TY  - JOUR
A1  - Malerz, Sebastian
A1  - Mudryk, Karen Denise
A1  - Tomaník, Lukáš
A1  - Stemer, Dominik
A1  - Hergenhahn, Uwe
A1  - Buttersack, Tillmann
A1  - Trinter, Florian
A1  - Seidel, Robert
A1  - Quevedo, Wilson
A1  - Goy, Claudia
A1  - Wilkinson, Iain
A1  - Thürmer, Stephan
A1  - Slavíček, Petr
A1  - Winter, Bernd
T1  - Following in Emil Fischer's footsteps: a site-selective probe of glucose acid-base chemistry
T2  - The journal of physical chemistry
N2  - Liquid-jet photoelectron spectroscopy was applied to determine the first acid dissociation constant (pKa) of aqueous-phase glucose while simultaneously identifying the spectroscopic signature of the respective deprotonation site. Valence spectra from solutions at pH values below and above the first pKa reveal a change in glucose’s lowest ionization energy upon the deprotonation of neutral glucose and the subsequent emergence of its anionic counterpart. Site-specific insights into the solution-pH-dependent molecular structure changes are also shown to be accessible via C 1s photoelectron spectroscopy. The spectra reveal a considerably lower C 1s binding energy of the carbon site associated with the deprotonated hydroxyl group. The occurrence of photoelectron spectral fingerprints of cyclic and linear glucose prior to and upon deprotonation are also discussed. The experimental data are interpreted with the aid of electronic structure calculations. Our findings highlight the potential of liquid-jet photoelectron spectroscopy to act as a site-selective probe of the molecular structures that underpin the acid–base chemistry of polyprotic systems with relevance to environmental chemistry and biochemistry.
Y1  - 2021
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/62954
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-629544
SN  - 1520-5215
N1  - L.T. and P.S. acknowledge support by the Czech Science Foundation, project no. 21-26601X (EXPRO). L.T. acknowledges Specific University Research grant no. A2_FCHI_2021_028. F.T. and B.W. acknowledge support from the MaxWater initiative of the Max-Planck-Gesellschaft. B.W. acknowledges funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and investigation programme (grant agreement no. 883759). R.S. and W.Q. acknowledge funding from the German Research Foundation through an Emmy-Noether grant (SE 2253/3-1). S.T. acknowledges support from the JSPS KAKENHI grant no. JP20K15229.
VL  - 125
IS  - 32
SP  - 6881
EP  - 6892
PB  - Soc.
CY  - Washington, DC
ER  -