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Published March 16, 2006 | public
Journal Article

Photoinduced Oligomerization of Aqueous Pyruvic Acid


The 320 nm-band photodecarboxylation of aqueous pyruvic acid (PA), a representative of the α-oxocarboxylic acids widely found in the atmospheric aerosol, yields 2,3-dimethyltartaric (A) and 2-(3-oxobutan-2-yloxy)-2-hydroxypropanoic (B) acids, rather than 3-hydroxy-2-oxobutanone as previously reported. A and B are identified by liquid chromatography with UV and ESI-MS detection, complemented by collisionally induced dissociation and ^2H and ^(13)C isotope labeling experiments. The multifunctional ether B gives rise to characteristic δ ∼ 80 ppm ^(13)C NMR resonances. Product quantum yields are proportional to [PA](a + [PA])^(-1) in the range [PA] = 5−100 mM. CO_2(g) release rates are halved, while A and B are suppressed by the addition of >1.5 mM TEMPO. A and B are only partially quenched in air-saturated solutions. These observations are shown to be consistent with an oligomerization process initiated by a bimolecular reaction between ^3PA* and PA producing ketyl, CH_3Ċ(OH)C(O)OH, and acetyl, CH_3C(O)·, radicals, rather than by the unimolecular decomposition of ^3PA* into 1-hydroxyethylidene, ^3HO(CH_3)C:  (+CO_2), or [CH_3C(O)· + ·C(O)OH] pairs. A arises from the dimerization of ketyl radicals, while B ensues the facile decarboxylation of the C_8β-ketoacid formed by association of acetyl radicals with the ketyl radical adduct of PA. Since the radical precursors to A and B are scavenged by O2 with a low probability per encounter (ksc ∼ 1 × 10^6 M^(-1) s^(-1)), PA is able to accrete into multifunctional polar species in aerated aqueous media under solar illumination.

Additional Information

© 2006 American Chemical Society. Received: October 24, 2005; In Final Form: January 10, 2006. This work was financed by NSF Grant ATM-0228140. This project benefited from the use of instrumentation made available by the Caltech Environmental Analysis Center. N. Dalleska provided valuable assistance with chromatographic analysis.

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