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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机译：基于过氧自由基的单分子β片段化（k_β）和它与氢原子供体的双分子反应（K_H）之间的竞争，已经开发并校准了一系列过氧自由基时钟。亚油酸甲酯或烯丙基苯并直接用α-生育酚或亚油酸甲酯校准，它们具有与过氧自由基（K_（H-生育酚）= 3.5 x 10〜6 M〜（-1）s〜（ -1），k_（H-亚油酸酯）= 62 M〜（-1）s〜（-1））。该过氧自由基时钟方法已成功应用于确定10〜0到10〜的抑制和传播速率常数7 M〜（-1）s〜（-1）。
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