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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Is vanadate reduced by thiols under biological conditions? Changing the Redox potential of V(V)/V(IV) by complexation in aqueous solution
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Is vanadate reduced by thiols under biological conditions? Changing the Redox potential of V(V)/V(IV) by complexation in aqueous solution

机译：钒在生物条件下会被硫醇还原吗？通过水溶液络合改变V（V）/ V（IV）的氧化还原电势

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Although dogma states that vanadate is readily reduced by glutathione, cysteine, and other thiols, there are several examples documenting that vanadium(V)-sulfur complexes can form and be observed. This conundrum has impacted life scientists for more than two decades. Investigation of this problem requires an understanding of both the complexes that form from vanadium(IV) and (V) and a representative thiol in aqueous solution. The reactions of vanadate and hydrated vanadyl cation with 2-mercaptoethanol have been investigated using multinuclear NMR, electron paramagnetic resonance (EPR), and UV-vis spectroscopy. Vanadate forms a stable complex of 2:2 stoichiometry with 2-mercaptoethanol at neutral and alkaline pH. In contrast, vanadate can oxidize 2-mercaptoethanol; this process is favored at low pH and high solute concentrations. The complex that forms between aqueous vanadium(IV) and 2-mercaptoethanol has a 1:2 stoichiometry and can be observed at high pH and high 2-mercaptoethanol concentration. The solution structures have been deduced based on coordination induced chemical shifts and speciation diagrams prepared. This work demonstrates that both vanadium(IV) and (V)-thiol complexes form and that redox chemistry also takes place. Whether reduction of vanadate takes place is governed by a combination of parameters: pH, solute- and vanadate-concentrations and the presence of other complexing ligands. On the basis of these results it is now possible to understand the distribution of vanadium in oxidation states (IV) and (V) in the presence of glutathione, cysteine, and other thiols and begin to evaluate the forms of the vanadium compounds that exert a particular biological effect including the insulin-enhancing agents, antiamoebic agents, and interactions with vanadium binding proteins.
机译：尽管教条指出，谷胱甘肽，半胱氨酸和其他硫醇可轻易还原钒酸盐，但仍有一些实例证明钒（V）-硫配合物可以形成并被观察到。这个难题已经影响生命科学家超过二十年了。要研究此问题，需要了解钒（IV）和（V）形成的络合物以及水溶液中的代表性硫醇。使用多核NMR，电子顺磁共振（EPR）和UV-vis光谱研究了钒酸盐和水合钒氧阳离子与2-巯基乙醇的反应。钒酸盐与2-巯基乙醇在中性和碱性pH下形成化学计量比为2：2的稳定络合物。相比之下，钒酸盐可以氧化2-巯基乙醇。在低pH和高溶质浓度下，此过程是有利的。钒（IV）水溶液和2-巯基乙醇之间形成的配合物的化学计量比为1：2，可以在高pH和2-巯基乙醇高浓度下观察到。根据配位诱导的化学位移和所形成的形态图推导了溶液的结构。这项工作表明钒（IV）和（V）-硫醇配合物都形成了，并且还发生了氧化还原化学反应。钒酸盐的还原是否发生取决于以下参数的组合：pH，溶质和钒酸盐的浓度以及其他络合配体的存在。根据这些结果，现在有可能了解在谷胱甘肽，半胱氨酸和其他硫醇存在下，氧化态（IV）和（V）中钒的分布，并开始评估钒化合物的形式，这些化合物能特定的生物学作用，包括胰岛素增强剂，抗阿米巴剂以及与钒结合蛋白的相互作用。

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