Title

Peroxyl Radical Clocks

Document Type

Article

Publication Date

4-28-2006

Comments

This article was published while author Jason G. Gillmore was at the Center in Mo lecular Toxicology, Vanderbilt University.

Abstract

A series of peroxyl radical clocks has been developed and calibrated based on the competition between the unimolecular β-fragmentation (kβ) of a peroxyl radical and its bimolecular reaction with a hydrogen atom donor (kH). These clocks are based on either methyl linoleate or allylbenzene and were calibrated directly with α-tocopherol or methyl linoleate, which have well-established rate constants for reaction with peroxyl radicals (kH-tocopherol = 3.5 × 106 M-1 s-1, kH-linoleate = 62 M-1 s-1). This peroxyl radical clock methodology has been successfully applied to determine inhibition and propagation rate constants ranging from 100 to 107 M-1 s-1.

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