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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.

Organic molecules, including α-hydroxyacids, are ubiquitous in the natural environment. Often found at water-air interfaces, organic molecules can alter the structure of the interface or participate in interfacial chemistry. Despite their prevalence in the environment, the structure and ordering of α-hydroxyacids have not been widely investigated at water-air interfaces, and the impact of the hydrophobic tail length on structure has not been explored. Here, for the first time, we use infrared reflection-absorption spectroscopy to assess the vibrational structure of α-hydroxyacids at a water surface as a function of surface partitioning and surface coverage. We study lactic acid, 2-hydroxyoctanoic acid, and 2-hydroxystearic acid, which have 1 carbon, 6 carbon, and 16 carbon tails, respectively. Vibrational features compared across the set of α-hydroxyacids studied here are used to determine the interaction of the polar headgroup with the water subphase and the ordering of the hydrophobic tail. We find that the carbonyl and α-hydroxyl groups participate in a complex hydrogen-bonding motif at the water-air interface that can be affected by the hydrophobic tail length and places the polar headgroup in or below the water-air interface. Furthermore, molecular ordering increases with the tail length or the surface coverage. The presence of the α-hydroxyl group causes the α-hydroxyacids to maintain a tilted orientation with respect to the surface normal even at high surface coverages. A combination of polar headgroup and hydrophobic tail effects dictates the overall orientation of α-hydroxyacids and can thus affect their ability to participate in chemistry and alter organic coatings on water surfaces.

The asymmetric water-air interface provides a dynamic aqueous environment with properties that are often very different than bulk aqueous or gaseous phases and promotes reactions that are thermodynamically, kinetically, or otherwise unfavorable in bulk water. Prebiotic chemistry faces a key challenge: water is necessary for life yet reduces the efficiency of many biomolecular synthesis reactions. This perspective considers water-air interfaces as auspicious reaction environments for abiotic synthesis. We discuss recent evidence that (1) water-air interfaces promote condensation reactions including peptide synthesis, phosphorylation, and oligomerization; (2) photochemistry at water-air interfaces may have been a significant source of prebiotic molecular complexity, given the lack of oxygen and increased availability of near-ultraviolet radiation on early Earth; and (3) water-air interfaces can promote spontaneous reduction and oxidation reactions, potentially providing protometabolic pathways. Life likely began within a relatively short time frame, and water-air interfaces offer promising environments for simultaneous and efficient biomolecule production.

Gas-phase reactions between pyruvic acid (PA) and HO2 radicals were examined using ab initio quantum chemistry and transition state theory. The rate coefficients were determined over a temperature range of 200-400 K including tunneling contributions. Six potential reaction pathways were identified. The two hydrogen abstraction reactions yielding the H2O2 product were found to have high barriers. The HO2 radical was also found to have a catalytic effect on the intramolecular hydrogen transfer reactions occurring by three distinct routes. These hydrogen-shift reactions are very interesting mechanistically although they are highly endothermic. The only reaction that contributes significantly to the consumption of PA is a multistep pathway involving a peroxy-radical intermediate, PA + HO2 → CH3COOH + OH + CO2. This exothermic process has potential atmospheric relevance because it produces an OH radical as a product. Atmospheric models currently have difficulty predicting accurate OH concentrations for certain atmospheric conditions, such as environments free of NOx and the nocturnal boundary layer. Reactions of this sort, although not necessary with PA, may account for a portion of this deficit. The present study helps settle the issue of the relative roles of reaction and photolysis in consumption of PA in the troposphere.

We study the primary photolysis dynamics of aqueous lactate induced by photo-excitation atλ= 200 nm. Our calculations indicate that both decarboxylation and dehydroxylation are energetically possible, but decarboxylation is favoured dynamically. UV pump - IR probe transient absorption spectroscopy shows that the photolysis is dominated by decarboxylation, whereas dehydroxylation is not observed. Analysis of the transient IR spectrum suggests that photo-dissociation of lactate primarily produces CO2and CH3CHOH−through the lowest singlet excited state of lactate, which has a lifetime ofτ= 11 ps. UV pump - VIS probe transient absorption spectroscopy of electrons from the dissociating lactate anion indicates that the anionic electron from the CO2˙−fragment is transferred to the CH3CHOH˙ counter radical during the decarboxylation process, and CO2˙−is consequently only observed as a minor photo-product. The photo-dissociation quantum yield after the full decay of the excited state is Φ(100ps) = 38 ± 5%.

