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Transition Metals in Catalysis
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Iron–sulfur (FeS) centers are essential protein cofactors in all forms of life. They are involved in many key biological processes. In particular, Fe-S centers not only serve as enzyme cofactors in catalysis and electron transfer, they are also indispensable for the biosynthesis of complex metal-containing cofactors. Among these cofactors are the molybdenum (Moco) and tungsten (Wco) cofactors. Both Moco/Wco biosynthesis and Fe-S cluster assembly are highly conserved among all kingdoms of life. After formation, Fe-S clusters are transferred to carrier proteins, which insert them into recipient apo-proteins. Moco/Wco cofactors are composed of a tricyclic pterin compound, with the metal coordinated to its unique dithiolene group. Moco/Wco biosynthesis starts with an Fe-S cluster-dependent step involving radical/S-adenosylmethionine (SAM) chemistry. The current lack of knowledge of the connection of the assembly/biosynthesis of complex metal-containing cofactors is due to the sheer complexity of their synthesis with regard to both the (genetic) regulation and (chemical) metal center assembly. Studies on these metal-cofactors/cofactor-containing enzymes are important for understanding fundamental cellular processes. They will also provide a comprehensive view of the complex biosynthesis and the catalytic mechanism of metalloenzymes that underlie metal-related human diseases.
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Keywords
- acetylene hydratase
- aldehyde:ferredoxin oxidoreductase
- benzoyl-CoA reductase
- Biology, Life Sciences
- carbon assimilation
- CCCP—carbonyl cyanide m-chlorophenyl-hydrazone
- CO dehydrogenase
- conformational changes
- density functional theory
- dihydrogen
- dithiolene ligand
- EIPA—5-(N-ethyl-N-isopropyl)-amiloride
- electron transfer
- electronic structure
- Energy conservation
- enzyme kinetics
- enzyme structure
- Fe-S cluster assembly
- FeGP cofactor
- fold-angle
- formate dehydrogenase
- formate hydrogenlyase
- frataxin
- Friedreich’s ataxia
- guanylylpyridinol
- hydrogen metabolism
- hydrogenase
- Iron
- iron-sulfur cluster
- ISC
- l-cysteine desulfurase
- magnetic moment
- Mathematics & science
- metallocofactor
- metal–dithiolene
- mixed-valence complex
- Moco
- Moco biosynthesis
- Molybdenum
- molybdenum cofactor
- MRP (multiple resistance and pH)-type Na+/H+ antiporter
- n/a
- nicotinamide adenine dinucleotide (NADH)
- NIF
- persulfide
- pseudo-Jahn–Teller effect
- pyranopterin molybdenum enzymes
- quantum/classical modeling
- Reference, information & interdisciplinary subjects
- Research & information: general
- SUF
- Sulfur
- tetra-nuclear nickel complex
- thione
- tungsten cofactor
- tungsten enzymes
- X-ray crystallography
- X-ray structure
- [Fe]-hydrogenase