PMID- 19473015
OWN - NLM
STAT- MEDLINE
DCOM- 20090804
LR  - 20131121
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Linking)
VI  - 131
IP  - 24
DP  - 2009 Jun 24
TI  - Thiolate S-oxygenation controls nitric oxide (NO) photolability of a synthetic 
      iron nitrile hydratase (Fe-NHase) model derived from mixed carboxamide/thiolate 
      ligand.
PG  - 8340-1
LID - 10.1021/ja9004656 [doi]
AB  - In order to determine the origin of the NO photolability of the active site of 
      Fe-containing nitrile hydratase (Fe-NHase), a model complex of the NO-bound 
      active site (dark form) has been isolated and structurally characterized. The 
      model, NEt(4)[(Cl(2)PhPepS)Fe(NO)(DMAP)] (2), is derived from a tetradentate 
      ligand comprising carboxamido N and thiolato S donor centers much like the donors 
      present in the active site of Fe-NHase. This Fe-NO(6) nitrosyl effectively 
      mimics the NO-bound active site in terms of structural and spectroscopic 
      parameters. However, this model lacks the key property of NO photolability. 
      Interestingly, S-oxygenation of the model complex results in formation of 
      Na[(Cl(2)PhPepSO(2)(2))Fe(NO)(DMAP)] (3), in which the -S donors are oxygenated 
      to -SO(2) moieties, and this species exhibits NO photolability. These results 
      indicate that S-oxygenation could be the key reason for the observed NO 
      photolability of the active site of the dark form of Fe-NHase.
FAU - Rose, Michael J
AU  - Rose MJ
AD  - Department of Chemistry and Biochemistry, University of California, Santa Cruz, 
      California 96064, USA.
FAU - Betterley, Nolan M
AU  - Betterley NM
FAU - Mascharak, Pradip K
AU  - Mascharak PK
LA  - eng
PT  - Journal Article
PT  - Research Support, U.S. Gov't, Non-P.H.S.
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
RN  - 0 (4-(dimethylamine)pyridine)
RN  - 0 (Amides)
RN  - 0 (Ferric Compounds)
RN  - 0 (Ligands)
RN  - 0 (Pyridines)
RN  - 0 (Sulfhydryl Compounds)
RN  - 31C4KY9ESH (Nitric Oxide)
RN  - EC 4.2.1.- (Hydro-Lyases)
RN  - EC 4.2.1.- (nitrile hydratase)
SB  - IM
MH  - Amides/*chemistry
MH  - Catalytic Domain
MH  - Electron Spin Resonance Spectroscopy
MH  - Ferric Compounds/chemical synthesis/*chemistry
MH  - Hydro-Lyases/*chemistry
MH  - Ligands
MH  - Nitric Oxide/*chemistry
MH  - Oxidation-Reduction
MH  - Photochemical Processes
MH  - Pyridines/chemistry
MH  - Sulfhydryl Compounds/*chemistry
EDAT- 2009/05/29 09:00
MHDA- 2009/08/06 09:00
CRDT- 2009/05/29 09:00
PHST- 2009/05/29 09:00 [entrez]
PHST- 2009/05/29 09:00 [pubmed]
PHST- 2009/08/06 09:00 [medline]
AID - 10.1021/ja9004656 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2009 Jun 24;131(24):8340-1. doi: 10.1021/ja9004656.