Nianyun Lin

Triplet state mechanism for electron transfer oxidation of DNA

The interaction of anthraquinone-2-sulfonate with nucleotides and DNA in acetonitrile and acetonitrile water solvent mixture have been studied using KrF laser photolysis aimed at elucidation of the reaction mechanism. Laser spectroscopy directly demonstrates that the initial species from interaction of anthraquinone-2-sulfonate with nucleotides are radical cations of nucleotides and radical anion of anthraquinone-2-sulfonate. In addition, formation of ion pair from interaction of any of nucleotides with anthraquinone-2-sulfonate is synchronous with decay of triplet anthraquinone-2-sulfonate, which has provided dynamic evidence for initiation of electron transfer from DNA bases to triplet anthraquinone-2-sulfonate. Moreover, direct observation of stabilized DNA guanyl radical cation from interaction of anthraquinone-2-sulfonate with DNA has provided initial evidence for selective cleavage of DNA at guanine moiety. The solvent-separated ion pairs in acetonitrile have evidently dissociated into free ions, thereby enabling independent study of the behavior of guanyl radical cations and radical anion of anthraquinone-2-sulfonate.

Studies on reactions of oxidizing sulfur–sulfur three-electron-bond complexes and reducing α-amino radicals derived from OH reaction with methionine in aqueous solution

The technique of pulse radiolysis with spectrophotometric detection has been used to investigate the possibility of electron transfer reactions between oxidizing sulfur-sulfur three-electron-bond complexes (Met2/S thereforeS+), or reducing alpha-amino radicals (CH3SCH2CH2CH.NH2) derived from reaction of methionine with OH radicals and hydroxycinnamic acid (HCA) derivatives, riboflavin (RF) or flavin adenine dinucleotide (FAD), respectively. The HCA derivatives, such as caffeic acid, ferulic acid, sinapic acid and chlorogenic acid, widely distributed phenolic acids in fruit and vegetables, have been identified as good antioxidants previously can rapidly and efficiently repair oxidizing three-electron-bond complexes via electron transfer. RF and FAD can oxidize reducing alpha-amino radicals derived from methionine. The electron transfer rate constants approximately 10(9) dm3 x mol(-1)x s(-1) were determined by following the build-up kinetics of species produced.

Reaction of reducing hydroxyl radical adducts of pyrimidine nucleotides with riboflavin and flavin adenine dinucleotide (FAD) via electron transfer: a pulse radiolysis study.

Using the techniques of pulse radiolysis with time-resolved spectrophotometric detection, it has been demonstrated that the interaction of reducing OH radical adducts of dCMP, TMP and UMP with riboflavin (RF) and flavin adenine dinucleotide (FAD) does proceed via an electron transfer reaction. From buildup kinetics of radical species, the rate constants of electron transfer from reducing OH adducts of pyrimidines to RF and FAD have been determined, respectively. It could be deduced that RF and FAD would reduce the probability of repair of the damaged DNA in the presence of enzymes and antioxidants, accordingly RF and FAD might have a radiosensitization effect on DNA damage.

Electron transfer from purine deoxynucleotides to deoxynucleotides deprotonated radical cations: in aqueous solution

Abstract In aqueous solution, the deprotonated radical cations of dCMP, TMP and Poly C created by SO 4 − can react with dAMP at a close to diffusion control rate constants which indicates a rapid electron transfer from dAMP to deprotonated radical cations of deoxynucleotides. Analogous reaction was found to occur between the deprotonated radical cation of dAMP, dCMP, TMP or Poly C and dGMP. The rate constants were determined to be 0.64–1.3×10 8 M −1 s −1 for electron transfer from dAMP toward deprotonated radical cations and 1.2–3.3×10 8 M −1 s −1 for the case of dGMP. Thus, the electron loss center caused by one electron oxidant or by ionizing radiation will end up at guanine in DNA.

Reaction of hydroxyl radical with phenylpropanoid glycoside and its derivatives by pulse radiolysis

The reaction of hydroxyl radical with 1 phenylpropanoid glycoside (PPG), cistanoside C, and its 3 derivatives: 1-0-β-D-2-(p-hydroxyphenyl)-ethanyl-glucose, 6-O-(E)-femloyl-glucose and 6-O-(E)-p-hydroxy-cinnarnoylglucose isolated from folk medicinal herbs was investigated by pulse radiolysis technique respectively. The reaction rate constants were determined by analysis of built-up trace of absorption at λmax of specific transient absorption spectra of PPG and its derivatives upon attacking · OH. All four compounds react with · OH at close to diffusion controlled rate (1. 03 × 109-19.139 × 109 L · mol−1 · s−1), suggesting that they are effective · OH scavengers. The results demonstrated that the numbers of phenolic hydroxyl groups of PPG and its derivatives are directly related to their scavenging activities. By comparing the reaction rates of · OH with 1-O-β-D-2-(p-hydroxyphenyl)-ethanyl-glucose, 6-O-(E)-feruloyl-glucose or 6-O-(E)-p-hydroxy-cinnomoyl-glucose, it is evident that the phenylethyl group is more impofiant than phenylacryloyl group for scavenging · OH.