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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

Links

DOI: 10.3390/books978-3-0365-0609-8

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