Nitrosation, thiols, and hemoglobin: energetics and kinetics.

Inorganic Chemistry
Willem H Koppenol

Abstract

Nitrosothiols are powerful vasodilators. Although the mechanism of their formation near neutral pH is an area of intense research, neither the energetics nor the kinetics of this reaction or of subsequent reactions have been addressed. The following considerations may help to guide experiments. (1) The standard Gibbs energy for the homolysis reaction RSNO → RS(•) + NO(•)(aq) is +110 ± 5 kJ mol(-1). (2) The electrode potential of the RSNO, H(+)/RSH, NO(•)(aq) couple is -0.20 ± 0.06 V at pH 7. (3) Thiol nitrosation by NO(2)(-) is favorable by 37 ± 5 kJ mol(-1) at pH 7. (4) N(2)O(3) is not involved in in vivo nitrosation mechanisms for thermodynamic--its formation from NO(2)(-) costs 59 kJ mol(-1)--or kinetic--the reaction being second-order in NO(2)(-)--reasons. (5) Hemoglobin (Hb) cannot catalyze formation of N(2)O(3), be it via the intermediacy of the reaction of Hb[FeNO(2)](2+) with NO(•) (+81 kJ mol(-1)) or reaction of Hb[FeNO](3+) with NO(2)(-) (+88 kJ mol(-1)). (6) Energetically and kinetically viable are nitrosations that involve HNO(2) or NO(•) in the presence of an electron acceptor with an electrode potential higher than -0.20 V. These considerations are derived from existing thermochemical and kinetics data.

References

Jan 25, 1975·Journal of Molecular Biology·R Cassoly, Q Gibson
Jun 4, 1996·Biochemistry·R F EichJ S Olson
Jan 31, 1997·The Journal of Biological Chemistry·A J GowH Ischiropoulos
Sep 14, 2000·The Journal of Biological Chemistry·C H TaboyA L Crumbliss
Sep 6, 2001·Journal of the American Chemical Society·M D BartbergerE J Toone
Aug 28, 2003·Journal of the American Chemical Society·Bernadette O Fernandez, Peter C Ford
Nov 5, 2003·Nature Medicine·Kenyatta CosbyMark T Gladwin
Mar 18, 2005·Annals of Biomedical Engineering·Ian G Zacharia, William M Deen
Mar 22, 2005·American Journal of Respiratory Cell and Molecular Biology·John M Robinson, Jack R Lancaster
Jul 17, 2007·Journal of the American Chemical Society·Willem H Koppenol
Nov 6, 2007·Nature Chemical Biology·Swati BasuDaniel B Kim-Shapiro
Nov 16, 2007·Inorganic Chemistry·Manuel SturzbecherWillem H Koppenol
Mar 11, 2008·Physical Chemistry Chemical Physics : PCCP·Qadir K TimerghazinAnn M English
May 14, 2009·Chemistry : a European Journal·Benedikt GallikerWillem H Koppenol
May 19, 2009·Nature Chemical Biology·David E SchwabDavid J Singel
Nov 3, 2009·Free Radical Biology & Medicine·Swati BasuDaniel B Kim-Shapiro
Nov 10, 2009·Nitric Oxide : Biology and Chemistry·Bradley I GoetzDaniel B Kim-Shapiro
Apr 22, 2010·Free Radical Biology & Medicine·Willem H KoppenolPatricia L Bounds
Oct 5, 2010·Chemical Research in Toxicology·Dustin HofstetterWillem H Koppenol
Nov 12, 2010·The Journal of Physical Chemistry. B·Horacio BottiRafael Radi
Dec 15, 2010·Archives of Biochemistry and Biophysics·Lisa K FolkesPeter Wardman
May 19, 2011·Chemistry : a European Journal·Kathrin H HopmannAbhik Ghosh

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Citations

Jun 21, 2012·Chemical Research in Toxicology·Dustin HofstetterWillem H Koppenol
Dec 10, 2013·Nitric Oxide : Biology and Chemistry·Daniel B Kim-Shapiro, Mark T Gladwin
Jun 17, 2014·Nitric Oxide : Biology and Chemistry·Rudolf WedmannMilos R Filipovic
Jun 30, 2012·Journal of the American Chemical Society·Milos R FilipovicIvana Ivanović-Burmazović
Oct 6, 2015·Nitric Oxide : Biology and Chemistry·Bojana BolićIvan Spasojević
Nov 7, 2012·Current Opinion in Chemical Biology·Brian C Smith, Michael A Marletta
Jun 13, 2015·The Journal of Organic Chemistry·Joyeth B DoradoMohammednoor Altarawneh
May 26, 2015·Nature Chemical Biology·Dario A VitturiFrancisco J Schopfer
Apr 30, 2013·Free Radical Biology & Medicine·Christine Helms, Daniel B Kim-Shapiro
Jan 16, 2013·The Journal of Physical Chemistry. B·Marat R Talipov, Qadir K Timerghazin
Oct 11, 2016·Nitric Oxide : Biology and Chemistry·Sarah L Wynia-Smith, Brian C Smith
Oct 31, 2016·Archives of Biochemistry and Biophysics·Jack R Lancaster
Nov 29, 2016·Antioxidants & Redox Signaling·Viktoria KuhnMiriam M Cortese-Krott
Sep 10, 2016·Biological Chemistry·Christine C HelmsDaniel B Kim-Shapiro
Apr 5, 2013·Journal of Computational Chemistry·Marat R TalipovQadir K Timerghazin
Jul 28, 2017·Current Medicinal Chemistry·Z C Félix GarzaJ Liebmann
Dec 5, 2014·The Journal of Biological Chemistry·Chen LiuDaniel B Kim-Shapiro
Mar 29, 2014·Physical Chemistry Chemical Physics : PCCP·Lena V IvanovaQadir K Timerghazin
Aug 30, 2018·Frontiers in Oncology·Emmanuelle BignonElena Papaleo
May 24, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Christian MolinaWillem H Koppenol
Jul 30, 2020·Nitric Oxide : Biology and Chemistry·Peter C Ford, Katrina M Miranda
Mar 21, 2013·The Journal of Physical Chemistry Letters·Qadir K Timerghazin, Marat R Talipov
Mar 19, 2019·Inorganic Chemistry·Ivana Ivanovic-Burmazovic, Milos R Filipovic
Jul 11, 2014·Journal of the American Chemical Society·Brian C SandersTodd C Harrop

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