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Title: Environmental Processing of Lipids Driven by Aqueous Photochemistry of α-Keto Acids

Abstract

Sunlight can initiate photochemical reactions of organic molecules though direct photolysis, photosensitization, and indirect processes, often leading to complex radical chemistry that can increase molecular complexity in the environment. α-Keto acids act as photoinitiators for organic species that are not themselves photoactive. Here, we demonstrate this capability through the reaction of two α-keto acids, pyruvic acid and 2-oxooctanoic acid, with a series of fatty acids and fatty alcohols. We show for five different cases that a cross-product between the photoinitiated α-keto acid and non-photoactive species is formed during photolysis in aqueous solution. Fatty acids and alcohols are relatively unreactive species, which suggests that α-keto acids are able to act as radical initiators for many atmospherically relevant molecules found in the sea surface microlayer and on atmospheric aerosol particles.

Authors:
 [1];  [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [4]
  1. Univ. of Colorado, Boulder, CO (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of Colorado, Boulder, CO (United States); Colorado State Univ., Fort Collins, CO (United States)
  3. Univ. of Colorado, Boulder, CO (United States); Univ. of California San Diego, La Jolla, CA (United States)
  4. Univ. of Colorado, Boulder, CO (United States)
  5. Cardiff Univ., Cardiff (United Kingdom)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1559143
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 5; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rapf, Rebecca J., Perkins, Russell J., Dooley, Michael R., Kroll, Jay A., Carpenter, Barry K., and Vaida, Veronica. Environmental Processing of Lipids Driven by Aqueous Photochemistry of α-Keto Acids. United States: N. p., 2018. Web. doi:10.1021/acscentsci.8b00124.
Rapf, Rebecca J., Perkins, Russell J., Dooley, Michael R., Kroll, Jay A., Carpenter, Barry K., & Vaida, Veronica. Environmental Processing of Lipids Driven by Aqueous Photochemistry of α-Keto Acids. United States. doi:10.1021/acscentsci.8b00124.
Rapf, Rebecca J., Perkins, Russell J., Dooley, Michael R., Kroll, Jay A., Carpenter, Barry K., and Vaida, Veronica. Wed . "Environmental Processing of Lipids Driven by Aqueous Photochemistry of α-Keto Acids". United States. doi:10.1021/acscentsci.8b00124. https://www.osti.gov/servlets/purl/1559143.
@article{osti_1559143,
title = {Environmental Processing of Lipids Driven by Aqueous Photochemistry of α-Keto Acids},
author = {Rapf, Rebecca J. and Perkins, Russell J. and Dooley, Michael R. and Kroll, Jay A. and Carpenter, Barry K. and Vaida, Veronica},
abstractNote = {Sunlight can initiate photochemical reactions of organic molecules though direct photolysis, photosensitization, and indirect processes, often leading to complex radical chemistry that can increase molecular complexity in the environment. α-Keto acids act as photoinitiators for organic species that are not themselves photoactive. Here, we demonstrate this capability through the reaction of two α-keto acids, pyruvic acid and 2-oxooctanoic acid, with a series of fatty acids and fatty alcohols. We show for five different cases that a cross-product between the photoinitiated α-keto acid and non-photoactive species is formed during photolysis in aqueous solution. Fatty acids and alcohols are relatively unreactive species, which suggests that α-keto acids are able to act as radical initiators for many atmospherically relevant molecules found in the sea surface microlayer and on atmospheric aerosol particles.},
doi = {10.1021/acscentsci.8b00124},
journal = {ACS Central Science},
number = 5,
volume = 4,
place = {United States},
year = {2018},
month = {4}
}

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