Microheterogeneous electrocatalytic chiral recognition at monoclinic vanadium-doped zirconias:: Enantioselective detection of glucose

被引:26
作者
Domenech, Antonio [1 ]
Alarcon, Javier
机构
[1] Univ Valencia, Fac Quim, Dept Quim Analit, E-46100 Valencia, Spain
[2] Univ Valencia, Fac Quim, Dept Quim Inorgan, E-46100 Valencia, Spain
关键词
D O I
10.1021/ac070623w
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
Synthetic tetragonal and monoclinic vanadium-doped zirconias (t- and m-VxZr1-xO2, 0.005 < x < 0.150) exert an effective catalytic effect toward the electrochemical oxidation of glucose in aqueous alkaline media. The catalytic effect of monoclinic specimens attached to carbon and fluorine-doped tin oxide electrodes exhibits a remarkable enantioselectivity, so that catalytic currents for the oxidation of L-glucose at +0.92 V vs AgCl/Ag are considerably larger than those obtained for the oxidation of D-glucose. This enantioselectivity can be associated with the existence of a noncentrosymmetric coordination of vanadium centers in the monoclinic crystalline form of zirconia. From the electrochemical results, it can be suggested that the electrocatalytic mechanism includes the formation of glucose-vanadium surface adducts and electron transfer between catalytic centers and the substrate. The interference from chloride ions in the electrocatalytic process is significantly decreased by covering the zirconia particles with a layer of amorphous silica. These results propose that incorporation of catalytically active centers into nonsentrosymmetric sites of inorganic crystalline materials can be taken as a plausible strategy for chiral recognition via electrocatalysis.
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收藏
页码:6742 / 6751
页数:10
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