Infrared spectroscopy of 2-oxo-octanoic acid in multiple phases.

Alpha-keto acids are environmentally and biologically relevant species whose chemistry has been shown to be influenced by their local environment. Vibrational spectroscopy provides useful ways to probe the potential inter- and intramolecular interactions available to them in several phases. We measure and compare the IR spectra of 2-oxo-octanoic acid (2OOA) in the gas phase, solid phase, and at the air-water interface. With theoretical support, we assign many of the vibrational modes in each of the spectra. In the gas phase, two types of conformers are identified and distinguished, with the intramolecularly H-bonded form being the dominant type, while the second conformer type identified does not have an intramolecular hydrogen bond. The van der Waals interactions between molecules in solid 2OOA manifest C-H and CO vibrations lower in energy than in the gas phase and we propose an intermolecular hydrogen bonding scheme for the solid phase. At the air-water interface the hydrocarbon tails of 2OOA do interact with each other while the carbonyls appear to interact with water in the subphase, but not with neighboring 2OOA as might be expected of a closely packed surfactant film.

Chemistry and Photochemistry of Pyruvic Acid at the Air-Water Interface.

Interfacial regions are unique chemical reaction environments that can promote chemistry not found elsewhere. The air-water interface is ubiquitous in the natural environment in the form of ocean surfaces and aqueous atmospheric aerosols. Here we investigate the chemistry and photochemistry of pyruvic acid (PA), a common environmental species, at the air-water interface and compare it to its aqueous bulk chemistry using two different experimental setups: (1) a Langmuir-Blodgett trough, which models natural water surfaces and provides a direct comparison between the two reaction environments, and (2) an atmospheric simulation chamber (CESAM) to monitor the chemical processing of nebulized aqueous PA droplets. The results show that surface chemistry leads to substantial oligomer formation. The sequence begins with the condensation of lactic acid (LA), formed at the surface, with itself and with pyruvic acid, and LA + LA - H2O and LA + PA - H2O are prominent among the products in addition to a series of higher-molecular-weight oligomers of mixed units of PA and LA. In addition, we see zymonic acid at the surface. Actinic radiation enhances the production of the oligomers and produces additional surface-active molecules known from the established aqueous photochemical mechanisms. The presence and formation of complex organic molecules at the air-water interface from a simple precursor like PA in the natural environment is relevant to contemporary atmospheric science and is important in the context of prebiotic chemistry, where abiotic production of complex molecules is necessary for abiogenesis.

pH Dependence of the Aqueous Photochemistry of α-Keto Acids.

α-Keto acids are important, atmospherically relevant species, and their photochemistry has been considered in the formation and processing of aerosols. Despite their atmospheric relevance, the photochemistry of these species has primarily been studied under extremely low pH conditions. Using a variety of analytical techniques, we characterize the extent of hydration and deprotonation for solutions of two α-keto acids, pyruvic acid and 2-oxooctanoic acid, as a function of pH. We find that changes in the initial solution composition govern the accessibility of different photochemical pathways, resulting in slowed photolysis under high pH conditions and a shift in photoproducts that can be predicted mechanistically.