| As an interdiscipline of modern chemistry, life science, material science, etc, supramolecular chemistry has attracted more and more attention of scientific workers. And the development of new material is a sign of the progress of modern civilization and the important material basis for social improvement. With the rapid development of science and technology and the eve growing demand of society, the design and preparation of multifunctional and high-powered materials are important challenges that human need to face constantly. Nowadays, some new organic-inorganic hybrid materials with the good synergy between different components and more excellent properties have been prepared by combining the supramolecular macrocycles owning molecular recognition performance with different inorganic materials. Through further functional regulation, the materials could be used in the sensor detection, drug delivery, smart response and other aspects. And it will provide the experimental basis for their application and research in a broader field and open new future of hybrid materials.In this dissertation, we have selected macrocyclic arens to be hybridized with different inorganic materials, and obtained hybrid materials with reserved recognition performance of supramolecular macrocycles and more superior properties than original inorganic. Then, the applications in different fields have been developed. In the paper, we have adopted the third generation of macrocyclic calixarene derivatives, namely the water-soluble sulfonatedcalix[4, 6]arenes(SC[4, 6]A), and the burgeoning macrocyclic pillarenes and their derivatives, namely perhydroxyl-pillar[5, 6]ene(P5, P6) and water-soluble carboxylatopillar[5]ene(CP5) to complex with mesoporous silica nanoparticles(MSNs), graphene and silica, respectively. And as a result, we got new type of organic-inorganic materials possessing different properties and functions. The main research contents of this paper are as follows:In the first part, we have made the sulfonatocalixar[4, 6]enes with two cavity sizes encircle the MSNs to block the pores of MSNs and get nanoreserviors for cargo delivery, by forming complexs through non-covalent and host-guest interaction with the alkylammonium stalks which were immobilized on the surfaces via cleavable disulfide bonds. Glutathione(GSH) could cleave the disulfide bonds and then the blocks were snapped from the stalks, resulting in the cargo release. The changing p H could fall down the stalks by weakening the interaction between the sulfonatocalixarenes and the alkylammonium molecules, that also resulting in the release of cargo. The good biocompatible, dual stimuli-induced and calixarene/MSN-based nanoreservior system could be used in drug delivery and intelligent controlled release.In the second part, CP5 molecules have been successfully attached onto the graphene surfaces via covalent bonds to obtain hybrid nanosheets owning apparently improving water-dispersibility. The functional hybrid materials showed the molecular recognition of CP5 and enhanced fluorescence quenching performance compared with native graphene. The sensing and detection of organic dyes have been achieved by taking full advantage of the hybrid materials.In the third part, perhydroxyl-pillar[5, 6]enes(P5, P6) have been modified to hydrophobic silica support via covalent to prepare new composite materials which could adsorb paraquat molecules. The adsorption and kinetic studies have been also investigated by a series of experiments. Contrast experiments showed that P6-modified materials had better adsorption behavior as P6 had higher binding constant with the adsorbate. This new type of organic-inorganic hybrid absorbent materials could be considered as an efficient adsorbent for the removal of pesticide residue. And it would lay the foundation for the design and preparation of similar new materials, broadening the research direction. |
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