Infrared Reflection Absorption Spectroscopy (IRRAS) of Water-Soluble Surfactants: Is it Surface-Specific?

Infrared reflection absorption spectroscopy (IRRAS) is commonly used to study the structure and chemistry of molecules residing at surfaces, including water surfaces, which has far-reaching applications including atmospheric chemistry and food science. However, there is some debate regarding the surface-specificity of IRRAS when examining soluble surfactants on aqueous solutions, and there is some evidence that the surface-specificity may differ between IRRAS of ionic surfactants and soluble organic acids. This paper presents infrared reflection absorption (IRRA) spectra of soluble organic acids underneath monolayers of insoluble surfactants, where the contributions from the insoluble surfactants are subtracted from the spectra to capture "subsurface effects". These "subsurface" spectra demonstrate that IRRA spectra of soluble organic acids are surface specific, and this observation is supported by a simplified model for reflections from "subsurface" layers. Finally, the observations presented here are compared to literature observations regarding the surface-specificity of IRRAS when studying ionic surfactants. Overall, this work demonstrates the utility of IRRAS for studying the structures and chemistry of soluble organic acids at aqueous surfaces.

Infrared Reflection-Absorption Spectroscopy of α-Keto Acids at the Air-Water Interface: Effects of Chain Length and Headgroup on Environmentally Relevant Surfactant Films.

A variety of organic surfactants are found at air-water interfaces in natural environments, including on the surfaces of aqueous aerosols. The structure and morphology of these organic films can have profound impacts on material transfer between the gas and condensed phases, the optical properties of atmospheric aerosol, and chemical processing at air-water interfaces. Combined, these effects can have significant impacts on climate via radiative forcing, but our understanding of organic films at air-water interfaces is incomplete. Here, we examine the impact of the polar headgroup and alkyl tail length on the structure and morphology of organic monolayers at the air-water interfaces. First, we focus on the substituted carboxylic acids, α-keto acids, using Langmuir isotherms and infrared reflection absorption spectroscopy (IR-RAS) to elucidate key structures and phase behaviors of α-keto acids with a range of surface activities. We show that the structure of α-keto acids, both soluble and insoluble, at water surfaces is a compromise between van der Waals interactions of the hydrocarbon tail and hydrogen bonding interactions involving the polar headgroup. Then, we use this new data set regarding α-keto acid films at water surfaces to examine the role of the polar headgroup on organic films using a similar substituted carboxylic acid (α-hydroxystearic acid), an unsubstituted carboxylic acid (stearic acid), and an alcohol (stearyl alcohol). We show that the polar headgroup and its hydrogen bonding interactions can significantly affect the orientation of amphiphiles at air-water interfaces. Here, we provide side-by-side comparisons of Langmuir isotherms and IR-RA spectra for a set of environmentally relevant organic amphiphiles with a range of alkyl tail lengths and polar headgroup structures.

Oxygen Effect on the Ultraviolet-C Photochemistry of Lactic Acid.

Lactic acid, a small α-hydroxyacid, is ubiquitous in both indoor and outdoor environments. Recently, the photochemistry of lactic acid has garnered interest among the abiotic organic chemistry community as it would have been present in abiotic settings and photoactive with the high-energy solar radiation that would have been available in the low oxygen early Earth environment. Additionally, we propose that the photochemistry of lactic acid is relevant to modern Earth during indoor ultraviolet-C (UVC) sterilization procedures as lactic acid is emitted by humans and is thus prevalent in indoor environments where UVC sterilization is increasingly being used. Here, we study the oxygen effect on the gas phase photolysis of lactic acid using Fourier-transform infrared (FTIR) spectroscopy and isotopically labeled oxygen (18O2). We find that the major products of gas phase lactic acid photolysis are CO2, CO, acetaldehyde, and acetic acid. Furthermore, these products are the same with or without added oxygen, but the partial pressures of produced CO2, CO, and acetaldehyde increase with the amount of added oxygen. Notably, the added oxygen is primarily incorporated into produced CO2 and CO, while little or none is incorporated into acetaldehyde. We combine the results presented here with those in the literature to propose a mechanism for the gas phase photolysis of lactic acid and the role of oxygen in this mechanism. Finally, we compare the output of a krypton-chloride excimer lamp (λ = 222 nm), one of the lamps proposed for UVC sterilization procedures, to the absorption of lactic acid. We show that lactic acid would be photoactive during UVC sterilization procedures, and we use the gas phase results presented here and aqueous lactic acid photolysis results previously published to assess potential byproducts from lactic acid reactions during UVC sterilization procedures.

Infrared Reflection-Absorption Spectroscopy of α-Hydroxyacids at the Water-Air Interface.

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.

Water-Air Interfaces as Environments to Address the Water Paradox in Prebiotic Chemistry: A Physical Chemistry Perspective.

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.

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.

Lactic Acid Spectroscopy: Intra- and Intermolecular Interactions.

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.