The gas-phase reaction of pyruvic acid (PA) with the OH radical is studied theoretically using accurate quantum chemistry and transition state theory. Two chemically distinct H-atom abstraction reactions and two distinct OH addition reactions have been identified. The rate coefficients for these four processes were calculated. Quantum tunneling was included in each rate using the small curvature tunneling method. The influence of the conformational structure of PA was found to be particularly intriguing. While the trans-cis structure was found to dominantly react by H-atom abstraction from the methyl site, the trans-trans conformer was found to react mostly through H-atom abstraction from the acid site. A general formalism was developed to model the kinetics of the reactions that involve multiple conformers, interconverting prereactive complexes, and multiple transition states. Comparison of the results obtained with available experimental rate observations reveals agreement with the trans-trans conformer of PA but disagreement with the results obtained for a full statistical mixture of reagents. The role of these reactions in the atmospheric processing of PA is discussed.

Gas-phase reactions between pyruvic acid (PA) and HO

International audience; 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.

Lactic acid, a relevant molecule in biology and the environment, is an α-hydroxy acid with a high propensity to form hydrogen bonds, both internally and to other hydrogen-bond-accepting molecules. This work includes the novel recording of infrared spectra of gas-phase lactic acid using Fourier transform infrared spectroscopy, and the vibrational absorption features of lactic acid are assigned with the aid of computationally simulated vibrational spectra with anharmonic corrections. Theoretical chemistry methods are used to relate intramolecular hydrogen-bond strengths to the relative stability of lactic acid conformers. The formation of hydrogen-bonded lactic acid dimers and 1:1 water complexes is investigated by simulated vibrational spectra and calculated thermodynamic parameters for the lactic acid monomer and dimer and its water complex in the gas phase. The results of this study are discussed in the context of environmental chemistry with an emphasis on indoor environments.

The conformer-specific reactivity of gas-phase pyruvic acid following the S1(nπ*) ← S0 excitation at λmax = 350 nm (290-380 nm) and the effect of water are investigated for the two lowest energy conformers. Conformer-specific gas-phase pyruvic acid photolysis rate constants and their respective populations are measured by monitoring their distinct vibrational OH-stretching frequencies. The geometry, relative energies, fundamental vibrational frequencies, and electronic transitions of the pyruvic acid conformers and their monohydrated complexes are calculated with density functional theory and ab initio methods. Results from experiment and theory show that the more stable conformer with an intramolecular hydrogen bond dominates the gas-phase photolysis of pyruvic acid. Water greatly affects the gas-phase pyruvic acid conformer population and photochemistry through hydrogen bonding interactions. The addition of water decreases the gas-phase relative population of the more stable conformer and decreases the molecule's gas-phase photolysis rate constants. The theoretical results show that even a single water molecule interrupts the intramolecular hydrogen bond, which is essential for the efficient photodissociation of gas-phase pyruvic acid. Results of this study suggest that the aqueous-phase photochemistry of pyruvic acid proceeds through hydrogen-bonded conformers lacking an intramolecular hydrogen bond.

We studied the reaction of electronically excited sulfur dioxide in the triplet state (3SO2) with a variety of alkane species, including propane, n-butane, isobutane, n-pentane, n-hexane, cyclohexa...

The reaction of electronically excited triplet state sulfur dioxide (3SO2) with water was investigated both theoretically and experimentally. The quantum chemical calculations find that the reaction leads to the formation of hydroxyl radical (OH) and hydroxysulfinyl radical (HOSO) via a low energy barrier pathway. Experimentally the formation of OH was monitored via its reaction with methane, which itself is relatively unreactive with 3SO2, making it a suitable probe of OH production from the reaction of 3SO2 and water. This reaction has implications for the formation of OH in environments that are assumed to be depleted in OH, such as volcanic plumes. This reaction also provides a mechanism for the formation of OH in planetary atmospheres with little or no oxygen (O2) or ozone (O3) present.

