基于杯芳烃和柱芳烃的有机—无机杂化材料的制备及在药物控释和传感检测方面的应用
发布时间：2018-08-20 18:43
【摘要】：作为近代化学、生命科学、材料科学等多学科交汇的学科,超分子化学的发展受到了越来越多的科研学者的关注。而新材料的发展是现代文明社会进步的标志和发展的重要物质基础。随着科学技术的突飞猛进及社会需求的日益增长,多功效、高性能的新材料的设计开发是人类需要不断面对的挑战。如今,科研人员通过将具有超分子识别能力的有机超分子大环主体与各类无机材料相结合,制备出了各组分协同且具更优异性能的有机-无机杂化材料,并通过进一步的功能调控,使其能在传感检测、药物传输、智能响应等方面有所应用,为其在更广领域的研究和应用提供实验依据,开启杂化材料的新未来。基于此,本论文选用超分子大环主体与各类无机材料进行杂化,在保留大环主体原有的主客体识别性能的基础上,制备出比原始无机材料性能更优的杂化材料,并开发其在不同领域的应用。文章中我们采用了第三代大环杯芳烃的衍生物,即水溶性磺化杯[4,6]芳烃(SC[4,6]A),和新兴大环柱芳烃及其衍生物,即羟基柱[5,6]芳烃(P5,P6)和水溶性羧基柱[5]芳烃(CP5),分别与介孔硅纳米粒子、二氧化硅和石墨烯三种无机材料进行复合,得到具有不同性质和功能的新型有机-无机杂化材料。本论文的主要研究内容如下:第一部分工作,我们将两种具有不同空腔大小的磺化杯芳烃,即磺化杯[4,6]芳烃,分别与修饰在介孔硅表面的带有动态二硫键的烷基氨分子链段通过非共价键主客体相互作用相结合,以封住介孔硅的孔道出口制备出了一类基于杯芳烃的纳米阀门药物控释体系。该纳米阀门通过在谷胱甘肽(GSH)的刺激下使介孔硅表面的二硫键断键,从而打开阀门使所装载的药物实现释放;或者是利用酸性p H条件下磺化杯芳烃与介孔硅表面小分子链段的主客体相互作用减弱而促使杯芳烃大环脱离介孔硅表面进而打开阀门使药物释放。这类具有双重刺激响应性和良好生物相容性的基于杯芳烃/介孔硅的纳米阀门体系可用于药物传输与智能控释领域。第二部分工作,我们成功的将羧基柱芳烃通过共价键复合到了还原氧化石墨烯表面,得到了柱芳烃与石墨烯的复合材料,大大提高了石墨烯在水中的分散性。此外,表面修饰柱芳烃的石墨烯材料仍然保持大环的主客体识别特性,并且与原始石墨烯相比,对于染料分子具有增强的荧光淬灭性能。这类复合材料被用于有机染料分子的传感和检测。第三部分工作,我们把不同尺寸的羟基柱[5,6]芳烃通过共价键连接到疏水的二氧化硅材料表面制备出了可用于吸附农药百草枯的杂化材料,并且通过一系列实验研究了这类材料在水溶液里的吸附动力学行为。通过实验对比显示,由于柱[6]芳烃与客体分子具有更强的主客体相互作用,从而使得其相应的吸附材料对百草枯具有更良好的吸附行为。这种新型的有机-无机复合吸附剂材料可以用于农药残留的吸附处理,同时也为类似新型杂化材料的设计和制备提供了研究基础,拓宽了研究方向。
[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.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TB33
本文编号：2194633
[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.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TB33
【参考文献】
相关期刊论文 前1条
1 朱义福;;还原型谷胱甘肽的稳定性研究[J];现代食品科技;2011年08期
，本文编号：2194633
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