TY - JOUR A1 - Bosserdt, Maria A1 - Gajovic-Eichelman, Nenad A1 - Scheller, Frieder W. T1 - Modulation of direct electron transfer of cytochrome c by use of a molecularly imprinted thin film JF - Analytical & bioanalytical chemistry N2 - We describe the preparation of a molecularly imprinted polymer film (MIP) on top of a self-assembled monolayer (SAM) of mercaptoundecanoic acid (MUA) on gold, where the template cytochrome c (cyt c) participates in direct electron transfer (DET) with the underlying electrode. To enable DET, a non-conductive polymer film is electrodeposited from an aqueous solution of scopoletin and cyt c on to the surface of a gold electrode previously modified with MUA. The electroactive surface concentration of cyt c was 0.5 pmol cm(-2). In the absence of the MUA layer, no cyt c DET was observed and the pseudo-peroxidatic activity of the scopoletin-entrapped protein, assessed via oxidation of Ampliflu red in the presence of hydrogen peroxide, was only 30 % of that for the MIP on MUA. This result indicates that electrostatic adsorption of cyt c by the MUA-SAM substantially increases the surface concentration of cyt c during the electrodeposition step, and is a prerequisite for the productive orientation required for DET. After template removal by treatment with sulfuric acid, rebinding of cyt c to the MUA-MIP-modified electrode occurred with an affinity constant of 100,000 mol(-1) L, a value three times higher than that determined by use of fluorescence titration for the interaction between scopoletin and cyt c in solution. The DET of cyt c in the presence of myoglobin, lysozyme, and bovine serum albumin (BSA) reveals that the MIP layer suppresses the effect of competing proteins. KW - Cytochrome c KW - Molecularly imprinted polymer film KW - Mercaptoundecanoic acid KW - Direct electron transfer KW - Scopoletin (7-hydroxy-6-methoxycoumarin) Y1 - 2013 U6 - https://doi.org/10.1007/s00216-013-7009-8 SN - 1618-2642 VL - 405 IS - 20 SP - 6437 EP - 6444 PB - Springer CY - Heidelberg ER -