A-Tocopherol , oxidation

Diirckheimer, W. Cohen, L. A. Mechanisms of a-tocopherol oxidation synthesis of the highly labile 9-hydroxy-a-tocopherone. Biochem. Biophys. Res. Commun. 1962,9,262-265. 

AH formulations of vitamin E must show low acidity, and contain not more than 0.004% heavy metals (reported as Pb) and not more than 10 ppm Pb. Eormulations that contain RRR-a-tocopherol must have a specific rotation of +24 ° for the oxidation product with alkaline potassium ferricyanide. 

Encouraged by the short synthesis of K vitamins, the chromium-mediated benzannulation was extended to the synthesis of vitamin E 68 [59]. The problem of imperfect regioselectivity of alkyne incorporation - which did not hamper the approach to vitamin K due to the final oxidation to the quinone - was tackled by demethylation of both regioisomeric hydroquinone monomethyl ethers 67 to give the unprotected hydroquinone. Subsequent ring closure yielded a-tocopherol (vitamin E) 68 (Scheme 39). 

Figure 45-6. Interaction and synergism between antioxidant systems operating in the lipid phase (membranes) of the cell and the aqueous phase (cytosol). (R-,free radical PUFA-00-, peroxyl free radical of polyunsaturated fatty acid in membrane phospholipid PUFA-OOH, hydroperoxy polyunsaturated fatty acid in membrane phospholipid released as hydroperoxy free fatty acid into cytosol by the action of phospholipase Aj PUFA-OH, hydroxy polyunsaturated fatty acid TocOH, vitamin E (a-tocopherol) TocO, free radical of a-tocopherol Se, selenium GSH, reduced glutathione GS-SG, oxidized glutathione, which is returned to the reduced state after reaction with NADPH catalyzed by glutathione reductase PUFA-H, polyunsaturated fatty acid.)...

BARTH T J, ZOLER J, KUBELER A, BORN A I and OSSWALD H (1997) Redifferentiation of oral dysplasic mucosa by the application of the anti-oxidants beta-carotene, a-tocopherol and vitamin C. Int J Vitam Nutr Res 67(5) 368-76. 

Therefore depending upon the conditions used to simulate either in vitro or in vivo oxidation, catechins or other phenolic compounds display differences in their antioxidant properties. Catechins also limited the consumption of a-tocopherol, allowing it to act as a scavenger within cell membranes whilst the catechins scavenged aqueous peroxyl radicals near the membrane surface (Pietta and Simonetti, 1998). 

PORKKALA-SARATAHO E K, NYYSSONEN K M, KAIKKONEN J E, POULSEN H E, HAYN E M, SALONEN R M, SALONEN J T (1998) A randomized, single-blind, placebo controlled trial of the effects of 200 mg a-tocopherol on the oxidation resistance of atherogenic hpoproteins, American Journal of Clinical Nutrition, 68, 1034-41. 

There has been some evidence of a higher antioxidant effect when both flavonoids and a-tocopherol are present in systems like LDL, low-density lipoproteins (Jia et al., 1998 Zhu et al, 1999). LDL will incorporate a-tocopherol, while flavonoids will be present on the outside in the aqueous surroundings. A similar distribution is to be expected for oil-in-water emulsion type foods. In the aqueous environment, the rate of the inhibition reaction for the flavonoid is low due to hydrogen bonding and the flavonoid will not behave as a chain-breaking antioxidant. Likewise, in beer, none of the polyphenols present in barley showed any protective effect on radical processes involved in beer staling, which is an oxidative process (Andersen et al, 2000). The polyphenols have, however, been found to act synergistically... 

In the water-like solvent tert-butyl alcohol, a-tocopherol was found to prevent lipid oxidation, showing a distinct lag-phase for oxygen consumption. This was in contrast to quercetin or epicatechin, which were only weak retarders of lipid oxidation without any clear antioxidative effect. Quercetin or epicatechin, when combined with a-tocopherol, increased the lag-phase for oxygen consumption as seen for a-tocopherol alone. The stoichiometric factor for a-tocopherol, a-TOH, as chain-breaking antioxidant has the value n = 2 according to the well-established mechanism ... 

Green tea Tea catechins (300 ppm is typically required) Raw minced beef, pork, poultry and fish Cooked red meat, poultry and fish Frozen chicken meat Effect up to four times that of a-tocopherol Inhibits pro-oxidative effect of added NaCl Protection of a-tocopherol in muscles when added to chicken feed Tang et al., 2001c Tang et al., 2001b Tang et al., 2002... 

Yeum, K.J. et al., The effect of a-tocopherol on the oxidative cleavage of P-carotene,... 

Interestingly, early examples of carotenoid autoxidation in the literature described the influence of lipids and other antioxidants on the autoxidation of carotenoids." " In a stndy by Budowski et al.," the influence of fat was fonnd to be prooxidant. The oxidation of carotenoids was probably not only cansed by molecnlar oxygen bnt also by lipid oxidation products. This now well-known phenomenon called co-oxidation has been stndied in lipid solntions, in aqueons solntions catalyzed by enzymes," and even in food systems in relation to carotenoid oxida-tion." The inflnence of a-tocopherol on the antoxidation of carotenoids was also stndied by Takahashi et al. ° who showed that carotene oxidation was snppressed as... 

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