The electrochemical response of NADH associated to two mesoporous aluminosilicates, MCM-41 and SBA-15, is described upon attachment of such materials into polymer-film electrodes. The studied materials display a significant electrocatalytic activity towards the oxidation of 1,4-dihydrobenzoquinone, H(2)Q. Two models for describing the electrocatalytic process, based on the general theory of mediated electrocatalysis and the Lovric and Scholz formulation of the voltammetry of microparticles are discussed. Voltammetric and chronoamperometric data indicate that the electrocatalytic process involves the formation of a surface-confined NADH-H(2)Q adduct in the case of SBA-15, while a surface reaction/regeneration scheme prevails for MCM-41. (c) 2006 Elsevier Ltd. All rights reserved.