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Mechanistic description of photochemical oligomer formation from aqueous pyruvic acid

Rapf, Rebecca J., Perkins, Russell J., Carpenter, Barry K. ORCID: and Vaida, Veronica 2017. Mechanistic description of photochemical oligomer formation from aqueous pyruvic acid. Journal of Physical Chemistry A 121 (22) , pp. 4272-4282. 10.1021/acs.jpca.7b03310

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The aqueous phase photochemistry of pyruvic acid, an important oxidation product of isoprene, is known to generate larger oligomeric species that may contribute to the formation of secondary organic aerosol in the atmosphere. Using high resolution negative mode electrospray ionization mass spectrometry, the aqueous photochemistry of dilute solutions of pyruvic acid (10, 1, and 0.5 mM) under anaerobic conditions was investigated. Even at the lowest concentration, covalently bonded dimers and trimers of pyruvic acid were observed as photochemical products. We calculate that it is energetically possible to photochemically generate parapyruvic acid, a dimer of pyruvic acid that is known to form via dark oligomerization processes. Subsequent photochemical reactions of parapyruvic acid with pyruvic acid form larger oligomeric products, such as 2,4-dihydroxy-2-methyl-5-oxohexanoic acid. A robust and relatively simple photochemical mechanism is discussed that explains both the conditional dependence and wide array of products that are observed.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Advanced Research Computing @ Cardiff (ARCCA)
Publisher: American Chemical Society
ISSN: 1089-5639
Date of First Compliant Deposit: 22 October 2018
Date of Acceptance: 16 May 2017
Last Modified: 07 Nov 2023 10:16

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