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@ARTICLE{Kotobi:491686,
author = {Kotobi, Amir and Schwob, Lucas and Vonbun-Feldbauer, Gregor
B. and Rossi, Mariana and Piero, Gasparotto and Feiler,
Christian and Berden, Giel and Oomens, Jos and Oostenrijk,
Bart Hendrik and Scuderi, Debora and Bari, Sadia and
Meißner, Robert H.},
title = {{R}econstructing the infrared spectrum of a peptide from
representative conformers of the full canonical ensemble},
journal = {Communications chemistry},
volume = {6},
number = {1},
issn = {2399-3669},
address = {[London]},
publisher = {Macmillan Publishers Limited, part of Springer Nature},
reportid = {PUBDB-2023-00346},
pages = {46},
year = {2023},
abstract = {Leucine enkephalin (LeuEnk), a biologically active
endogenous opioid pentapeptide, has been under intense
investigation because it is small enough to allow efficient
use of sophisticated computational methods and large enough
to provide insights into low-lying minima of its
conformational space. Here, we reproduce and interpret
experimental infrared (IR) spectra of this model peptide in
gas phase using a combination of replica-exchange molecular
dynamics simulations, machine learning, and ab initio
calculations. In particular, we evaluate the possibility of
averaging representative structural contributions to obtain
an accurate computed spectrum that accounts for the
corresponding canonical ensemble of the real experimental
situation. Representative conformers are identified by
partitioning the conformational phase space into
subensembles of similar conformers. The IR contribution of
each representative conformer is calculated from ab initio
and weighted according to the population of each cluster.
Convergence of the averaged IR signal is rationalized by
merging contributions in a hierarchical clustering and the
comparison to IR multiple photon dissociation experiments.
The improvements achieved by decomposing clusters containing
similar conformations into even smaller subensembles is
strong evidence that a thorough assessment of the
conformational landscape and the associated hydrogen bonding
is a prerequisite for deciphering important fingerprints in
experimental spectroscopic data.},
cin = {FS-BIG},
ddc = {540},
cid = {I:(DE-H253)FS-BIG-20220318},
pnm = {633 - Life Sciences – Building Blocks of Life: Structure
and Function (POF4-633) / HIDSS-0002 - DASHH: Data Science
in Hamburg - Helmholtz Graduate School for the Structure of
Matter $(2019_IVF-HIDSS-0002)$ / DFG project 390715994 - EXC
2056: CUI: Advanced Imaging of Matter (390715994) / DFG
project 194651731 - EXC 1074: Hamburger Zentrum für
ultraschnelle Beobachtung (CUI): Struktur, Dynamik und
Kontrolle von Materie auf atomarer Skala (194651731)},
pid = {G:(DE-HGF)POF4-633 / $G:(DE-HGF)2019_IVF-HIDSS-0002$ /
G:(GEPRIS)390715994 / G:(GEPRIS)194651731},
experiment = {EXP:(DE-MLZ)External-20140101},
typ = {PUB:(DE-HGF)16},
pubmed = {36869192},
UT = {WOS:000943127000001},
doi = {10.1038/s42004-023-00835-3},
url = {https://bib-pubdb1.desy.de/record/491686},
}