de.mpg.escidoc.pubman.appbase.FacesBean
English
 
Help Guide Disclaimer Contact us Login
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Exploring the conformational preferences of 20-residue peptides in isolation: Ac-Ala19-Lys + H+ vs. Ac-Lys-Ala19 + H+ and the current reach of DFT

MPS-Authors
http://pubman.mpdl.mpg.de/cone/persons/resource/persons22084

Schubert,  Franziska
Theory, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21421

Rossi,  Mariana
Theory, Fritz Haber Institute, Max Planck Society;
Physical and Theoretical Chemistry Laboratory, University of Oxford;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21325

Baldauf,  Carsten
Theory, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons32738

Pagel,  Kevin
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Institut für Chemie und Biochemie - Organische Chemie, Freie Universität Berlin;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22220

Warnke,  Stephan
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21614

Helden,  Gert von
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21507

Filsinger,  Frank
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21780

Kupser,  Peter
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21859

Meijer,  Gerard
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Radboud University Nijmegen;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22064

Scheffler,  Matthias
Theory, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21379

Blum,  Volker
Theory, Fritz Haber Institute, Max Planck Society;
Duke University, MEMS Department, Durham, NC 27708, USA;

Locator
There are no locators available
Fulltext (public)

c4cp05541a.pdf
(Publisher version), 4MB

Supplementary Material (public)
There is no public supplementary material available
Citation

Schubert, F., Rossi, M., Baldauf, C., Pagel, K., Warnke, S., Helden, G. v., et al. (2015). Exploring the conformational preferences of 20-residue peptides in isolation: Ac-Ala19-Lys + H+ vs. Ac-Lys-Ala19 + H+ and the current reach of DFT. Physical Chemistry Chemical Physics, 17(11), 7373-7385. doi:10.1039/C4CP05541A.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-C5B9-9
Abstract
A reliable, quantitative prediction of the structure of peptides based on their amino-acid sequence information is an ongoing challenge. We here explore the energy landscape of two unsolvated 20-residue peptides that result from a shift of the position of one amino acid in otherwise the same sequence. Our main goal is to assess the performance of current state-of-the-art density- functional theory for predicting the structure of such large and complex systems, where weak interactions such as dispersion or hydrogen bonds play a crucial role. For validation of the theoretical results, we employ experimental gas-phase ion mobility-mass spectrometry and IR spectroscopy. While unsolvated Ac-Ala19-Lys + H+ will be shown to be a clear helix seeker, the structure space of Ac-Lys-Ala19 + H+ is more complicated. Our first-principles structure-screening strategy using the dispersion-corrected PBE functional (PBE+vdWTS ) identifies six distinctly different structure types competing in the low-energy regime (≈16 kJ/mol). For these structure types, we analyze the influence of the PBE and the hybrid PBE0 functional coupled with either a pairwise dispersion correction (PBE+vdWTS, PBE0+vdWTS) or a many-body dispersion correction (PBE+MBD∗, PBE0+MBD∗). We also take harmonic vibrational and rotational free energy into account. Including this, the PBE0+MBD∗ functional predicts only one unique conformer to be present at 300 K. We show that this scenario is consistent with both experiments.