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Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface.
J Am Chem Soc ; 137(26): 8348-51, 2015 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-26068588
We report on experiments that probe photosensitized chemistry at the air/water interface, a region that does not just connect the two phases but displays its own specific chemistry. Here, we follow reactions of octanol, a proxy for environmentally relevant soluble surfactants, initiated by an attack by triplet-state carbonyl compounds, which are themselves concentrated at the interface by the presence of this surfactant. Gas-phase products are determined using PTR-ToF-MS, and those remaining in the organic layer are determined by ATR-FTIR spectroscopy and HPLC-HRMS. We observe the photosensitized production of carboxylic acids as well as unsaturated and branched-chain oxygenated products, compounds that act as organic aerosol precursors and had been thought to be produced solely by biological activity. A mechanism that is consistent with the observations is detailed here, and the energetics of several key reactions are calculated using quantum chemical methods. The results suggest that the concentrating nature of the interface leads to its being a favorable venue for radical reactions yielding complex and functionalized products that themselves could initiate further secondary chemistry and new particle formation in the atmospheric environment.





Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: J Am Chem Soc Ano de publicação: 2015 Tipo de documento: Artigo País de afiliação: França