Zinc Thiolate Reactivity toward Nitrogen Oxides: Insights into the Interaction of Zn[superscript 2+] with S-Nitrosothiols and Implications for Nitric Oxide Synthase

Zinc thiolate complexes containing N[subscript 2]S tridentate ligands were prepared to investigate their reactivity toward reactive nitrogen species, chemistry proposed to occur at the zinc tetracysteine thiolate site of nitric oxide synthase (NOS). The complexes are unreactive toward nitric oxide (...

Full description

Bibliographic Details
Main Authors: Kozhukh, Julia (Contributor), Lippard, Stephen J. (Contributor)
Other Authors: Massachusetts Institute of Technology. Department of Chemistry (Contributor)
Format: Article
Language:English
Published: American Chemical Society (ACS), 2013-11-18T13:43:29Z.
Subjects:
Online Access:Get fulltext
LEADER 01958 am a22002173u 4500
001 82152
042 |a dc 
100 1 0 |a Kozhukh, Julia  |e author 
100 1 0 |a Massachusetts Institute of Technology. Department of Chemistry  |e contributor 
100 1 0 |a Kozhukh, Julia  |e contributor 
100 1 0 |a Lippard, Stephen J.  |e contributor 
700 1 0 |a Lippard, Stephen J.  |e author 
245 0 0 |a Zinc Thiolate Reactivity toward Nitrogen Oxides: Insights into the Interaction of Zn[superscript 2+] with S-Nitrosothiols and Implications for Nitric Oxide Synthase 
260 |b American Chemical Society (ACS),   |c 2013-11-18T13:43:29Z. 
856 |z Get fulltext  |u http://hdl.handle.net/1721.1/82152 
520 |a Zinc thiolate complexes containing N[subscript 2]S tridentate ligands were prepared to investigate their reactivity toward reactive nitrogen species, chemistry proposed to occur at the zinc tetracysteine thiolate site of nitric oxide synthase (NOS). The complexes are unreactive toward nitric oxide (NO) in the absence of dioxygen, strongly indicating that NO cannot be the species directly responsible for S-nitrosothiol formation and loss of Zn[superscript 2+] at the NOS dimer interface in vivo. S-Nitrosothiol formation does occur upon exposure of zinc thiolate solutions to NO in the presence of air, however, or to NO[subscript 2] or NOBF[subscript 4], indicating that these reactive nitrogen/oxygen species are capable of liberating zinc from the enzyme, possibly through generation of the S-nitrosothiol. Interaction between simple Zn[superscript 2+] salts and preformed S-nitrosothiols leads to decomposition of the −SNO moiety, resulting in release of gaseous NO and N[subscript 2]O. The potential biological relevance of this chemistry is discussed. 
520 |a National Science Foundation (U.S.) (Grant CHE0907905) 
520 |a National Institutes of Health (U.S.) (Grant 1A10RR013886-01) 
546 |a en_US 
655 7 |a Article 
773 |t Inorganic Chemistry