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

Details

• Journal Title:
  ACS Central Science
• Personal Author:
  Rapf, Rebecca J. ; Perkins, Russell J. ; Dooley, Michael R. ; Kroll, Jay A. ; Carpenter, Barry K. ; Vaida, Veronica
• NOAA Program & Office:
  CIRES (Cooperative Institute for Research in Environmental Sciences)
• Description:
  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.
• Keywords:
  Biochemistry
• Source:
  ACS Cent. Sci. 2018, 4, 5, 624–630
• DOI:
  https://doi.org/10.1021/acscentsci.8b00124
• Document Type:
  Journal Article
• Rights Information:
  Accepted Manuscript
• Compliance:
  Submitted
• Main Document Checksum:
  urn:sha-512:ba870c460d6be529ef5094a48db2b022e12f8a295b832d96bea3e27c1b9e684e7caf4c25def90f3596dd8e59e04f12d1c9afeb358f5d2f94dd0a074e3f1d3f57
• Download URL:
  https://repository.library.noaa.gov/view/noaa/26972/noaa_26972_DS1.pdf
• File Type:
  [PDF - 601.09 KB ]