A Comparison of the Reactions of N-Methyl-3-dehydropyridinium Cation with Adenine, Cytosine, Thymine and Uracil in the Gas Phase and in Aqueous Solution

摘要

The types of products and relative rates of reaction for each nucleobase differ in the two environments, which can be explained by solvation effects. Hydrogen atom abstraction as a final product is seen only in the gas phase, not in aqueous solution. With solvent caging, any hydrogen atom abstraction products can further react in the reaction complex to form other products. Only reactions involving addition of the nucleobase to the radical site are seen as final products in solution, which can be explained by solvent caging. Mechanistic studies need to be performed to determine how the addition of OH to thymine adduct occurs.