Pyruvic acid is an atmospherically abundant α-keto-acid that degrades efficiently from the troposphere via gas-phase photolysis. To explore conditions relevant to the environment, 2–12 ppm pyruvic acid is irradiated by a solar simulator in the environmental simulation chamber, CESAM. The combination of the long path length available in the chamber and its low surface area to volume ratio allows us to quantitatively examine the quantum yield and photochemical products of pyruvic acid. Such details are new to the literature for the low initial concentrations of pyruvic acid employed here. We determined photolysis quantum yields of ϕobsN2 = 0.84 ± 0.1 in nitrogen and ϕobsAir = 3.2 ± 0.5 in air, which are higher than those reported by previous studies that used higher partial pressures of pyruvic acid. The quantum yield greater than unity in air is due to secondary chemistry, driven by O2, that emerges under the conditions in these experiments. The low concentration of pyruvic acid and the resulting oxygen ef...

Biological membranes are a crucial aspect of living systems, controlling the organization and distribution of different chemical components. Control of membrane permeability is especially important for processes such as electron transport in metabolism and signal propagation in nerve cells. In this work, we show that the amino acid phenylalanine produces increased membrane permeability, which is likely responsible for some of the deleterious symptoms associated with high biological phenylalanine concentrations that occur with the genetic disorder phenylketonuria.

The gas phase ultraviolet spectrum and stability of 1,1-dihydroxyacetone (the geminal diol of methylglyoxal) are investigated using spectroscopic and computational methods. Experimental gas phase electronic spectra recorded in the ultraviolet–visible range were used to follow the hydration of methylglyoxal. We show that upon the addition of water, methylglyoxal hydrates to form the geminal diol. The electronic spectra of methylglyoxal and its geminal diol conformers were calculated using TD-DFT and LR-CC methods to facilitate experimental peak assignments. The lowest energy electronic transition of the diol is experimentally measured and compared with the results of the theoretical calculations. We find that upon formation of the diol, the lowest-energy transition of methylglyoxal (centered around ∼430 nm) vanishes, and the remaining transitions, including the methylglyoxal diol absorptions (λmax = 240 nm), fall outside the available solar actinic flux in the troposphere. This likely has significant impac...

The chemistry of pyruvic acid is of great interest due to its essential role in metabolism for all life and its role in atmospheric chemistry. Pyruvic acid under a wide range of conditions, including normal storage conditions, will spontaneously dimerize to form zymonic acid. We isolated zymonic acid and, using a variety of 1D and 2D NMR techniques, identified it as a single structure as a solid or dissolved in DMSO. When in aqueous solution, however, we identified a mixture of five different tautomers and hydrates in equilibrium with each other with no single dominant form. The kinetics of this conversion were studied in situ via NMR. The reactivity of the tautomers and hydrates in aqueous solution is investigated and discussed in terms of aqueous reaction mechanisms. There is strong evidence for a direct, reversible conversion from an enol to a geminal diol without passing through a ketone intermediate, which implies the reversible addition of water across a double bond under ambient conditions. Additionally, there is evidence for a base catalyzed lactone ring formation, which is in essence a base catalyzed esterification reaction. The equilibrium between pyruvic acid and its oligomers in aqueous solution is of consequence in the natural environment.

In this work, we investigate the impact of pressure and oxygen on the kinetics of and products from the gas-phase photolysis of pyruvic acid. The results reveal a decrease in the photolysis quantum yield as pressure of air or nitrogen is increased, a trend not yet documented in the literature. A Stern—Volmer analysis demonstrates this effect is due to deactivation of the singlet state of pyruvic acid when the photolysis is performed in nitrogen, and from quenching of both the singlet and triplet state in air. Consistent with previous studies, acetaldehyde and CO2 are observed as the major products; however, other products, most notably acetic acid, are also identified in this work. The yield of acetic acid increases with increasing pressure of buffer gas, an effect that is amplified by the presence of oxygen. At least two mechanisms are necessary to explain the acetic acid, including one that requires reaction of photolysis intermediates with O2. These findings extend the fundamental understanding of the gas-phase photochemistry of pyruvic acid, highlighting the importance of pressure on the photolysis quantum yields and products.

