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High-temperature electrocatalysis using thermophilic P450 CYP119: dehalogenation of CCl4 to CH4
Emek Blair1, John Greaves, Patrick J Farmer
1Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
Abstract:
The use of a thermophilic cytochrome P450, CYP119, in electrocatalytic dehalogenations of C1 halocarbon solvents is studied. Temperature stable enzyme-modified electrodes were constructed using sol-gel and polymeric surfactant approaches. CYP119 deposited in a dimethyldidodecylammonium poly(p-styrene sulfonate) (DDAPSS) film has good retention of electrochemical activity up to 80 degrees C. At potentials approaching the FeII/I couple, the CYP119/DDAPSS films demonstrate high catalytic dehalogenations of the C1 chloromethanes CCl4, CHCl3, and CH2Cl2. Product analysis identified mixtures of sequentially dechlorinated products up to methane; no evidence for radical-coupled products was observed. The yield of methane from the CYP119-catalyzed reduction of CCl4 is increased 35-fold from 25 degrees C to 55 degrees C. In combination with the lack of C2 products, the facility of an overall eight-electron reductive dehalogenation suggests that the substrate is constrained within the protein during electrocatalytic turnover.
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