NMR studies of solvent-assisted proton transfer in a biologically relevant Schiff base: toward a distinction of geometric and equilibrium H-bond isotope effects

Journal of the American Chemical Society
Shasad SharifHans-Heinrich Limbach

Abstract

The tautomeric equilibrium in a Schiff base, N-(3,5-dibromosalicylidene)-methylamine 1, a model for the hydrogen bonded structure of the cofactor pyridoxal-5'-phosphate PLP which is located in the active site of the enzyme, was measured by means of 1H and 15N NMR and deuterium isotope effects on 15N chemical shifts at variable temperature and in different organic solvents. The position of the equilibrium was estimated using the one-bond 1J(OHN) and vicinal 3J(H(alpha)CNH) scalar coupling constants. Additionally, DFT calculations of a series of Schiff bases, N-(R1-salicylidene)-alkyl(R2)amines, were performed to obtain the hydrogen bond geometries. The latter made it possible to investigate a broad range of equilibrium positions. The increase of the polarity of the aprotic solvent shifts the proton in the intramolecular OHN hydrogen bond closer to the nitrogen. The addition of methanol and of hexafluoro-2-propanol to 1 in aprotic solvents models the PLP-water interaction in the enzymatic active site. The alcohols, which vary in acidity and change the polarity around the hydrogen bond, also stabilize the equilibrium, so that the proton is shifted to the nitrogen.

References

Jan 23, 1999·Current Opinion in Structural Biology·J N Jansonius
Aug 6, 2000·Solid State Nuclear Magnetic Resonance·B KamieńskiA Szady-Chełmieniecka
Feb 28, 2001·Proceedings of the National Academy of Sciences of the United States of America·M D BartbergerK N Houk
Sep 17, 2004·Chemistry : a European Journal·Hans-Heinrich LimbachGleb S Denisov

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Citations

Oct 15, 2013·Archives of Biochemistry and Biophysics·Michael D Toney
Mar 4, 2011·Journal of the American Chemical Society·Yen-lin Lin, Jiali Gao
Jun 21, 2011·Journal of the American Chemical Society·Stepan B LesnichinHans-Heinrich Limbach
Mar 6, 2012·Journal of the American Chemical Society·Anna-Carin C CarlssonMáté Erdélyi
Aug 3, 2012·The Journal of Physical Chemistry. a·Tomoko Nakano, Yuichi Masuda
Jun 28, 2011·Biochimica Et Biophysica Acta·Hans-Heinrich LimbachMichael D Toney
Nov 22, 2011·Chemical Biology & Drug Design·Manoharan Muthu TamizhRamasamy Karvembu
Dec 6, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Lucjan SobczykAleksander Filarowski
Oct 27, 2007·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Almudena PeronaJosé Elguero
Jan 5, 2014·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·David Ortegón-ReynaFrancisco Martínez-Martínez
Apr 14, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Manjaly J AjithaYousung Jung
Feb 26, 2008·Magnetic Resonance in Chemistry : MRC·Janet E Del BeneJosé Elguero
May 15, 2009·Physical Chemistry Chemical Physics : PCCP·Patricio F Provasi, Stephan P A Sauer
Jul 22, 2010·Physical Chemistry Chemical Physics : PCCP·Alexandra DosHans-Heinrich Limbach
Feb 4, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Poul Erik Hansen
Apr 25, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Valeriia V MulloyarovaPeter M Tolstoy
Oct 30, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Juncheng LeiVincenzo Barone
Mar 29, 2007·The Journal of Physical Chemistry. B·Shasad SharifHans-Heinrich Limbach
Oct 28, 2019·Journal of the American Chemical Society·Hancheng XiWei-Hong Zhu
Dec 12, 2017·The Journal of Physical Chemistry. B·Yuta SaegusaTakahiko Kojima
May 4, 2011·Journal of the American Chemical Society·Benjamin KoeppeHans-Heinrich Limbach
Sep 21, 2010·The Journal of Physical Chemistry. a·Peter M TolstoyHans-Heinrich Limbach
Jul 20, 2018·The Journal of Organic Chemistry·Yen H NguyenBrett VanVeller

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