The surface chemistry and photochemistry of gas-phase pyruvic acid (CH3COCOOH) on two oxides, Al2O3 and TiO2, have been investigated using transmission Fourier transform infrared spectroscopy and m...

The adsorption of gas-phase pyruvic acid (CH3COCOOH) on hydroxylated silica particles has been investigated at 296 K using transmission Fourier transform infrared (FTIR) spectroscopy and theoretical simulations. Under dry conditions (

We studied the reaction of electronically excited sulfur dioxide in the triplet state (

The reaction of electronically excited triplet state sulfur dioxide (

The intramolecular hydrogen bonding in methyl lactate was studied with Fourier transform infrared (FTIR) spectroscopy, intracavity laser photoacoustic spectroscopy, and cavity ring-down spectroscopy. Vapor phase spectra were recorded in the ΔvOH = 1-4 OH-stretching regions, and the observed OH-stretching transitions were compared with theoretical results. Transition frequencies and oscillator strengths were obtained using a one-dimensional anharmonic oscillator local mode model with potential energy and dipole moment surfaces calculated at the CCSD(T)-F12a/VDZ-F12 level. The three most abundant conformers of methyl lactate all appear to possess an intramolecular hydrogen bond, with the hydroxyl group forming a hydrogen bond with either the carbonyl or ester oxygen. The intramolecular hydrogen bonds were investigated theoretically by analyses based on electron density topology, natural bond orbital analysis, and visualization of the electrostatic potential energy.

The aqueous phase photochemistry of pyruvic acid, an important oxidation product of isoprene, is known to generate larger oligomeric species that may contribute to the formation of secondary organic aerosol in the atmosphere. Using high resolution negative mode electrospray ionization mass spectrometry, the aqueous photochemistry of dilute solutions of pyruvic acid (10, 1, and 0.5 mM) under anaerobic conditions was investigated. Even at the lowest concentration, covalently bonded dimers and trimers of pyruvic acid were observed as photochemical products. We calculate that it is energetically possible to photochemically generate parapyruvic acid, a dimer of pyruvic acid that is known to form via dark oligomerization processes. Subsequent photochemical reactions of parapyruvic acid with pyruvic acid form larger oligomeric products, such as 2,4-dihydroxy-2-methyl-5-oxohexanoic acid. A robust and relatively simple photochemical mechanism is discussed that explains both the conditional dependence and wide array of products that are observed.

The aqueous phase photochemistry of a series of amphiphilic α-keto acids with differing linear alkyl chain lengths was investigated, demonstrating the ability of sunlight-initiated reactions to build molecular complexity under environmentally relevant conditions. We show that the photochemical reaction mechanisms for α-keto acids in aqueous solution are robust and generalizable across alkyl chain lengths. The organic radicals generated during photolysis are indiscriminate, leading to a large mixture of photoproducts that are observed using high-resolution electrospray ionization mass spectrometry, but these products are identifiable following literature photochemical mechanisms. The alkyl oxoacids under study here can undergo a Norrish Type II reaction to generate pyruvic acid, increasing the diversity of observed photoproducts. The major products of this photochemistry are covalently bonded dimers and trimers of the starting oxoacids, many of which are multi-tailed lipids. The properties of these oligomers are discussed, including their spontaneous self-assembly into aggregates.

Aerosol and molecular processing in the atmosphere occurs in a complex and variable environment consisting of multiple phases and interfacial regions. To explore the effects of such conditions on the reactivity of chemical systems, we employ an environmental simulation chamber to investigate the multiphase photolysis of pyruvic acid, which photoreacts in the troposphere in aqueous particles and in the gas phase. Upon irradiation of nebulized pyruvic acid, acetic acid and carbon dioxide are rapidly generated, which is consistent with previous literature on the bulk phase photolysis reactions. Additionally, we identify a new C6 product, zymonic acid, a species that has not previously been reported from pyruvic acid photolysis under any conditions. Its observation here, and corresponding spectroscopic signatures, indicates it could be formed by heterogeneous reactions at the droplet surface. Prior studies of the aqueous photolysis of pyruvic acid have shown that high-molecular-weight compounds are formed via...

