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Peroxyl radical clocks.

Bill Roschek·Keri A Tallman·Christopher L Rector·Jason G Gillmore·Derek A Pratt·Carlo Punta·Ned A Porter
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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).

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CalibrationChromatography, High Pressure LiquidLinoleic AcidsOxidation-ReductionPeroxidesVitamin EJournal ArticleResearch Support, N.I.H., ExtramuralResearch Support, Non-U.S. Gov'tResearch Support, U.S. Gov't, Non-P.H.S.

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Bill Roschek, Keri A Tallman, Christopher L Rector, Jason G Gillmore, Derek A Pratt, Carlo Punta, Ned A Porter. 2006-04-28. Peroxyl radical clocks.. https://doi.org/10.1021/jo0601462

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