Photochemistry of the pyruvate anion produces CO2, CO, CH3–, CH3, and a low energy electron

Connor J. Clarke; Jemma A. Gibbard; Lewis Hutton; Jan R.R. Verlet; Basile F.E. Curchod

doi:10.1038/s41467-022-28582-4

Photochemistry of the pyruvate anion produces CO₂, CO, CH₃^–, CH₃, and a low energy electron

Connor J. Clarke
, Jemma A. Gibbard
, Lewis Hutton
, Jan R.R. Verlet^*
, Basile F.E. Curchod^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

20 Citations (Scopus)

129 Downloads (Pure)

Abstract

The photochemistry of pyruvic acid has attracted much scientific interest because it is believed to play critical roles in atmospheric chemistry. However, under most atmospherically relevant conditions, pyruvic acid deprotonates to form its conjugate base, the photochemistry of which is essentially unknown. Here, we present a detailed study of the photochemistry of the isolated pyruvate anion and uncover that it is extremely rich. Using photoelectron imaging and computational chemistry, we show that photoexcitation by UVA light leads to the formation of CO₂, CO, and CH₃⁻. The observation of the unusual methide anion formation and its subsequent decomposition into methyl radical and a free electron may hold important consequences for atmospheric chemistry. From a mechanistic perspective, the initial decarboxylation of pyruvate necessarily differs from that in pyruvic acid, due to the missing proton in the anion.

Original language	English
Article number	937
Journal	Nature Communications
Volume	13
Issue number	1
Early online date	17 Feb 2022
DOIs	https://doi.org/10.1038/s41467-022-28582-4
Publication status	Published - Dec 2022

Bibliographical note

Funding Information:
Jemma A. Gibbard is grateful for support from a Ramsay Memorial Fellowship. Connor J. Clarke is thankful for the supporting Durham Doctoral Scholarship. This project has received funding from the European Research Council (ERC) under the European Union?s Horizon 2020 research and innovation programme (Grant agreement No. 803718, project SINDAM). This article is based upon work from COST Action CA18212 ? Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology), and made use of the facilities of the Hamilton HPC Service of Durham University.

Funding Information:
Jemma A. Gibbard is grateful for support from a Ramsay Memorial Fellowship. Connor J. Clarke is thankful for the supporting Durham Doctoral Scholarship. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant agreement No. 803718, project SINDAM). This article is based upon work from COST Action CA18212 — Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology), and made use of the facilities of the Hamilton HPC Service of Durham University.

Publisher Copyright:
© 2022, The Author(s).

Research Groups and Themes

Physical & Theoretical

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Cite this

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title = "Photochemistry of the pyruvate anion produces CO2, CO, CH3–, CH3, and a low energy electron",

abstract = "The photochemistry of pyruvic acid has attracted much scientific interest because it is believed to play critical roles in atmospheric chemistry. However, under most atmospherically relevant conditions, pyruvic acid deprotonates to form its conjugate base, the photochemistry of which is essentially unknown. Here, we present a detailed study of the photochemistry of the isolated pyruvate anion and uncover that it is extremely rich. Using photoelectron imaging and computational chemistry, we show that photoexcitation by UVA light leads to the formation of CO2, CO, and CH3−. The observation of the unusual methide anion formation and its subsequent decomposition into methyl radical and a free electron may hold important consequences for atmospheric chemistry. From a mechanistic perspective, the initial decarboxylation of pyruvate necessarily differs from that in pyruvic acid, due to the missing proton in the anion.",

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note = "Funding Information: Jemma A. Gibbard is grateful for support from a Ramsay Memorial Fellowship. Connor J. Clarke is thankful for the supporting Durham Doctoral Scholarship. This project has received funding from the European Research Council (ERC) under the European Union?s Horizon 2020 research and innovation programme (Grant agreement No. 803718, project SINDAM). This article is based upon work from COST Action CA18212 ? Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology), and made use of the facilities of the Hamilton HPC Service of Durham University. Funding Information: Jemma A. Gibbard is grateful for support from a Ramsay Memorial Fellowship. Connor J. Clarke is thankful for the supporting Durham Doctoral Scholarship. This project has received funding from the European Research Council (ERC) under the European Union{\textquoteright}s Horizon 2020 research and innovation programme (Grant agreement No. 803718, project SINDAM). This article is based upon work from COST Action CA18212 — Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology), and made use of the facilities of the Hamilton HPC Service of Durham University. Publisher Copyright: {\textcopyright} 2022, The Author(s).",

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