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Title
| - pH-Induced Changes in Adsorbed Cytochrome c. Voltammetric andSurface-Enhanced Resonance Raman Characterization PerformedSimultaneously at Chemically Modified Silver Electrodes
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Abstract
| - The influence of pH on the redox properties of cytochrome c (cyt c) adsorbed on roughened silver electrodeschemically modified with a self-assembled monolayer (SAM) of 11-mercapto-1-undecanoic acid (MUA) was studiedwith voltammetric techniques in combination with surface-enhanced resonance Raman scattering (SERRS). Theexperiments were performed simultaneously on the same electrode sample in a homemade spectroelectrochemical cellsuitable for such applications. At pH 7.0 cyt c was found in its native state; at higher pH values (ranging from 8.0to 9.0) the redox properties of the adsorbed protein varied considerably, featuring a redox behavior which does notresemble the one reported for the alkaline transition. Our results instead indicate the presence of an electrochemicallyinactive 6cLS species immobilized on MUA at pH 9.0. The pH-induced conformational changes observed for cyt cimmobilized on the SAM of MUA were found to be repeatable and chemically reversible, meaning that the recoveryof the electrochemical signal due to the native protein occurred instantaneously (on the second time scale) when theelectrode was switched back to pH 7.0. The pH-induced changes observed were attributed to a conformational changeinvolving a heme reorientation with respect to the electrode surface.
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