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On the Origins of Core-Electron Chemical Shifts of Small Biomolecules in Aqueous Solution: Insights from Photoemission and ab Initio Calculations of Glycine(aq)

Ottosson, Niklas; Borve, Knut J.; Spangberg, Daniel; Bergersen, Henrik; Saethre, Leif J.; Faubel, Manfred; Pokapanich, Wandared; Öhrwall, Gunnar LU ; Bjorneholm, E. and Winter, Bernd (2011) In Journal of the American Chemical Society 133(9). p.3120-3130
Abstract
The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon is binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak... (More)
The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon is binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
133
issue
9
pages
3120 - 3130
publisher
The American Chemical Society
external identifiers
  • wos:000289455200051
  • scopus:79952271680
ISSN
1520-5126
DOI
10.1021/ja110321q
language
English
LU publication?
yes
id
18b68419-64cc-4ec8-8811-0be5d4756cab (old id 1965554)
date added to LUP
2011-05-20 13:58:26
date last changed
2017-07-30 04:18:32
@article{18b68419-64cc-4ec8-8811-0be5d4756cab,
  abstract     = {The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon is binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine.},
  author       = {Ottosson, Niklas and Borve, Knut J. and Spangberg, Daniel and Bergersen, Henrik and Saethre, Leif J. and Faubel, Manfred and Pokapanich, Wandared and Öhrwall, Gunnar and Bjorneholm, E. and Winter, Bernd},
  issn         = {1520-5126},
  language     = {eng},
  number       = {9},
  pages        = {3120--3130},
  publisher    = {The American Chemical Society},
  series       = {Journal of the American Chemical Society},
  title        = {On the Origins of Core-Electron Chemical Shifts of Small Biomolecules in Aqueous Solution: Insights from Photoemission and ab Initio Calculations of Glycine(aq)},
  url          = {http://dx.doi.org/10.1021/ja110321q},
  volume       = {133},
  year         = {2011},
}