Proton Sharing in Polycarboxylic Acids in Aqueous Solution
We investigate proton sharing in biologically relevant polycarboxylic acids in aqueous solutions using liquid-jet X-ray photoelectron spectroscopy. In contrast to techniques that record time-averaged proton positions, like nuclear magnetic resonance, photoelectron spectroscopy captures instantaneous proton distribution due to its ultrafast probing time scale. The method is, therefore, uniquely sensitive to the occurrence of proton sharing in an aqueous environment, as demonstrated here. We only observe significant proton sharing dynamics in maleic acid, where its monoanionic form shows a single, delocalized peak in the carbon 1s spectrum. Conversely, succinic acid, fumaric acid, malic acid, glutaric acid, and citric acid exhibit distinct peaks corresponding to separate, localized COOH and COO– groups, instead of shared protons. Our results reveal that intramolecular proton sharing in water is rather an exception for most biologically relevant polycarboxylic acids. This highlights the importance of enzyme-driven structural changes of polycarboxylic acids associated with proton sharing during metabolic processes.
Authors
- Ngoc Lan Le Nguyen
- Ronny Golnak (ORCID: https://orcid.org/0000-0002-5461-5284)
- Lukáš Tomaník (ORCID: https://orcid.org/0000-0003-2547-2488)
- Jiří Tůma (ORCID: https://orcid.org/0000-0002-0934-2272)
- Harmanjot Kaur (ORCID: https://orcid.org/0000-0001-6577-4638)
- G. Öhrwall (ORCID: https://orcid.org/0000-0002-5795-8047)
- Bernd Winter (ORCID: https://orcid.org/0000-0002-5597-8888)
- Petr Slavíček (ORCID: https://orcid.org/0000-0002-5358-5538)
- H. Christian Schewe (ORCID: https://orcid.org/0000-0003-3232-5486)
- Bruno Credidio
Institutions
- Lund University (SE)
- Helmholtz-Zentrum Berlin für Materialien und Energie (DE)
- Fritz Haber Institute of the Max Planck Society (DE)
- Institute of Spectroscopy (RU)
- Czech Academy of Sciences, J. Heyrovský Institute of Physical Chemistry (CZ)
- MAX IV Laboratory (SE)
- Czech Academy of Sciences, Institute of Organic Chemistry and Biochemistry (CZ)
- Freie Universität Berlin (DE)
- University of Chemistry and Technology, Prague (CZ)
Publication Details
- Journal
- JACS Au
- Published
- 2026-05-11
- DOI
- https://doi.org/10.1021/jacsau.6c00377
- Primary Topic
- Photochemistry and Electron Transfer Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Univerzita Karlova v Praze
- Grantová Agentura České Republiky
- Horizon 2020 Framework Programme
- HORIZON EUROPE European Research Council