Abstract
In addition to the classical N-H⋯O[double bond, length as m-dash]C non-covalent interaction, less conventional types of hydrogen bonding, such as N-H⋯S, may play a key role in determining the molecular structure. In this work, using theoretical calculations in combination with spectroscopic analysis in both gas phase and solution phase, we demonstrate that both these H-bonding modes exist simultaneously in low-energy conformers of capped derivatives of Attc, a thietane α-amino acid. 6-Membered ring inter-residue N-H⋯S interactions (C6γ), assisted by hyperconjugation between the thietane ring and the backbone, combine with 5-membered ring intra-residue backbone N-H⋯O[double bond, length as m-dash]C interactions (C5) to provide a C5-C6γ feature that stabilizes a planar geometry in the monomer unit. Two contiguous C5-C6γ features in the planar dimer implicate an unprecedented three-centre H-bond of the type C[double bond, length as m-dash]O⋯H(N)⋯SR2, while the trimer adopts two C5-C6γ features separated by a Ramachandran α-type backbone configuration. These low-energy conformers are fully characterized in the gas phase and support is presented for their existence in solution state.
References
Jan 1, 1991·Proteins·L M GregoretF E Cohen
Jan 1, 1985·Advances in Protein Chemistry·G D RoseJ A Smith
Jan 1, 1984·Progress in Biophysics and Molecular Biology·E N Baker, R E Hubbard
Sep 15, 1995·Journal of Molecular Biology·Z S DerewendaU Derewenda
Jan 12, 1996·Science·D A Dougherty
Jan 1, 1997·Annual Review of Physical Chemistry·C L Perrin, J B Nielson
Feb 19, 2000·Biopolymers·R J ZauharW J Welsh
Sep 5, 2002·Biopolymers·C TonioloC Peggion
Mar 20, 2003·Angewandte Chemie·Emmanuel A MeyerFrançois Diederich
Apr 25, 2006·Chemistry & Biology·Haizhong TangGregory N Tew
Dec 18, 2008·Proteins·Peng ZhouZhicai Shang
Oct 13, 2009·The Journal of Physical Chemistry. a·Eric GloaguenMichel Mons
Apr 29, 2010·The Journal of Chemical Physics·Stefan GrimmeHelge Krieg
Jul 14, 2010·Nature Chemical Biology·Gail J BartlettDerek N Woolfson
Oct 15, 2010·The Journal of Chemical Physics·Dmitrij Rappoport, Filipp Furche
Jul 28, 2012·Journal of Computational Chemistry·Frank Weinhold
Aug 4, 2012·The Journal of Biological Chemistry·Christopher C ValleyJonathan N Sachs
Oct 11, 2012·The Journal of Biological Chemistry·Scott Horowitz, Raymond C Trievel
Jul 31, 2013·Biopolymers·Cristina PeggionClaudio Toniolo
Apr 24, 2014·Physical Chemistry Chemical Physics : PCCP·Bin YanAnouk M Rijs
Dec 9, 2014·Physical Chemistry Chemical Physics : PCCP·Mohammad AlauddinMichel Mons
Mar 26, 2015·Topics in Current Chemistry·Eric Gloaguen, Michel Mons
May 6, 2015·Chemical Society Reviews·Y LanM A Rogers
Aug 12, 2015·The Journal of Physical Chemistry Letters·V Rao MundlapatiHimansu S Biswal
Mar 15, 2012·The Journal of Physical Chemistry Letters·Himansu S BiswalMichel Mons
Jan 27, 2016·Journal of the American Chemical Society·Timothy W CravenKent Kirshenbaum
Oct 7, 2016·Physical Chemistry Chemical Physics : PCCP·Joseph R GordTimothy S Zwier
Oct 25, 2016·Nature Chemical Biology·Robert W Newberry, Ronald T Raines
Sep 7, 2017·The Journal of Physical Chemistry Letters·V Rao MundlapatiHimansu S Biswal
Oct 23, 2018·Angewandte Chemie·V Rao MundlapatiHimansu S Biswal
Jun 28, 2019·ACS Chemical Biology·Robert W Newberry, Ronald T Raines
Nov 2, 2019·Physical Chemistry Chemical Physics : PCCP·Valérie BrennerMichel Mons
Citations
Sep 12, 2020·Physical Chemistry Chemical Physics : PCCP·Gildas GoldsztejnMichel Mons
Sep 24, 2020·Physical Chemistry Chemical Physics : PCCP·Gildas GoldsztejnJosé Luis Alonso
Mar 2, 2021·Amino Acids·José Luis Viveros-CeballosMario Ordóñez
Mar 21, 2021·Amino Acids·Venkateswara Rao MundlapatiDavid J Aitken
Jul 27, 2021·Inorganic Chemistry·Ransel BarzagaSergio Díaz-Tendero
Nov 6, 2020·Chemical Reviews·Eric GloaguenMarkus Gerhards