Radical cations of vitamin E

Radical cations of vitamin E
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DOI:
10.1039/b110970g
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发表时间:
2002-01-01
影响因子:
3.3
通讯作者:
Joela, H
Joela, H
中科院分区:
化学2区
文献类型:
--
作者:
Lehtovuori, P;Joela, H

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维生素E化合物(α-、β-、γ-和δ-生育酚以及α-、β-、γ-和δ-生育三烯酚)的自由基阳离子首次在不同溶剂中成功制备。通过EPR和ENDOR谱求解了它们的未成对电子分布,并对各向同性超精细耦合进行了归属。各向同性超精细耦合常数的理论计算(UB 3LYP)与实验研究。自由基阳离子被观察到存在的中性自由基形成的中间产物。此外,从生育酚和生育三烯酚的自由基阳离子中释放质子产生中性自由基,这在ENDOR光谱中检测到。讨论了作为各种生育酚和生育三烯酚化合物的生物活性的量度的自由基阳离子的羟基质子的进一步反应的效力。
Radical cations of vitamin E compounds (alpha-, beta-, gamma- and delta-tocopherols and alpha-, beta-, gamma- and delta-tocotrienols) were for the first time successfully prepared in different solvents. Their unpaired electron distribution was solved by means of EPR and ENDOR spectroscopy and assignment of isotropic hyperfine couplings was performed. The isotropic hyperfine coupling constants calculated theoretically (UB3LYP) were comparable to those studied experimentally. Radical cations were observed to exist as an intermediate product in the formation of the neutral radical. Moreover, loosening the proton from the radical cation of a tocopherol and from a tocotrienol produced the neutral radical, which was detected in the ENDOR spectrum. The potency of the hydroxyl proton of the radical cation for further reactions as a measure of the biological activity of various tocopherol and tocotrienol compound is discussed.