Observation of the closing of individual hydrogen bonds during TFE-induced helix formation in a peptide

Protein Science : a Publication of the Protein Society
V A JaravineS Grzesiek

Abstract

Helix formation of an S-peptide analog, comprising the first 20 residues of Ribonuclease A and two additional N-terminal residues, was studied by measuring hydrogen bond (H-bond) (h3)J(NC') scalar couplings as a function of 2,2,2-trifluoroethanol (TFE) concentration. The (h3)J(NC') couplings give direct evidence for the closing of individual backbone N-H***O = C H-bonds during the TFE-induced formation of secondary structure. Whereas no (h3)J(NC') correlations could be detected without TFE, alpha-helical (i,i +4) H-bond correlations were observed for the amides of residues A5 to M15 in the presence of TFE. The analysis of individual coupling constants indicates that alpha-helix formation starts at the center of the S-peptide around residue E11 and proceeds gradually from there to both peptide ends as the TFE concentration is increased. At 60% to 90% TFE, well-formed alpha-helical H-bonds were observed for the amides hydrogens of residues K9 to Q13, whereas H-bonds of residues T5 to A8, H14, and M15 are affected by fraying. No intramolecular backbone H-bonds are present at and beyond the putative helix stop signal D16. As the (h3)J(NC') constants represent ensemble averages and the dependence of (h3)J(NC') on H-bond lengths is v...Continue Reading

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Citations

Feb 16, 2008·Nature Protocols·Florence CordierStephan Grzesiek
Jan 10, 2009·Proceedings of the National Academy of Sciences of the United States of America·Beat FierzThomas Kiefhaber
Dec 20, 2015·Biophysical Journal·Rebecca L NewcomerAndrei T Alexandrescu
Apr 17, 2002·Journal of Molecular Biology·Florence Cordier, Stephan Grzesiek
Feb 18, 2016·The Journal of Physical Chemistry Letters·Levani ZandarashviliJunji Iwahara
Sep 23, 2003·Protein Science : a Publication of the Protein Society·Andrei T Alexandrescu, Richard A Kammerer
Jun 6, 2006·Protein Science : a Publication of the Protein Society·Roberto K SalinasRolf Boelens
Mar 2, 2011·Journal of Peptide Science : an Official Publication of the European Peptide Society·Andreas Reiner
Jul 12, 2016·Journal of Chemical Theory and Computation·Karl T DebiecLillian T Chong
Sep 30, 2016·The Journal of Physical Chemistry. B·Abhijnan ChattopadhyayJunji Iwahara
Apr 18, 2008·European Journal of Mass Spectrometry·Xianmei Cai, Chhabil Dass
Dec 13, 2006·Chemistry : a European Journal·Massimo BellandaPaolo Scrimin
Oct 16, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Xiao-Nan Jiang, Chang-Sheng Wang
Dec 15, 2011·Organic & Biomolecular Chemistry·Emiliana De SantisAlison A Edwards
Jul 3, 2003·Journal of the American Chemical Society·Robert Wieczorek, J J Dannenberg
Oct 28, 2004·Journal of the American Chemical Society·Robert Wieczorek, J J Dannenberg
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Sep 30, 2004·Journal of the American Chemical Society·Robert Wieczorek, J J Dannenberg
Oct 20, 2005·Journal of the American Chemical Society·Robert Wieczorek, J J Dannenberg
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Nov 21, 2007·The Journal of Physical Chemistry. a·Itzam De GortariMike Payne
Aug 19, 2004·Journal of the American Chemical Society·Darón I FreedbergRichard W Pastor

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