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@ARTICLE{Grabowsky:92553,
author = {Grabowsky, S. and Kalinowski, R. and Weber, M. and
Förster, D. and Paulmann, C. and Luger, P. and DESY},
title = {{T}ransferability and {R}eproducibility in
{E}lectron-{D}ensity {S}tudies - {B}ond {T}opological and
{A}tomic {P}roperties of {T}ripeptides of the {T}ype
{L}-{A}lanyl-{X}-{L}-{A}lanine},
journal = {Acta crystallographica / B},
volume = {65},
issn = {0108-7681},
address = {Oxford [u.a.]},
publisher = {Wiley-Blackwell},
reportid = {PHPPUBDB-11693},
pages = {488-501},
year = {2009},
abstract = {In the last decade three different data bank approaches
have been developed that are intended to make
electron-density examinations of large biologically
important molecules possible. They rely on Bader's concept
of transferability of submolecular fragments with retention
of their electronic properties. Therefore, elaborate studies
on the quantification of transferability in experiment and
theory are still very important. Tripeptides of the type
L-alanyl-X-L-alanine (X being any of the 20 naturally
encoded amino acids) serve as a model case between amino
acids and proteins. The two experimental electron-density
determinations (L-alanyl-L-histidinyl-L-alanine and
L-alanyl-L-phenylalanyl-L-alanine, highly resolved
synchrotron X-ray diffraction data sets) performed in this
study and theoretical calculations on all 20 different
L-alanyl-X-L-alanine molecules contribute to a better
estimation of transferability in the peptide case. As a
measure of reproducibility and transferability, standard
deviations from averaging over bond-topological and atomic
properties of atoms or bonds that are considered equal in
their chemical environments were calculated. This way,
transferability and reproducibility indices were introduced.
It can be shown that experimental transferability indices
generally slightly exceed experimental reproducibility
indices and that these larger deviations can be attributed
to chemical effects such as changes in the geometry (bond
lengths and angles), the polarization pattern and the
neighboring sphere due to crystal packing. These effects can
partly be separated from each other and quantified with the
help of gas-phase calculations at optimized and experimental
geometries. Thus, the degree of transferability can be
quantified in very narrow limits taking into account
experimental errors and chemical effects.},
keywords = {Alanine: chemistry / Crystallography, X-Ray / Electrons /
Models, Molecular / Oligopeptides: chemistry / Quantum
Theory / Oligopeptides (NLM Chemicals) / Alanine (NLM
Chemicals)},
cin = {HASYLAB},
ddc = {530},
cid = {$I:(DE-H253)HASYLAB_-2012_-20130307$},
pnm = {DORIS Beamline F1 (POF1-550)},
pid = {G:(DE-H253)POF1-F1-20130405},
experiment = {EXP:(DE-H253)D-F1-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:19617685},
UT = {WOS:000268019100011},
doi = {10.1107/S0108768109016966},
url = {https://bib-pubdb1.desy.de/record/92553},
}