We present a brief review of long wavelength, red-light initiated chemistry from excited vibrational levels of the ground electronic state of atmospheric trace species. When sunlight driven electronic state reactions are not effective, photochemical processes occurring by vibrational overtone excitation have been found to be important in reactions of oxidized atmospheric compounds (acids, alcohols and peroxides) prevalent in the Earth's atmosphere. This review focuses on the fundamental energetic, mechanistic and dynamical aspects of unimolecular reactions of vibrationally excited atmospheric species. We will discuss the relevance of these red light initiated reactions to address the discrepancies between atmospheric measurements and results of standard atmospheric models.

Gas-phase vibrational spectra of 2-aminoethanol and 3-aminopropanol were recorded up to the third OH-stretching overtone using Fourier transform infrared spectroscopy, cavity ringdown spectroscopy, and intracavity laser photoacoustic spectroscopy. The experimental investigation was supplemented by local mode calculations, and the intramolecular interactions were investigated using atoms in molecules (AIM) and noncovalent interactions (NCI) theories. All calculations were performed at the CCSD(T)-F12a/VDZ-F12 level of theory. For both compounds the most abundant conformer has a structure that allows for hydrogen bond interaction from the OH group to the N atom of the amino group (OH-N). The spectra show signals from both hydrogen bonded and free OH stretches, implying the presence of several conformers. We observe hydrogen-bond-like interactions in both compounds. The red shift of the bonded OH-stretching frequency and intensity enhancement of the fundamental transition suggest that the hydrogen bond interaction is more pronounced in 3-aminopropanol. AIM analysis supports the presence of a hydrogen bond in 3-aminopropanol but not in 2-aminoethanol, whereas NCI analysis shows hydrogen bonding in both compounds with the stronger interaction found in 3-aminopropanol.

The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH 3 COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH 3 CHOHCOCH 3 ), lactic acid (CH 3 CHOHCOOH), acetic acid (CH 3 COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols.

Mixed organic films composed of molecules with differing hydrophobic groups are relevant to environmental interfaces such as the surface of atmospheric aerosols due to the complex composition of atmospheric emissions. In this work, mixed films composed of oxidized aromatics (benzaldehyde, benzoic acid) and stearic acid are studied using Langmuir trough methods, infrared reflection–absorption spectroscopy (IRRAS), and MD simulations, showing modifications to the surface due to both the hydrophobic and hydrophilic identity of the aromatic molecules. Aromatics are a known component of crude oil, and once released into the atmosphere through an event such as an oil spill, they can be weathered to produce varying degrees of oxidized products like benzaldehyde or benzoic acid. Molecules released through such anthropogenic processes are shown here to have complex interactions with organics released through biogenic emissions (like stearic acid) at the aqueous interface, resulting in diverse surface morphologies ...

We have monitored changes in the infrared spectrum of gas-phase ketene in the presence of water vapor at 295 K. The products observed from ketene hydration are acetic acid, acetic acid dimer, and acetic anhydride. The time-dependence of product formation supports a reaction mechanism in which ketene hydrates to form acetic acid, which then combines with another acetic acid monomer to form a dimer, or with ketene to form acetic anhydride. These results show that ketene can undergo hydration under atmospherically-relevant temperatures and relative humidities. This reaction could be a source of atmospheric carboxylic acids, especially in biomass burning plumes.

The ionization state of organic molecules at the air-water interface and the related problem of the surface pH of water have significant consequences on the catalytic role of the surface in chemical reactions and are currently areas of intense research and controversy. In this work, infrared reflection-absorption spectroscopy (IRRAS) is used to identify changes in the ionization state of L-phenylalanine in the surface region versus the bulk aqueous solution. L-phenylalanine has the unique advantage of possessing two different hydrophilic groups, a carboxylic acid and an amine base, which can deprotonate and protonate respectively depending on the ionic environment they experience at the water surface. In this work, the polar group vibrations in the surface region are identified spectroscopically in varying bulk pH solutions, and are subsequently compared with the ionization state of the polar groups of molecules residing in the bulk environment. The polar groups of L-phenylalanine at the surface transition to their deprotonated state at bulk pH values lower than the molecules residing in the bulk, indicating a decrease in their pK(a) at the surface, and implying an enhanced hydroxide ion concentration in the surface region relative to the bulk.