Widening the Product Profile of Carbon Dioxide Reduction by Vanadium Nitrogenase.
Two reaction systems based on vanadium nitrogenase were previously shown to reduce CO2 to hydrocarbons: 1) an enzyme-based system that used both components of V nitrogenase for ATP-dependent reduction of CO2 to ≤C2 hydrocarbons; and 2) a cofactor-based system that employed SmI2 to supply electrons to the isolated V cluster for an ATP-independent reduction of CO2 to ≤C3 hydrocarbons. Here, we report ATP-independent reduction of CO2 to hydrocarbons by a reaction system comprising Eu(II) DTPA and the VFe protein of V nitrogenase. Combining features of both enzyme- and cofactor-based systems, this system exhibits improved C-C coupling and a broader product profile of ≤C4 hydrocarbons. The C-C coupling does not employ CO2 -derived CO, and it is significantly enhanced in D2 O. These observations afford initial insights into the characteristics of this unique reaction and provide a potential template for future design of catalysts to recycle the greenhouse gas CO2 into useful products.
Department of Molecular Biology and Biochemistry, University of California in Irvine, 2230/2236 McGaugh Hall, Irvine, CA, 92697-3900, USA.
Johannes G
JG
Rebelein
Department of Molecular Biology and Biochemistry, University of California in Irvine, 2230/2236 McGaugh Hall, Irvine, CA, 92697-3900, USA. yilinh@uci.edu.
Yilin
Y
Hu
Department of Molecular Biology and Biochemistry, University of California in Irvine, 2230/2236 McGaugh Hall, Irvine, CA, 92697-3900, USA. mribbe@uci.edu.|Department of Chemistry, University of California in Irvine, 2236 McGaugh Hall, Irvine, CA, 92697-2025, USA. mribbe@uci.edu.
Markus W
MW
Ribbe
D016948:Azotobacter vinelandii / Q000737:chemistry / Q000201:enzymology* / Q000378:metabolism; D002245:Carbon Dioxide / Q000378:metabolism*; D002248:Carbon Monoxide / Q000378:metabolism; D005063:Europium / Q000378:metabolism; D006838:Hydrocarbons / Q000737:chemistry / Q000378:metabolism*; D008958:Models, Molecular; D009591:Nitrogenase / Q000378:metabolism*; D010084:Oxidation-Reduction
D006838:Hydrocarbons; D002245:Carbon Dioxide; D005063:Europium; D002248:Carbon Monoxide; D009591:Nitrogenase
CO2 reduction; C−C coupling reactions; V nitrogenase; enzyme catalysis; hydrocarbon formation; oxidoreductases