Synthesis And Properties Of Azo-calix[4]arene Carboxylic Acid Derivatives

The structure of calixarene is flexible and has many points modified,and it also has the unique ability to self-assemble.So the derivatization of calixarene is always a very popular research projects in the area of super molecular chemistry.The main work of this paper based on calix[4]arene,conducted chemical modification of its upper rim and lower rim.We introduced azo-group into the upper rim and carboxy and ethoxycarbonyl groups into the lower rim respectively,design and synthesis of a series of azocalix[4]arene derivatives containing esters,carboxylic acid.UV-visible and fluorescence spectra were used to identified their effects on metal ions,and part of calix[4]arene carboxylic acid derivatives were studied with biological macromolecules bovine serum albumin(BSA).There are four parts in this paper.The first chapter is an overview of calixarene,describes the latest research progress and the development of calixarene.Calixarene has characteristics of a flexible structure and ease of modification,etc.Diazo-coupling reaction is an important method used to modificate the upper rim of calixarene.Introducing-N=N-as coloration group,may make calixarene form the host molecule of color change.The various functional groups could be connected to the lower rim.These calix[4]arene derivatives have selectively recognition abilities to kinds of ions and biomolecules.In addition,calixarene derivatives containing hydrophilic groups have been got attention gradually in biological macromolecules area.The next two chapters are the main parts of this paper.Main content is as follows:① Two precursors of calixarene were synthesized,p-tert-butylcalix[4]arene and calix[4]arene and calixaren.② By selective etherisation,the calix[4]arene derivative with different unit(ethoxycarbonyl)methoxy at the lower rim were synthesized,25,27-bis[(ethoxycarbonyl)-methoxy]-26,28-dihydroxycalix[4]arene(compound C)and 5,26,27-tri[(ethoxycarbonyl)-methoxy]-28-hydroxycalix[4]arene(compound D).③ Ten azocalix[4]arene derivatives which contain different azobenzene groups at the upper rim and ethoxycarbonyl ylmethoxy groups at the lower rim were synthesized based on compound D.A part of azo-calix[4]arene were hydrolyzed to give six azocalixarens contained carboxyl group at the lower rim.All of ten componuds have never been reported.④ All of the products are characterized by IR,ESI-MS,1H-NMR and 13C-NMR⑤ The recognition of azocalix[4]arene derivatives with various metal ions were mensurate by UV-visible and fluorescence spectra.The result shows that the fluorescence spectra of azo-calix[4]arene derivatives which contain anthraquinone at the upper rim and ethoxycarbonyl ylmethoxy groups at the lower rim has the specific recognition for Hg2+,and it can be formed similar to the effect of the fluorescent swith with Y3+.The UV-visible spectra of azo-calix[4]arene derivatives containing carboxyphenyl groups at the upper rim and ethoxycarbonyl ylmethoxy at the lower rim has the specific recognition for Pb2+,and they need a certain response time.⑥ By the means of fluorescence spectra,we have studied the interaction of macromolecules bovine serum albumin(BSA)and azo-calixarene derivatives containing methylphenyl groups at three upper rim and carboxyl groups at the lower rim.The result shows that the effect is better and the strength is relative to the substitution position of methyl groups on the azobenzene,and the derivatives have a strong effect with tryptophan residues on the BSA.⑦ The fourth chapter is the conclusion of the paper and discussion of further work.