Scientists Find Proton Sharing Rare in Most Biological Acids
Researchers using advanced X-ray spectroscopy discovered that proton sharing—a chemical behavior long debated in textbooks—occurs in only one of six common biological acids tested in water. The finding suggests enzymes may actively engineer molecular structures to enable proton sharing during metabolism, pointing to new targets for drug design and bioprocess optimization.
Originaltitel: 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.