Kinetic studies of the antioxidant action of vitamin E derivatives have been carried out by means of stopped-flow spectroscopy and femtosecond spectroscopy. Both the electron transfer and the proton tunneling play important roles in the antioxidant reaction of vitamin E. The transition state has the property of the charge-transfer species. The proton tunneling takes place below the transition state. The tunneling allows the proton to cut a corner on the potential energy surface. Mechanism of the prooxidant reaction of vitamin E is also discussed.
The effect of vitamin B_6 deficiency on the biosynthesis of arachidonic acid (20 : 4n-6) from linoleic acid (18 : 2n-6) in rat liver microsomes was studied. Rats fed on a vitamin B_6-deficient diet containing 70% casein for 5 weeks displayed a striking decrease mainly in the activity of terminal Δ6-desaturase (D6D) of the 18 : 2n-6 desaturation system. The decreased activity of D6D seemed to be due to a decrease in the microsomal content of phosphatidylcholine (PC). The activities of choline phosphokinase and choline phosphotransferase decreased clearly. Additionally, the molar ratio of S-adenosylmethionine/S-adenosylhomocysteine in liver decreased drastically and the methylation of phosphatidylethanolamine to PC was repressed. Results in this study demonstrate that vitamin B_6 deficiency modified methionine metabolism and decreased f\choline utilization, which indirectly affected PC biosynthesis, and finally depressed the 18 : 2n-6 desaturation which brought about the decrease of the biosynthesis of 20 : 4n-6.