Issue 29, 2024

Liquid-jet photoemission spectroscopy as a structural tool: site-specific acid–base chemistry of vitamin C

Abstract

Liquid-jet photoemission spectroscopy (LJ-PES) directly probes the electronic structure of solutes and solvents. It also emerges as a novel tool to explore chemical structure in aqueous solutions, yet the scope of the approach has to be examined. Here, we present a pH-dependent liquid-jet photoelectron spectroscopic investigation of ascorbic acid (vitamin C). We combine core-level photoelectron spectroscopy and ab initio calculations, allowing us to site-specifically explore the acid–base chemistry of the biomolecule. For the first time, we demonstrate the capability of the method to simultaneously assign two deprotonation sites within the molecule. We show that a large change in chemical shift appears even for atoms distant several bonds from the chemically modified group. Furthermore, we present a highly efficient and accurate computational protocol based on a single structure using the maximum-overlap method for modeling core-level photoelectron spectra in aqueous environments. This work poses a broader question: to what extent can LJ-PES complement established structural techniques such as nuclear magnetic resonance? Answering this question is highly relevant in view of the large number of incorrect molecular structures published.

Graphical abstract: Liquid-jet photoemission spectroscopy as a structural tool: site-specific acid–base chemistry of vitamin C

Supplementary files

Article information

Article type
Paper
Submitted
13 Apr 2024
Accepted
12 Jun 2024
First published
28 Jun 2024
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2024,26, 19673-19684

Liquid-jet photoemission spectroscopy as a structural tool: site-specific acid–base chemistry of vitamin C

L. Tomaník, M. Pugini, K. Mudryk, S. Thürmer, D. Stemer, B. Credidio, F. Trinter, B. Winter and P. Slavíček, Phys. Chem. Chem. Phys., 2024, 26, 19673 DOI: 10.1039/D4CP01521E

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