Department of Chemistry and Biochemistry, University of Windsor, Windsor, OntarioN9B3P4, Canada.
NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland20878, United States.
Biochemistry. 2022 Nov 1;61(21):2366-2376. doi: 10.1021/acs.biochem.2c00405. Epub 2022 Oct 13.
The function of vitamin E in biomembranes remains a prominent topic of discussion. As its limitations as an antioxidant persist and novel functions are discovered, our understanding of the role of vitamin E becomes increasingly enigmatic. As a group of lipophilic molecules (tocopherols and tocotrienols), vitamin E has been shown to influence the properties of its host membrane, and a wealth of research has connected vitamin E to polyunsaturated fatty acid (PUFA) lipids. Here, we use contrast-matched small-angle neutron scattering and differential scanning calorimetry to integrate these fields by examining the influence of vitamin E on lipid domain stability in PUFA-based lipid mixtures. The influence of α-tocopherol, γ-tocopherol, and α-tocopherylquinone on the lateral organization of a 1:1 lipid mixture of saturated distearoylphosphatidylcholine (DSPC) and polyunsaturated palmitoyl-linoleoylphosphatidylcholine (PLiPC) with cholesterol provides a complement to our growing understanding of the influence of tocopherol on lipid phases. Characterization of domain melting suggests a slight depression in the transition temperature and a decrease in transition cooperativity. Tocopherol concentrations that are an order of magnitude higher than anticipated physiological concentrations (2 mol percent) do not significantly perturb lipid domains; however, addition of 10 mol percent is able to destabilize domains and promote lipid mixing. In contrast to this behavior, increasing concentrations of the oxidized product of α-tocopherol (α-tocopherylquinone) induces a proportional increase in domain stabilization. We speculate how the contrasting effect of the oxidized product may supplement the antioxidant response of vitamin E.
维生素 E 在生物膜中的功能仍然是一个讨论的焦点。随着其作为抗氧化剂的局限性的持续存在和新功能的发现,我们对维生素 E 作用的理解变得越来越神秘。作为一组亲脂性分子(生育酚和生育三烯酚),维生素 E 已被证明会影响其宿主膜的性质,并且大量研究将维生素 E 与多不饱和脂肪酸(PUFA)脂质联系起来。在这里,我们使用对比匹配的小角中子散射和差示扫描量热法通过检查维生素 E 对基于 PUFA 的脂质混合物中脂质域稳定性的影响来整合这些领域。α-生育酚、γ-生育酚和α-生育酚醌对饱和二硬脂酰基磷脂酰胆碱(DSPC)和多不饱和棕榈酰亚油酰磷脂酰胆碱(PLiPC)与胆固醇 1:1 脂质混合物的侧向组织的影响提供了对生育酚对脂质相影响的理解的补充。结构域熔化的特性表明转变温度略有降低,转变协同性降低。比预期的生理浓度(2 摩尔百分比)高一个数量级的生育酚浓度不会显著干扰脂质结构域;然而,添加 10 摩尔百分比能够使结构域不稳定并促进脂质混合。与这种行为相反,α-生育酚的氧化产物(α-生育酚醌)的浓度增加会导致结构域稳定程度成比例增加。我们推测氧化产物的对比效果如何补充维生素 E 的抗氧化反应。