期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 107, 期 12, 页码 5282-5287出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0910347107
关键词
free radicals; Marcus theory; proton-coupled electron transfer; reactive oxygen species; oxyl radicals
资金
- National Institutes of Health [GM50422]
- University of Washington, Department of Chemistry
Chemical reactions that involve net hydrogen atom transfer (HAT) are ubiquitous in chemistry and biology, from the action of antioxidants to industrial and metalloenzyme catalysis. This report develops and validates a procedure to predict rate constants for HAT reactions of oxyl radicals (RO center dot) in various media. Our procedure uses the Marcus cross relation (CR) and includes adjustments for solvent hydrogen-bonding effects on both the kinetics and thermodynamics of the reactions. Kinetic solvent effects (KSEs) are included by using Ingold's model, and thermodynamic solvent effects are accounted for by using an empirical model developed by Abraham. These adjustments are shown to be critical to the success of our combined model, referred to as the CR/KSE model. As an initial test of the CR/KSE model we measured self-exchange and cross rate constants in different solvents for reactions of the 2,4,6-tri-tert-butylphenoxyl radical and the hydroxylamine 2,2'-6,6'-tetramethylpiperidin-1-ol. Excellent agreement is observed between the calculated and directly determined cross rate constants. We then extend the model to over 30 known HAT reactions of oxyl radicals with OH or CH bonds, including biologically relevant reactions of ascorbate, peroxyl radicals, and alpha-tocopherol. The CR/KSE model shows remarkable predictive power, predicting rate constants to within a factor of 5 for almost all of the surveyed HAT reactions.
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