Mechanism of the OH Radical Addition to Adenine from Quantum-Chemistry Determinations of Reaction Paths and Spectroscopic Tracking of the Intermediates

2016 ◽  
Vol 82 (1) ◽  
pp. 276-288 ◽  
Author(s):  
Antonio Francés-Monerris ◽  
Manuela Merchán ◽  
Daniel Roca-Sanjuán
Keyword(s):  
Quantum Chemistry ◽  
Radical Addition ◽  
Oh Radical ◽  
Reaction Paths

BrHgO• + C2H4 and BrHgO• + HCHO in Atmospheric Oxidation of Mercury: Determining Rate Constants of Reactions with Pre-Reactive Complexes and a Bifurcation

2019 ◽  
Author(s):  
Khoa T. Lam ◽  
Curtis J. Wilhelmsen ◽  
Theodore Dibble
Keyword(s):  
Hydrogen Atom ◽  
Quantum Chemistry ◽  
Transition State ◽  
Rate Constant ◽  
Rate Constants ◽  
Minimum Energy ◽  
Atmospheric Oxidation ◽  
Minimum Energy Path ◽  
Oh Radical ◽  
Hydrogen Atoms

Models suggest BrHgONO to be the major Hg(II) species formed in the global oxidation of Hg(0), and BrHgONO undergoes rapid photolysis to produce the thermally stable radical BrHgO•. We previously used quantum chemistry to demonstrate that BrHgO• can, like OH radical, readily can abstract hydrogen atoms from sp<sup>3</sup>-hybridized carbon atoms as well as add to NO and NO<sub>2</sub>. In the present work, we reveal that BrHgO• can also add to C<sub>2</sub>H<sub>4</sub> to form BrHgOCH<sub>2</sub>CH<sub>2</sub>•, although this addition appears to proceed with a lower rate constant than the analogous addition of •OH to C<sub>2</sub>H<sub>4</sub>. Additionally, BrHgO• can readily react with HCHO in two different ways: either by addition to the carbon or by abstraction of a hydrogen atom. The minimum energy path for the BrHgO• + HCHO reaction bifurcates, forming two pre-reactive complexes, each of which passes over a separate transition state to form a different product.

Abinitio SCF MO calculations on the reactions of OH radical with pyridine and pyridinium ion

1982 ◽  
Vol 60 (7) ◽  
pp. 813-819 ◽  
Author(s):  
M. C. Anthony ◽  
W. L. Waltz ◽  
P. G. Mezey
Keyword(s):  
Hydroxyl Radical ◽  
Experimental Information ◽  
Electron Delocalization ◽  
Oh Radical ◽  
Reaction Paths ◽  
Mo Calculations ◽  
Relative Stabilities ◽  
Electrophilic Character ◽  
Determining Factor ◽  
Pyridinium Ion

Relative energies of various products formed in the reaction of pyridine and pyridinium ion with the hydroxyl radical are calculated using non-empirical SCF MO techniques. The favourable electron delocalization in the meta-products, rather than the electrophilic character of the OH radical is the determining factor of relative stabilities. Calculated energy barriers along approximate reaction paths correlate with the available experimental information.

Kinetics and Products of OH Radical Addition to Baicalin

1995 ◽  
Vol 142 (2) ◽  
pp. 227 ◽  
Author(s):  
Xujia Zhang ◽  
Jilan Wu ◽  
Zhongli Cai ◽  
Side Yao ◽  
Zhihua Zuo ◽  
...  
Keyword(s):  
Radical Addition ◽  
Oh Radical

Regioselectivity of the OH Radical Addition to Uracil in Nucleic Acids. A Theoretical Approach Based on QM/MM Simulations

2017 ◽  
Vol 13 (10) ◽  
pp. 5089-5096 ◽  
Author(s):  
Juan Aranda ◽  
Antonio Francés-Monerris ◽  
Iñaki Tuñón ◽  
Daniel Roca-Sanjuán
Keyword(s):  
Nucleic Acids ◽  
Theoretical Approach ◽  
Radical Addition ◽  
Oh Radical
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