Document Detail


The case of the missing NO-hemoglobin: spectral changes suggestive of heme redox reactions reflect changes in NO-heme geometry.
MedLine Citation:
PMID:  14514887     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
When low levels of gaseous nitric oxide (NO) are equilibrated with deoxygenated Hb, all NO added can be accounted for in terms of hexacoordinate and pentacoordinate forms of NO-Hb, despite recent reports on NO disappearance from heme groups to form nitroxyl anions or S-nitrosated Hb at low ratios of NO to Hb. We demonstrate that a fraction of the spectral signature of fully nitrosylated (largely hexacoordinate) Hb disappears as the pentacoordinate state forms and reappears when pentacoordinate NO-Hb is reconverted to the hexacoordinate condition. We show that the spectral changes associated with these reversible shifts in NO- heme geometry can be remarkably well approximated as variations in the contributions from fully nitrosylated Hb and oxidized Hb (MetHb). As a result, increases in the level of pentacoordinate NO-Hb that occur at low NO to Hb ratios can be misinterpreted as increases in MetHb levels associated with NO-dependent heme oxidation. Conversely, any decrease in levels of pentacoordinate NO-Hb can be misinterpreted as a disappearance of MetHb associated with NO-dependent heme reduction. Transitions between pentacoordinate and hexacoordinate forms of NO-Hb with spectral changes suggestive of changes in levels of heme-bound NO are sensitive to the protein's quaternary conformation and can be brought about by alterations in anion levels or the degree of heme saturation with either O2 or NO.
Authors:
Angela Fago; Alvin L Crumbliss; Jim Peterson; Linda L Pearce; Celia Bonaventura
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Publication Detail:
Type:  In Vitro; Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, P.H.S.     Date:  2003-09-26
Journal Detail:
Title:  Proceedings of the National Academy of Sciences of the United States of America     Volume:  100     ISSN:  0027-8424     ISO Abbreviation:  Proc. Natl. Acad. Sci. U.S.A.     Publication Date:  2003 Oct 
Date Detail:
Created Date:  2003-10-15     Completed Date:  2003-12-04     Revised Date:  2009-11-18    
Medline Journal Info:
Nlm Unique ID:  7505876     Medline TA:  Proc Natl Acad Sci U S A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  12087-92     Citation Subset:  IM    
Affiliation:
Nicholas School of the Environment and Earth Sciences, Duke University, Beaufort, NC 28516, USA.
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MeSH Terms
Descriptor/Qualifier:
Electron Spin Resonance Spectroscopy
Heme / chemistry*,  metabolism*
Hemoglobin A, Glycosylated / chemistry*,  metabolism*
Hemoglobins / chemistry,  metabolism
Humans
Kinetics
Methemoglobin / chemistry,  metabolism
Nitric Oxide / chemistry*,  metabolism*
Oxidation-Reduction
Spectrophotometry
Grant Support
ID/Acronym/Agency:
HL 58248/HL/NHLBI NIH HHS; HL 61411/HL/NHLBI NIH HHS; HL 71064/HL/NHLBI NIH HHS
Chemical
Reg. No./Substance:
0/Hemoglobin A, Glycosylated; 0/Hemoglobins; 0/hemoglobin A, glycosylated-nitric oxide complex; 10102-43-9/Nitric Oxide; 14875-96-8/Heme; 9008-02-0/deoxyhemoglobin; 9008-37-1/Methemoglobin
Comments/Corrections

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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