Insight into the Mechanism of [NiFe] Hydrogenases by means of Magnetic Resonance Experiments and DFT Calculations [article]

Matthias Stein, Wolfgang Lubitz, Technische Universität Berlin, Technische Universität Berlin
Hydrogenases are enzymes that catalyze the heterolytic splitting of molecular hydrogen. [NiFe] hydrogenases utilize a heterobimetallic cluster to accomplish this task. Some of the redox states of the active centre are paramagnetic and are thus accessible by EPR spectroscopy. The Ni-A, Ni-B and Ni-C forms were investigated by pulsed 1H-ENDOR spectroscopy in protein single crystals and frozen solution, respectively. Density functional theory (DFT) calculations provided insight into the electronic
more » ... into the electronic structure of the paramagnetic intermediates. By means of relativistic DFT calculations using the ZORA Hamiltonian, magnetic resonance parameters (g- and A-tensors) were calculated from first principles. Thus, a correlation between structure and g-values could be established for the [NiFe] hydrogenase. A plausible reaction mechanism which involves participation of the protein environment could be proposed.
doi:10.14279/depositonce-381 fatcat:ycnxcknje5fbziam6g3ua6bsv4