Study On The Synthesis And Properties Of New Materals And Their Application In Electroanalytical Chemistry

With the development of supermolecular chemistry and molectroics, tetrathiafulvalene (TTF) has played an important role as a functional format of molecular and supermolecules for its special characters such as particular electrochemical action, assembly and good derivability. In this paper, four amphiphilic TTF derivatives were synthesized and characterized by kinds of techniques to ensure the molecular structures. The electrochemical properties and LB film characters of TTF obtained derivatives were also studied. Chemically modified electrode is an active sphere in electrochemistry and electroanalytical chemistry. Graphene has attracted attention increasingly since it was discovered in 2004, and the application of graphene as modified electrode materials has increased for its special properties. The contents of this paper are as follows:1. Synthesis of Amphiphilic Tetrathiafulvalene DerivativesThe 1,3-dithionle-2-thiones 4a and 4b were prepared by the reaction of di(tetraethylammonium) bis(1,3-dithiol-2-thione-4,5-dithiolate) zincate (Compounds 1) with myristyl bromide and octadecyl bromide in refluxing acetonitrile, respectively. Then, two tetrathiafulvalene 5a and 5b were obtained by the cross-coupling of 4a and 4b with 4,5-biscyanoethylthio-1,3-dithiole-2-one (Compounds 3) mediated by triethylphosphite, respectively. And the sequent reaction of 5a and 5b with 2-(2-iodoethoxy)ethanol in the presence of caseium hydroxide afforded tetrathiafulvalene 6a and 6b, which reacted with tosyl chloride to convert corresponding tetrathiafulvalene tosylates 7a and 7b. A series of amphiphilic tetrathiafulvalene 8a-8d were easily synthesized by the reaction of 7a and 7b with 2-mercapto-thiadiazoles in the presence of sodium hydroxide, respectively. All amphiphilic tetrathiafulvalene 8a-8d were characterized by 1H NMR,13C NMR, IR, MS.2. The study of electrochemical response and LB film characters of four amphiphilic TTF derivativesWe researched for the electrochemical response and LB film characters of the four amphiphilicity TTF derivatives 8a-8d obtained. And the effect of some group on electrochemical properties and amphiphilicity was discussed. Moreover, kinetics parameters of electrode process was detected using proper electrochemical methods.3. Synthesis of graphene oxide and its application in modified electrodeWe successfully synthesized graphene oxide, then a novel electrochemical sensor for the detection of trace amounts of colchicine based on graphene oxide (GO)-Nafion composite film modified glassy carbon electrode (GCE) was developed. The sensor exhibited excellent electrocatalytic activity for the oxidation of colchicine, displaying as a low detection limit of 1.5×10-8 in 0.1 mol L-1 H2SO4 solution. The method was also applied successfully to detect colchicine in the medicinal tablets.