Spectroscopic Observation of Calcium-Induced Reorientation of Cellobiose Dehydrogenase Immobilized on Electrodes and its Effect on Electrocatalytic Activity
Kielb P, Sezer M, Katz S, Lopez F, Schulz C, Gorton L, Ludwig R, Wollenberger U, Zebger I, Weidinger IM (2015)
Publication Type: Journal article
Publication year: 2015
Journal
Book Volume: 16
Pages Range: 1960-1968
Journal Issue: 9
Abstract
Cellobiose dehydrogenase catalyzes the oxidation of various carbohydrates and is considered as a possible anode catalyst in biofuel cells. It has been shown that the catalytic performance of this enzyme immobilized on electrodes can be increased by presence of calcium ions. To get insight into the Ca2+-induced changes in the immobilized enzyme we employ surface-enhanced vibrational (SERR and SEIRA) spectroscopy together with electrochemistry. Upon addition of Ca2+ ions electrochemical measurements show a shift of the catalytic turnover signal to more negative potentials while SERR measurements reveal an offset between the potential of heme reduction and catalytic current. Comparing SERR and SEIRA data we propose that binding of Ca2+ to the heme induces protein reorientation in a way that the electron transfer pathway of the catalytic FAD center to the electrode can bypass the heme cofactor, resulting in catalytic activity at more negative potentials. A new road: Electrochemistry combined with surface enhanced vibrational (SERR and SEIRA) spectroscopy are employed to obtain mechanistic insight into the catalytic performance of cellobiose dehydrodegane (MtCDH) immobilized on noble metal electrodes in the presence of Ca2+ ions. The results show induced reorientation of the enzyme on the electrode, which leads to a new electron transfer pathway between the protein and the electrode.
Involved external institutions
Technische Universität Berlin
Germany (DE)
Lund University / Lunds universitet
Sweden (SE)
Universität für Bodenkultur Wien (BOKU) / University of Natural Resources and Life Sciences, Vienna
Austria (AT)
Universität Potsdam
Germany (DE)
Germany (DE)
Lund University / Lunds universitet
Sweden (SE)
Universität für Bodenkultur Wien (BOKU) / University of Natural Resources and Life Sciences, Vienna
Austria (AT)
Universität Potsdam
Germany (DE)
How to cite
APA:
Kielb, P., Sezer, M., Katz, S., Lopez, F., Schulz, C., Gorton, L.,... Weidinger, I.M. (2015). Spectroscopic Observation of Calcium-Induced Reorientation of Cellobiose Dehydrogenase Immobilized on Electrodes and its Effect on Electrocatalytic Activity. ChemPhysChem, 16(9), 1960-1968. https://doi.org/10.1002/cphc.201500112
MLA:
Kielb, Patrycja, et al. "Spectroscopic Observation of Calcium-Induced Reorientation of Cellobiose Dehydrogenase Immobilized on Electrodes and its Effect on Electrocatalytic Activity." ChemPhysChem 16.9 (2015): 1960-1968.
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