Carbon Monoxide. Toxic Gas and Fuel for Anaerobes and Aerobes: Carbon Monoxide Dehydrogenases - The Metal-Driven Biogeochemistry of Gaseous Compounds in the Environment - page 36

Chapter 3
Carbon Monoxide. Toxic Gas and Fuel
for Anaerobes and Aerobes:
Carbon Monoxide Dehydrogenases

Jae-Hun Jeoung, Jochen Fesseler, Sebastian Goetzl, and Holger Dobbek

Contents
ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

1 INTRODUCTION . . . . . . . . . . . . .............................................................. 38

1.1 Chemistry of Carbon Monoxide . . . .................................................. 38

1.2 Carbon Monoxide in the Biosphere .................................................. 40

1.2.1 Biological Cycle of Carbon Monoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

1.2.2 Use of Carbon Monoxide under Aerobic and Anaerobic Conditions . . .... 41

2 STRUCTURE AND FUNCTION OF CARBON MONOXIDE
DEHYDROGENASES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

2.1 Cu,Mo-Containing Carbon Monoxide Dehydrogenases . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

2.1.1 Structure of Cu,Mo-Carbon Monoxide Dehydrogenases ................... 44

2.1.2 Spectroscopic Investigations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

2.1.3 Enzymatic Activity ........................................................... 47

2.1.4 Reaction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

2.2 Monofunctional Ni,Fe-Containing Carbon Monoxide Dehydrogenases ........... 49

2.2.1 Function, Distribution, and Overall Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

2.2.2 Electronic States and Structure of Cluster C ................................ 50

2.2.3 Pathways and Channels Involved in Catalysis .............................. 52

2.2.4 Inhibited States of Cluster C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

2.2.5 Mechanism of Reversible Carbon Dioxide Reduction at Cluster C . . . . . . . . 55

2.3 Bifunctional Ni,Fe-Containing Carbon Monoxide Dehydrogenases . . . . . . . . . ...... 56

2.3.1 Classification and Distribution . .............................................. 56

2.3.2 Structural Characterization of Bacterial CODH/ACS . ...................... 58

2.3.3 Substrate Binding and Reaction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

2.4 Cu,Mo versus Ni,Fe: Parallels and Differences in Catalytic Strategies . . . . . . . . . . . . 62

3 CONCLUDING REMARKS AND FUTURE DIRECTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

ABBREVIATIONS ............................................................................. 65

ACKNOWLEDGMENT . . . . . . . . . . ............................................................. 65

REFERENCES . ................................................................................. 65