刺激響應(yīng)性和良好生物相容性的基于杯芳烴/介孔硅的納米閥門體系可用于藥物傳輸與智能控釋領(lǐng)域。第二部分工作,我們成功的將羧基柱芳烴通過共價鍵復(fù)合到了還原氧化石墨烯表面,得到了柱芳烴與石墨烯的復(fù)合材料,大大提高了石墨烯在水中的分散性。此外,表面修飾柱芳烴的石墨烯材料仍然保持大環(huán)的主客體識別特性,并且與原始石墨烯相比,對于染料分子具有增強的熒光淬滅性能。這類復(fù)合材料被用于有機染料分子的傳感和檢測。第三部分工作,我們把不同尺寸的羥基柱[5,6]芳烴通過共價鍵連接到疏水的二氧化硅材料表面制備出了可用于吸附農(nóng)藥百草枯的雜化材料,并且通過一系列實驗研究了這類材料在水溶液里的吸附動力學(xué)行為。通過實驗對比顯示,由于柱[6]芳烴與客體分子具有更強的主客體相互作用,從而使得其相應(yīng)的吸附材料對百草枯具有更良好的吸附行為。這種新型的有機-無機復(fù)合吸附劑材料可以用于農(nóng)藥殘留的吸附處理,同時也為類似新型雜化材料的設(shè)計和制備提供了研究基礎(chǔ),拓寬了研究方向。
[Abstract]:The development of supramolecular chemistry has attracted more and more researchers'attention as the interdisciplinary subject of modern chemistry, life science, material science and so on. The development of new materials is the symbol of the progress of modern civilization and an important material basis for its development. Nowadays, by combining the organic supramolecular macrocyclic host with various inorganic materials with supramolecular recognition ability, researchers have prepared organic-inorganic hybrid materials with more excellent properties and synergistic components, and through further work. It can be used in sensor detection, drug delivery, intelligent response and so on. It provides experimental basis for its research and application in a wider field, and opens a new future for hybrid materials. In this paper, we use the derivatives of the third generation macrocyclic calixarenes, namely water-soluble sulfonated calixarenes (SC [4,6] A), and new macrocyclic aromatic hydrocarbons and their derivatives, namely hydroxyl column [5,6] aromatic hydrocarbons (P5, P6) and water-soluble. Carboxyl column [5] aromatic hydrocarbons (CP5) were compounded with mesoporous silica nanoparticles, silica and graphene to obtain novel organic-inorganic hybrid materials with different properties and functions. Calixarene-based drug delivery systems for nanovalves were prepared by non-covalent host-guest interactions of calixarene [4,6] aromatic hydrocarbons and alkylammonia molecular segments with dynamic disulfide bonds modified on the surface of mesoporous silicon to seal the pore exit of mesoporous silicon. The valves were stimulated by glutathione (GSH). The disulfide bond on the surface of mesoporous silicon is broken to open the valve to release the drug loaded; or the interaction between the sulfonated calixarene and the host and guest of the small molecular segments on the surface of mesoporous silicon is weakened under acidic P H conditions to cause the calixarene macroring to detach from the surface of mesoporous silicon and then open the valve to release the drug. Calixarene/mesoporous silicon nanovalve systems with high stimulus responsiveness and good biocompatibility can be used in the field of drug delivery and intelligent controlled release. The dispersity of graphene in water was investigated. In addition, the surface-modified column aromatic graphene materials retained the host-guest recognition properties of macrocyclic rings and exhibited enhanced fluorescence quenching properties for dye molecules as compared with the original graphene. These composites were used for sensing and detecting organic dye molecules. Hydroxyl column [5,6] aromatic hydrocarbons of different sizes were covalently bonded to hydrophobic silica surface to prepare hybrid materials for adsorbing paraquat. A series of experiments were carried out to study the adsorption kinetics of these materials in aqueous solution. This new organic-inorganic composite adsorbent material can be used for the adsorption of pesticide residues. It also provides a basis for the design and preparation of new hybrid materials and broadens the research direction.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：TB33

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相關(guān)期刊論文 前1條

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本文編號：2194633