Molecular Associations of Vitamin E

Department of Biochemistry, King's College London, London SE2 9NH, United Kingdom.
Vitamins & Hormones (Impact Factor: 2.04). 02/2007; 76:67-98. DOI: 10.1016/S0083-6729(07)76004-1
Source: PubMed


To understand how vitamin E fulfills its functions in membranes and lipoproteins, it is necessary to know how it associates with the lipid components of these structures and the effects its presence has on their structure and stability. Studies of model membrane systems containing vitamin E have proved to be an informative approach to address these questions. A review of the way vitamin E interacts with phospholipid bilayers, how it distributes within the structure, its motional diffusion characteristics, and orientation has been undertaken. The effect of vitamin E on membrane stability and permeability has been described. The tendency of vitamin E to form complexes with certain phospholipids is examined as is the way modulation of protein functions takes place. Finally, recent evidence relevant to the putative role of vitamin E in protecting membranes from free radical attack and the consequences of lipid oxidation in lipoproteins and membranes is examined.

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    • "Of course, a considerable amount of work has focused on the biochemical aspects of a-tocopherol in model membranes of liposomes and vesicles [7] [8] [9]. Despite the complexities involved, to be able to explain and predict the antioxidant actions of tocopherol in membranes, we need to know how its orientation and dynamics within a bilayer [10] [11] [12] is affected by the nature of the bulk phospholipids. "
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    ABSTRACT: Vitamin E (α-tocopherol) has long been recognized as the major antioxidant in biological membranes, and yet many structurally related questions persist of how the vitamin functions. For example, the very low levels of α-tocopherol reported for whole cell extracts question how this molecule can successfully protect the comparatively enormous quantities of PUFA-containing phospholipids found in membranes that are highly susceptible to oxidative attack. The contemporary realization that membranes laterally segregate into regions of distinct lipid composition (domains), we propose, provides the answer. We hypothesize α-tocopherol partitions into domains that are enriched in polyunsaturated phospholipids, amplifying the concentration of the vitamin in the place where it is most needed. These highly disordered domains depleted in cholesterol are analogous, but organizationally antithetical, to the well-studied lipid rafts. We review here the ideas that led to our hypothesis. Experimental evidence in support of the formation of PUFA-rich domains in model membranes is presented, focusing upon docosahexaenoic acid that is the most unsaturated fatty acid commonly found. Physical methodologies are then described to elucidate the nature of the interaction of α-tocopherol with PUFA and to establish that the vitamin and PUFA-containing phospholipids co-localize in non-raft domains.
    Molecular Nutrition & Food Research 05/2010; 54(5):641 - 651. DOI:10.1002/mnfr.200900439 · 4.60 Impact Factor
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    ABSTRACT: An interesting strategy for protecting skin from excessive exposure to free radicals is to support the skin endogenous antioxidant system. As the balance between different skin antioxidants is very important, a combined therapy using at least two antioxidants is desirable. In the present work, o/w, w/o, and gel-like microemulsions (ME), all composed of the same ingredients, were selected as carrier systems for dermal delivery of vitamins C and E. Gel-like ME was found to offer the best protection for both vitamins, although other ME also significantly increased their stability compared with that solution. In the presence of vitamin C no decrease in vitamin E content occurred. To obtain ME appropriate for dermal use, their viscosity was increased by adding thickening agents. On the basis of visual examination of viscosity and physical stability of thickened systems, several thickeners were selected. The addition of thickener significantly increased the viscosity of ME and changed the behavior of systems from ideal Newtonian to thixotropic. Finally, the stability of both vitamins was examined as a function of thickening agent and of the location of vitamins in the ME. The addition of thickeners changed the stability of at least one vitamin, but the systems generally still protected vitamins better than solutions. It is likely that the changes in internal organization of ME resulting from the addition of thickener, confirmed by thermal analysis and changes in solubility of oxygen in the outer phase, were the most important factors that influenced the stability of vitamins in thickened systems.
    Drug Delivery 05/2007; 14(4):235-45. DOI:10.1080/10717540601067786 · 2.56 Impact Factor
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    ABSTRACT: The familiar role of tocols (tocopherols and tocotrienols) as lipid-soluble chain-terminating inhibitors of lipid peroxidation is currently in the midst of a reinterpretation. New biological activities have been described for tocols that apparently are not dependent on their well-established antioxidant behaviour. These activities could well be real, but there remain large gaps in our understanding of the behaviour of tocols in membranes, especially when it comes to the alpha-, beta-, gamma-, delta-chroman methylation patterns and the seemingly special nature of tocotrienols. It is inappropriate to make conclusions and develop models based on in vivo (or cell culture) results with reference to in vitro measurements of antioxidant activity. When present in biological membranes, tocols will experience a large variation in the local composition of phospholipids and the presence of neutral lipids such as cholesterol, both of which would be expected to change the efficiency of antioxidant action. It is likely that tocols are not homogeneously dispersed in a membrane, but it is still not known whether any specific combination of lipid head group and acyl chains are conferred special protection from peroxidation, nor do we currently appreciate the structural role that tocols play in membranes. Tocols may enhance curvature stress or counteract similar stresses generated by other lipids such as lysolipids. This review will outline what is known about the location and behaviour of tocols in phospholipid bilayers. We will draw mainly from the biophysical literature, but will attempt to extend the discussion to biologically relevant phenomena when appropriate. We hope that it will assist researchers when designing new experiments and when critically assessing the results, in turn providing a more thorough understanding of the biochemistry of tocols.
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