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@ARTICLE{Credidio:619676,
author = {Credidio, Bruno and Thürmer, Stephan and Stemer, Dominik
and Pugini, Michele and Trinter, Florian and Vokrouhlický,
Jakub and Slavicek, Petr and Winter, Bernd},
title = {{F}rom {G}as to {S}olution: {T}he {C}hanging {N}eutral
{S}tructure of {P}roline upon {S}olvation},
journal = {The journal of physical chemistry / A},
volume = {128},
number = {47},
issn = {1089-5639},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PUBDB-2024-07815},
pages = {10202-10212},
year = {2024},
note = {Open Access},
abstract = {Liquid-jet photoelectron spectroscopy (LJ-PES) and
electronic-structure theory were employed to investigate the
chemical and structural properties of the amino acid
l-proline in aqueous solution for its three ionized states
(protonated, zwitterionic, and deprotonated). This is the
first PES study of this amino acid in its biologically
relevant environment. Proline’s structure in the aqueous
phase under neutral conditions is zwitterionic, distinctly
different from the nonionic neutral form in the gas phase.
By analyzing the carbon 1s and nitrogen 1s core levels as
well as the valence spectra of aqueous-phase proline, we
found that the electronic structure is dominated by the
protonation state of each constituent molecular site (the
carboxyl and amine groups) with small yet noticeable
interference across the molecule. The site-specific nature
of the core-level spectra enables the probing of individual
molecular constituents. The valence photoelectron spectra
are more difficult to interpret because of the overlapping
signals of proline with the solvent and pH-adjusting agents
(HCl and NaOH). Yet, we are able to reveal subtle effects of
specific (hydrogen-bonding) interaction with the solvent on
the electronic structure. We also demonstrate that the
relevant conformational space is much smaller for
aqueous-phase proline than for its gas-phase analogue. This
study suggests that caution must be taken when comparing
photoelectron spectra for gaseous- and aqueous-phase
molecules, particularly if those molecules are readily
protonated/deprotonated in solution.},
cin = {DOOR ; HAS-User / FS-PETRA-S},
ddc = {530},
cid = {I:(DE-H253)HAS-User-20120731 /
I:(DE-H253)FS-PETRA-S-20210408},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / FS-Proposal:
II-20210015 (II-20210015) / DFG project G:(GEPRIS)509471550
- Dynamik photoionisations-induzierter Prozesse in
laser-präparierten Molekülen in der Gasphase und der
wässrigen Phase (509471550) / AQUACHIRAL - Chiral
aqueous-phase chemistry (883759)},
pid = {G:(DE-HGF)POF4-6G3 / G:(DE-H253)II-20210015 /
G:(GEPRIS)509471550 / G:(EU-Grant)883759},
experiment = {EXP:(DE-H253)P-P04-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {39536145},
UT = {WOS:001353932300001},
doi = {10.1021/acs.jpca.4c05628},
url = {https://bib-pubdb1.desy.de/record/619676},
}