title: Peroxyl radical clocks.
abstract: A series of peroxyl radical clocks has been developed and calibrated based on the competition between the unimolecular beta-fragmentation (k(beta)) of a peroxyl radical and its bimolecular reaction with a hydrogen atom donor (k(H)). These clocks are based on either methyl linoleate or allylbenzene and were calibrated directly with alpha-tocopherol or methyl linoleate, which have well-established rate constants for reaction with peroxyl radicals (k(H-tocopherol) = 3.5 x 10(6) M(-1) s(-1), k(H-linoleate) = 62 M(-1) s(-1)). This peroxyl radical clock methodology has been successfully applied to determine inhibition and propagation rate constants ranging from 10(0) to 10(7) M(-1) s(-1).
authors.affiliation: Department of Chemistry and Center in Molecular Toxicology, Vanderbilt University, Nashville, Tennessee 37235, USA.
authors.forename: Bill
authors.initials: B
authors.lastname: Roschek
authors.forename: Keri A
authors.initials: KA
authors.lastname: Tallman
authors.forename: Christopher L
authors.initials: CL
authors.lastname: Rector
authors.forename: Jason G
authors.initials: JG
authors.lastname: Gillmore
authors.forename: Derek A
authors.initials: DA
authors.lastname: Pratt
authors.forename: Carlo
authors.initials: C
authors.lastname: Punta
authors.forename: Ned A
authors.initials: NA
authors.lastname: Porter
mesh_terms: D002138:Calibration; D002851:Chromatography, High Pressure Liquid; D008041:Linoleic Acids / Q000737:chemistry; D010084:Oxidation-Reduction; D010545:Peroxides / Q000737:chemistry*; D014810:Vitamin E / Q000737:chemistry
chemical_list: D008041:Linoleic Acids; D010545:Peroxides; D014810:Vitamin E; C005575:methyl linoleate; C049375:perhydroxyl radical