In order to develop novel electroactive hosts for biosensor design, the possibility to use nanostructured vanadate phases as alternatives to well-known V2O5 gels was studied. For this purpose, the formation of M[V3O8] and Mx[V6O16] (x = 1 and 2) oxides by the sol–gel process has been studied over a wide range of cations (M+ = Li+, Na+, K+, Cs+, and NH4+; M2+ = Ca2+, Mg2+ and Ba2+). By a combination of XRD, 51V NMR and SEM studies, it was possible to evidence the influence of the nature and hydration state of cations on the size and morphology of the resulting particles as well as on the kinetics of their formation. On this basis, K2[V6O16] was evaluated for glucose oxidase encapsulation, either via impregnation or co-precipitation methods. When compared to V2O5, these novel bioelectrodes exhibit higher stability under pH conditions of optimum enzymatic activity, as well as better sensitivity, and reproducibility for glucose detection via amperometric titration.
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