TY  - JOUR
A1  - Stripp, Sven T.
A1  - Duffus, Benjamin R.
A1  - Fourmond, Vincent
A1  - Leger, Christophe
A1  - Leimkühler, Silke
A1  - Hirota, Shun
A1  - Hu, Yilin
A1  - Jasniewski, Andrew
A1  - Ogata, Hideaki
A1  - Ribbe, Markus W.
T1  - Second and outer coordination sphere effects in nitrogenase, hydrogenase, formate dehydrogenase, and CO dehydrogenase
JF  - Chemical reviews : CR
N2  - Gases like H-2, N-2, CO2, and CO are increasingly recognized as critical feedstock in "green" energy conversion and as sources of nitrogen and carbon for the agricultural and chemical sectors. However, the industrial transformation of N-2, CO2, and CO and the production of H-2 require significant energy input, which renders processes like steam reforming and the Haber-Bosch reaction economically and environmentally unviable. Nature, on the other hand, performs similar tasks efficiently at ambient temperature and pressure, exploiting gas-processing metalloenzymes (GPMs) that bind low-valent metal cofactors based on iron, nickel, molybdenum, tungsten, and sulfur. Such systems are studied to understand the biocatalytic principles of gas conversion including N-2 fixation by nitrogenase and H-2 production by hydrogenase as well as CO2 and CO conversion by formate dehydrogenase, carbon monoxide dehydrogenase, and nitrogenase. In this review, we emphasize the importance of the cofactor/protein interface, discussing how second and outer coordination sphere effects determine, modulate, and optimize the catalytic activity of GPMs. These may comprise ionic interactions in the second coordination sphere that shape the electron density distribution across the cofactor, hydrogen bonding changes, and allosteric effects. In the outer coordination sphere, proton transfer and electron transfer are discussed, alongside the role of hydrophobic substrate channels and protein structural changes. Combining the information gained from structural biology, enzyme kinetics, and various spectroscopic techniques, we aim toward a comprehensive understanding of catalysis beyond the first coordination sphere.
Y1  - 2022
U6  - https://doi.org/10.1021/acs.chemrev.1c00914
SN  - 0009-2665
SN  - 1520-6890
VL  - 122
IS  - 14
SP  - 11900
EP  - 11973
PB  - American Chemical Society
CY  - Washington, DC
ER  -