Lower degree of dissociation of pyruvic acid at water surfaces than in bulk

Dominika Lesnicki; Veronika Wank; Jenee D. Cyran; Ellen H. G. Backus; Marialore Sulpizi

doi:10.1039/d2cp01293f

Lower degree of dissociation of pyruvic acid at water surfaces than in bulk

Dominika Lesnicki
, Veronika Wank
, Jenee D. Cyran
, Ellen H. G. Backus (Corresponding author)
, Marialore Sulpizi (Corresponding author)

Department of Physical Chemistry

Publications: Contribution to journal › Article › Peer Reviewed

Abstract

Understanding the acid/base behavior of environmentally relevant organic acids is of key relevance for accurate climate modelling. Here we investigate the effect of pH on the (de)protonation state of pyruvic acid at the air-water interface and in bulk by using the analytical techniques surface-specific vibrational sum frequency generation and attenuated total reflection spectroscopy. To provide a molecular interpretation of the observed behavior, simulations are carried out using a free energy perturbation approach in combination with electronic structure-based molecular dynamics. In both the experimental and theoretical results we observe that the protonated form of pyruvic acid is preferred at the air-water interface. The increased proton affinity is the result of the specific microsolvation at the interface.

Original language	English
Pages (from-to)	13510-13513
Number of pages	4
Journal	Physical Chemistry Chemical Physics
Volume	24
Issue number	22
DOIs	https://doi.org/10.1039/d2cp01293f
Publication status	Published - 10 May 2022

Funding

The authors thank the Max Planck Institute for Polymer Research for use of the laboratories and Grazia Gonella for fruitful discussions. The calculations were performed on the supercomputer of the High Performance Computing Center (HLRS) of Stuttgart (grant 2DSFG) and on the supercomputer Mogon at the Johannes Gutenberg University Mainz (hpc.unimainz.de). This project has received funding from the Deutsche Forschungsgemeinschaft under the TRR146 project (project A4). M. S. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germanys Excellence Strategy-EXC 2033-390677874-RESOLV.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 13 Climate Action

Austrian Fields of Science 2012

104016 Photochemistry
104017 Physical chemistry

Keywords

PHOTOCHEMISTRY
DENSITY
BASE

Access to Document

10.1039/d2cp01293fLicence: CC BY-NC 3.0

https://phaidra.univie.ac.at/o:1645628Licence: CC BY-NC 3.0

Cite this

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title = "Lower degree of dissociation of pyruvic acid at water surfaces than in bulk",

abstract = "Understanding the acid/base behavior of environmentally relevant organic acids is of key relevance for accurate climate modelling. Here we investigate the effect of pH on the (de)protonation state of pyruvic acid at the air-water interface and in bulk by using the analytical techniques surface-specific vibrational sum frequency generation and attenuated total reflection spectroscopy. To provide a molecular interpretation of the observed behavior, simulations are carried out using a free energy perturbation approach in combination with electronic structure-based molecular dynamics. In both the experimental and theoretical results we observe that the protonated form of pyruvic acid is preferred at the air-water interface. The increased proton affinity is the result of the specific microsolvation at the interface.",

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AU - Lesnicki, Dominika

AU - Wank, Veronika

AU - Cyran, Jenee D.

AU - Backus, Ellen H. G.

AU - Sulpizi, Marialore

PY - 2022/5/10

Y1 - 2022/5/10

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AB - Understanding the acid/base behavior of environmentally relevant organic acids is of key relevance for accurate climate modelling. Here we investigate the effect of pH on the (de)protonation state of pyruvic acid at the air-water interface and in bulk by using the analytical techniques surface-specific vibrational sum frequency generation and attenuated total reflection spectroscopy. To provide a molecular interpretation of the observed behavior, simulations are carried out using a free energy perturbation approach in combination with electronic structure-based molecular dynamics. In both the experimental and theoretical results we observe that the protonated form of pyruvic acid is preferred at the air-water interface. The increased proton affinity is the result of the specific microsolvation at the interface.

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Lower degree of dissociation of pyruvic acid at water surfaces than in bulk

Abstract

Funding

UN SDGs

Austrian Fields of Science 2012

Keywords

Access to Document

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