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@ARTICLE{Graen:315907,
author = {Graen, Timo and Inhester, Ludger and Clemens, Maike and
Grubmüller, Helmut and Groenhof, Gerrit},
title = {{T}he {L}ow {B}arrier {H}ydrogen {B}ond in the
{P}hotoactive {Y}ellow {P}rotein: {A} {V}acuum {A}rtifact
{A}bsent in the {C}rystal and {S}olution},
journal = {Journal of the American Chemical Society},
volume = {138},
number = {51},
issn = {1520-5126},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PUBDB-2016-06146},
pages = {16620 - 16631},
year = {2016},
note = {© American Chemical Society},
abstract = {There has been considerable debate on the existence of a
low-barrier hydrogen bond (LBHB) in the photoactive yellow
protein (PYP). The debate was initially triggered by the
neutron diffraction study of Yamaguchi et al. ( Proc. Natl.
Acad. Sci., U. S. A., 2009, 106, 440−444) who suggested a
model in which a neutral Arg52 residue triggers the
formation of the LBHB in PYP. Here, we present an
alternative model that is consistent within the error
margins of the Yamaguchi structure factors. The model
explains an increased hydrogen bond length without nuclear
quantum effects and for a protonated Arg52. We tested both
models by calculations under crystal, solution, and vacuum
conditions. Contrary to the common assumption in the field,
we found that a single PYP in vacuum does not provide an
accurate description of the crystal conditions but instead
introduces strong artifacts, which favor a LBHB and a large
1H NMR chemical shift. Our model of the crystal environment
was found to stabilize the two Arg52 hydrogen bonds and
crystal water positions for the protonated Arg52 residue in
free MD simulations and predicted an Arg52 pKa upshift with
respect to PYP in solution. The crystal and solution
environments resulted in almost identical 1H chemical shifts
that agree with NMR solution data. We also calculated the
effect of the Arg52 protonation state on the LBHB in 3D
nuclear equilibrium density calculations. Only the charged
crystal structure in vacuum supports a LBHB if Arg52 is
neutral in PYP at the previously reported level of theory (
J. Am. Chem. Soc., 2014, 136, 3542−3552). We attribute the
anomalies in the interpretation of the neutron data to a
shift of the potential minimum, which does not involve
nuclear quantum effects and is transferable beyond the
Yamaguchi structure.},
cin = {FS-CFEL-3},
ddc = {540},
cid = {I:(DE-H253)FS-CFEL-3-20120731},
pnm = {6211 - Extreme States of Matter: From Cold Ions to Hot
Plasmas (POF3-621)},
pid = {G:(DE-HGF)POF3-6211},
experiment = {EXP:(DE-MLZ)NOSPEC-20140101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000391081800014},
pubmed = {pmid:27966904},
doi = {10.1021/jacs.6b05609},
url = {https://bib-pubdb1.desy.de/record/315907},
}