Contrasting reactions of hydrated electron and formate radical with 2-thio analogues of cytosine and uracil

Literature Information

Publication Date 2016-09-29
DOI 10.1039/C6CP04483B
Impact Factor 3.676
Authors

Kavanal P. Prasanthkumar, Juan R. Alvarez-Idaboy, Pavitra V. Kumar, Beena G. Singh, K. Indira Priyadarsini


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Abstract

2-Thiocytosine (TC) and 2-thiouracil (TU) were subjected to hydrated electron (eaq−), formate radical (CO2˙−) and 2-hydroxypropan-2-yl radical ((CH3)2˙COH) reactions in aqueous medium. Transients were characterized by absorption spectroscopy and the experimental findings were rationalized by DFT calculations at LC-ωPBE and M06-2X levels using a 6-311+G(d,p) basis set and SMD solvation. In eaq− reactions, a ring N-atom protonated radical of TC and an exocyclic O-atom protonated radical of TU were observed via addition of eaq− and subsequent protonation by solvent molecules. However, two competing but simultaneous mechanisms are operative in CO2˙− reactions with TC and TU. The first one corresponds to formations of N(O)-atom protonated radicals (similar to eaq− reactions); the second mechanism led to 2 center–3 electron, sulfur–sulfur bonded neutral dimer radicals, TCdim˙ and TUdim˙. DFT calculations demonstrated that H-abstraction by CO2˙− from TC(TU) results in S-centered radical which upon combination with TC(TU) provide the dimer radical. In some cases, DFT energy profiles were further validated by CBS-QB3//M06-2X calculations. This is the first time report for a contradictory behavior in the mechanisms of eaq− and CO2˙− reactions with any pyrimidines or their thio analogues.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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