Kinetics of the Oxidation of Thymine and Thymidine by Triplet 2,2′-Dipyridyl in Aqueous Solutions at Different pH Values | Zendy

Xuan Truong Nguyen | Zendy; Günter Grampp | Zendy; Alexandra V. Yurkovskaya | Zendy; Nikita N. Lukzen | Zendy

Open Access

Kinetics of the Oxidation of Thymine and Thymidine by Triplet 2,2′-Dipyridyl in Aqueous Solutions at Different pH Values

Author(s) -

Xuan Truong Nguyen,

Günter Grampp,

Alexandra V. Yurkovskaya,

Nikita N. Lukzen

Publication year - 2013

Publication title -

the journal of physical chemistry a

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.756

H-Index - 235

eISSN - 1520-5215

pISSN - 1089-5639

DOI - 10.1021/jp4022882

Subject(s) - chemistry , thymine , flash photolysis , aqueous solution , reaction rate constant , photochemistry , nucleobase , reactivity (psychology) , electron transfer , kinetics , quenching (fluorescence) , cyclic voltammetry , thymidine , inorganic chemistry , electrochemistry , fluorescence , dna , electrode , alternative medicine , pathology , quantum mechanics , medicine , biochemistry , physics

The photo-oxidation of the nucleobase, thymine (Thy), and nucleoside, thymidine (dThy), by dipyridyl (DP) has been investigated in aqueous solution using time-resolved laser flash photolysis. The pH dependence of the oxidation rate constants is measured within a large pH scale. As a consequence, the chemical reactivity of the reactants existing in solution at a certain range of pH is predicted. Bimolecular rate constants of the quenching reactions between triplet dipyridyl and thymine and thymidine are, respectively, kq = 2.4 × 10(7) M(-1) s(-1) (pH < 5.8) and kq = 1.0 × 10(7) M(-1) s(-1) (5.8 < pH < 9.8). Cyclic voltammetry was used to measure the potentials of thymine oxidation and dipyridyl reduction in water at pH < 7. Both results give hints for a proton coupled electron-transfer (PCET) reaction from thymine to triplet dipyridyl.

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