【作者】 王雪莹；

【导师】 罗川南；

【作者基本信息】 济南大学 ， 分析化学， 2010， 硕士

【摘要】 本文将具有不同的带电性、良好的水溶性或者光谱活性等不同性质的官能团引入杯芳烃母体上,不仅显著增强了杯芳烃的水溶性,亦拓宽了杯芳烃衍生物在光谱分析以及分子识别等方面的应用范围。本文合成了水溶性以及光谱活性的杯芳烃衍生物,并研究了杯[8]芳烃磺酸钠与喹诺酮类药物以及吩噻嗪类药物之间的相互作用,并进一步研究了杯芳烃衍生物作为药物载体在药物缓释控释中的应用。论文主要包括以下几个方面:第一部分概述了杯芳烃的研究意义,水溶性杯芳烃以及偶氮杯芳烃衍生物的合成研究进展,杯芳烃及其衍生物的分子识别研究现状以及本论文研究的主要内容。第二部分采用一步法合成了对叔丁基杯[n]芳烃(n=4,8)以及脱对叔丁基杯[n]芳烃,并将磺酸基以及对磺酸基苯偶氮基引入到脱对叔丁基杯芳烃上,合成了杯[8]芳烃磺酸钠和对磺酸基苯偶氮杯[n]芳烃(n=4,8)。利用红外光谱法、元素分析法等对合成产物的结构进行了表征,同时利用薄层色谱法跟踪反应过程,利用液相色谱法对合成产物的纯度进行了表征,并对实验过程中影响产率的主要因素进行了讨论。第三部分利用荧光光谱法研究了杯[8]芳烃磺酸钠与诺氟沙星、杯[8]芳烃磺酸钠与环丙沙星在水溶液中的形成包络物的最佳条件。同时,利用荧光光谱法研究了包络物之间的主客体包络行为并测定了包络物的结合常数和结合比。实验结果表明,当向诺氟沙星、环丙沙星的水溶液中加入杯[8]芳烃磺酸钠溶液时,均出现荧光猝灭现象。接着向超分子包络体系中加入牛血清白蛋白(BSA)以后,荧光强度得到恢复。表明蛋白质可以与包络体系中的喹诺酮类药物竞争杯[8]芳烃磺酸钠,进一步说明可用于喹诺酮类药物的储存和定点释控。第四部分利用荧光光谱以及紫外吸收光谱法研究了杯[n]芳烃磺酸钠与吩噻嗪类药物亚甲基蓝以及甲苯胺蓝之间的包络作用,通过与喹诺酮类药物包络的比较,以及不同空腔尺寸的杯芳烃磺酸钠对吩噻嗪类药物包络作用的比较,研究了杯[n]芳烃磺酸钠作为主体化合物与药物进行包络的主要作用方式。第五部分以亚甲基蓝为探针测定了牛奶中蛋白质的含量,采用荧光光度法研究了杯[6]磺酸钠—亚甲基蓝—牛血清蛋白体系。讨论了杯[6]芳烃磺酸钠—甲苯胺蓝超分子体系的最佳形成条件,建立了一种灵敏度高的检测方法。方法用于实际样品测定中,结果令人满意。第六部分对论文的工作进行了总结,并对以后的工作进行了展望。更多还原

【Abstract】 Supramolecular Chemistry originated from the discovery of crown ethers and was further developed as host-guest chemistry and supramolecular chemistry by D. J. Cram and J. M. Lehn. Calixarene was the representative of the third generation supramolecular. Different functional groups were introduced to the calixarene in this paper. With their different electric, good water solubility and spectral activity of nature, not only water-soluble ability of calixarene was enhanced significantly, but also the application of calixarene derivatives in the spectrum and molecular recognition was enlarged. Water-soluble calixarene derivatives and spectral activity of calixarene derivatives were synthesized in this paper .In order to study the feasibility of the p-sulfoniccalix[8]arene as controlled-release drug delivery agents in pharmaceutical industry, the inclusion behavior between p-sulfoniccalix[8]arene and quinolones or quinolones drugs were investigated. This study demonstrated the potential application of calixarene derivatives in biology and pharmaceutics. There were some paragraphs in this paper as following.The research significance of calixarene, the research of water-soluble calixarene derivatives and azobenzene calixarene derivatives, the applications of calixarene and its derivatives in molecular recognition, the main content and characteristic of this paper were summarized in first paragraph.Tert-butylcalix[n]arene (n=4,8) and intermediate de-tert-butylcalix[n]arene were synthesized with one-step method in the second paragraph, and further benzene sulfonic acid and the acid azo introduced into the off-tert-butyl calixarenes, the synthesis of a calix[8]arene, calix sulfobenzylidene[n]arene (n=4,8). Infrared spectroscopy, ultraviolet spectroscopy, elemental analysis were used to characterize the structure of the synthesized product , the reaction process was tracked using thin layer chromatography, and the purity of the synthesized product was characterized with liquid chromatography. Finally, the product factors in the experiment were discussed.In the third paragraph, the inclusion behavior between p-sulfoniccalix[8]arene and quinolones drugs were investigated by fluorescence spectroscopy. The optimum conditions of forming host-guest systems in aqueous solution were studied.Meanwhile, in order to discuss the mechanism of inclusion process, the various influence on the inclusion process, such as temperature, pH value, concentrations of host and guest compounds, surfactants, organic solvent were also examined. On the base of experimental results, the association constant K and combined ratio (n) were calculated. Subsequently, the addition of bovine serum albumin (BSA) solution into the host-guest system leads to the recovery of fluorescence intensity. It is indicated that BSA may destruct the SC8A-NFLX inclusion complex, and liberate the NFLX into solution.In the fourth paragraph, the inclusion behavior between p-sulfoniccalix[n]arene and phenothiazine methylene blue and toluidine bule with fluorescence spectroscopy and UV absorption spectroscopy. The mechanism of inclusion process between p-sulfoniccalix[n]arene and quinolones drugs were discussed.In the fifth paragraph, the protein in milk was determinated using methylene blue as the probe with fluorescence spectrophotometry of p-sulfoniccalix[6]arene-methylene blue -BSA system. The best formation conditions of the calix [6] arene-methylene blue supramolecular systems were discussed, and a low detection limit, high sensitivity detection method was established. The method was used in real samples and the experiment results were satisfactoryIn the sixth paragraph, the jobs in this paper were summarized and the jobs in future were also discussed.更多还原