The Research On The Electrochemical Properties Of Anticancer-activity Arene Ruthenium Complexes And Their Interaction With DNA

For its high selectivity, low cytotoxicity and antimetastaticproperties, Water-soluble arene-Ru（II） complexes providing bothhydrophilic as well as hydrophobic properties hold a high potential forthe development of metal-based anticancer drugs, and now they becomesthe focus of the research. The research on interactions of anticancer drugswith DNA is among the most active and important fields forunderstanding special DNA sequence recognition and designing newfunctional drugs. In this paper, the Electrochemistry behaviors of threesingle-gear arene-Ru（II） complexes and one double-gear arene-Ru（II）complex have been studied, the interaction of single-gear arene-Ru（II）complexes with DNA have also been studied, adopting Electrochemicaland UV-vis spectrophotometric methods. The main results are expressedas follows:1. Two arene-Ru（II） complexes {[Ru（Cym）Cl₂]2（TMP）} and[Ru（cym）（DMSO）Cl₂]（Cym=Cymene,DMSO=dimethyl sulfoxide,TMP=2,3,5,6-Tetramethylpyrazine）are synthesized, whose structure arecharacterized by1H NMR,13C NMR and IR spectrum.2. the electrochemistry behaviors of four arene-Ru（II）complexes{[Ru（Cym）Cl₂]2（TMP）},[Ru（Cym）（DMSO）Cl₂],[Ru（Cym）（DMAP）Cl₂],{[Ru（Cym）（en）Cl]PF6}（DMAP=4-dimethylaminopyridine,en=Ethylenediamine）have been studied. Thermodynamic and kineticparameters of electrode reaction process, such as Electron transfernumber（n）, Electron transfer coefficient （α）, reaction rate constant（ks）,Diffusion coefficient（D）,etc. are obtained.For double-gearcomplex{[Ru（Cym）（en）Cl]PF6},There is one-step irreversible reduction process on the surface of glassy carbon electrode, with RuIIreducing toRuI. For three single-gear arene-Ru（II） complexes,there are one-stepreduction,but one to three steps ranging in oxidation process, the redoxare all about the conversion between RuIIand RuIII.The difference ofthree single-gear arene-Ru（II） complexes in oxidation process is causedby hydrolysis of complexes. While steric hindrance of coordination groupwill affect The occurrence of hydrolysis reaction and hydrolysis degree ofruthenium complexes.3. The interaction of three single-gear arene-Ru（II） complexes{[Ru（Cym）Cl₂]₂}（TMP）,[Ru（cym）（DMSO）Cl₂],and[Ru（Cym）（DMAP）Cl₂] with DNA have also been studied, adopting cyclicvoltammetry and UV-vis spectrophotometric method, finding thecombination mode of three kinds of complexes with DNA are allElectrostatic interaction. Combined degree of RuIIIand RuIIwith DNA arealmost equal to each other. The existence of DNA makes the reversibilityof electron transfer process of RuIII/RuIIbecome worse,and accelerateadsorption of RuIIIcomplex on the surface of glassy carbon electrode.Through calculation, the combined ratio and binding constants ofcomplexes with DNA are Obtained.Among which, the binding capacityof Ru（Cym）（DMSO）Cl₂with DNA phosphate skeleton is the strongest,and the binding constant is greatest, for the electronegativity of itshydrolysis product and least steric hindrance.