TY  - JOUR
A1  - Büchner, Robby
A1  - Fondell, Mattis
A1  - Mascarenhas, Eric Johnn
A1  - Pietzsch, Annette
A1  - Vaz da Cruz, Vinícius
A1  - Föhlisch, Alexander
T1  - How hydrogen bonding amplifies isomeric differences in pyridones toward strong changes in acidity and tautomerism
T2  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - Steric hindrance of hydration and hydrogen bond enhancement by localized charges have been identified as key factors for the massive chemical differences between the hydroxypyridine/pyridone isomers in aqueous solution. While all isomers occur mainly in the hydroxypyridine form in the gas phase, they differ by more than 3 orders of magnitude both in their acidity and tautomeric equilibrium constants upon hydration. By monitoring the electronic and solvation structures as a function of the protonation state and the O- substitution position on the pyridine ring, the amplification of the isomeric differences in aqueous solution has been investigated. Near-edge X-ray absorption fine structure (NEXAFS) measurements at the N K-edge served as the probe of the chemical state. The combination of molecular dynamics simulations, complete active space self-consistent field (CASSCF), and time-dependent density functional theory (TD-DFT) spectral calculations contributes to unraveling the principles of tautomerism and acidity in multiple biochemical systems based on tautomerism.
Y1  - 2021
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/61246
SN  - 1520-6106
SN  - 1520-5207
VL  - 125
IS  - 9
SP  - 2372
EP  - 2379
PB  - American Chemical Society
CY  - Washington
ER  -