Roschek Bill, Tallman Keri A, Rector Christopher L, Gillmore Jason G, Pratt Derek A, Punta Carlo, Porter Ned A
Department of Chemistry and Center in Molecular Toxicology, Vanderbilt University, Nashville, Tennessee 37235, USA.
J Org Chem. 2006 Apr 28;71(9):3527-32. doi: 10.1021/jo0601462.
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).
基于过氧自由基的单分子β-裂解（k(β)）与其与氢原子供体的双分子反应（k(H)）之间的竞争，已开发并校准了一系列过氧自由基时钟。这些时钟基于亚油酸甲酯或烯丙基苯，并直接用α-生育酚或亚油酸甲酯进行校准，它们与过氧自由基反应的速率常数已得到充分确定（k(H-生育酚)=3.5×10(6) M(-1) s(-1)，k(H-亚油酸酯)=62 M(-1) s(-1)）。这种过氧自由基时钟方法已成功应用于确定范围从10(0)到10(7) M(-1) s(-1)的抑制和传播速率常数。
