Issue 8, 2024

Transition from vehicle to Grotthuss proton transfer in a nanosized flask: cryogenic ion spectroscopy of protonated p-aminobenzoic acid solvated with D2O

Abstract

Proton transfer (PT) is one of the most ubiquitous reactions in chemistry and life science. The unique nature of PT has been rationalized not by the transport of a solvated proton (vehicle mechanism) but by the Grotthuss mechanism in which a proton is transported to the nearest proton acceptor along a hydrogen-bonded network. However, clear experimental evidence of the Grotthuss mechanism has not been reported yet. Herein we show by infrared spectroscopy that a vehicle-type PT occurs in the penta- and hexahydrated clusters of protonated p-aminobenzoic acid, while Grotthuss-type PT is observed in heptahydrated clusters, indicating a change in the PT mechanism depending on the degree of hydration. These findings emphasize the importance of the usually ignored vehicle mechanism as well as the degree of hydration. It highlights the possibility of controlling the PT mechanism by the number of water molecules in chemical and biological environments.

Graphical abstract: Transition from vehicle to Grotthuss proton transfer in a nanosized flask: cryogenic ion spectroscopy of protonated p-aminobenzoic acid solvated with D2O

Supplementary files

Article information

Article type
Edge Article
Submitted
16 Oct 2023
Accepted
18 Jan 2024
First published
19 Jan 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 2725-2730

Transition from vehicle to Grotthuss proton transfer in a nanosized flask: cryogenic ion spectroscopy of protonated p-aminobenzoic acid solvated with D2O

K. Hirata, K. Akasaka, O. Dopfer, S. Ishiuchi and M. Fujii, Chem. Sci., 2024, 15, 2725 DOI: 10.1039/D3SC05455A

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