Rousseau-Richard C, Richard C, Martin R
Laboratoire de Chimie Radicalaire, UA 328 du CNRS, Université de Nancy I, Vandoeuvre, France.
FEBS Lett. 1988 Jun 20;233(2):307-10. doi: 10.1016/0014-5793(88)80448-4.
The kinetics of bimolecular decay of alpha-tocopheroxyl free radicals (T) was studied by ESR mainly in ethanol and heptanol solvents. A second-order kinetic law was observed during the whole course of reaction (-d[T]/dt = 2k[T]2) and the following rate constants were determined with good accuracy in the temperature range 281-321 K: ethanol: log(2k) = 8.2 +/- 0.5--(6.6 +/- 0.7 kcal/mol)/(2.3RT) M-1.s-1; heptanol: log(2k) = 6.1 +/- 0.4--(4.3 +/- 0.6 kcal/mol)/(2.3RT) M-1.s-1. The global rate constant clearly increases with solvent polarity.
主要在乙醇和庚醇溶剂中通过电子自旋共振（ESR）研究了α-生育酚自由基（T）双分子衰变的动力学。在整个反应过程中观察到二级动力学规律（-d[T]/dt = 2k[T]²），并且在281 - 321 K的温度范围内准确测定了以下速率常数：乙醇：log(2k) = 8.2 ± 0.5 - (6.6 ± 0.7 kcal/mol)/(2.3RT) M⁻¹·s⁻¹；庚醇：log(2k) = 6.1 ± 0.4 - (4.3 ± 0.6 kcal/mol)/(2.3RT) M⁻¹·s⁻¹。整体速率常数明显随溶剂极性增加。
