Interfacial carbonyl groups of propylene carbonate facilitate the reversible binding of nitrogen dioxide.

The interaction of NO2 with organic interfaces is critical in the development of NO2 sensing and trapping technologies, and equally so to the atmospheric processing of marine and continental aerosol. Recent studies point to the importance of surface oxygen groups in these systems, however the role of specific functional groups on the microscopic level has yet to be fully established. In the present study, we aim to provide fundamental information on the interaction and potential binding of NO2 at atmospherically relevant organic interfaces that may also help inform innovation in NO2 sensing and trapping development. We then present an investigation into the structural changes induced by NO2 at the surface of propylene carbonate (PC), an environmentally relevant carbonate ester. Surface-sensitive vibrational spectra of the PC liquid surface are acquired before, during, and after exposure to NO2 using infrared reflection-absorption spectroscopy (IRRAS). Analysis of vibrational changes at the liquid surface reveal that NO2 preferentially interacts with the carbonyl of PC at the interface, forming a distribution of binding symmetries. At low ppm levels, NO2 saturates the PC surface within 10 minutes and the perturbations to the surface are constant over time during the flow of NO2. Upon removal of NO2 flow, and under atmospheric pressures, these interactions are reversible, and the liquid surface structure of PC recovers completely within 30 min.

New Insights into Cation- and Temperature-Driven Protein Adsorption to the Air-Water Interface through Infrared Reflection Studies of Bovine Serum Albumin.

The chemistry and structure of the air-ocean interface modulate biogeochemical processes between the ocean and atmosphere and therefore impact sea spray aerosol properties, cloud and ice nucleation, and climate. Protein macromolecules are enriched in the sea surface microlayer and have complex adsorption properties due to the unique molecular balance of hydrophobicity and hydrophilicity. Additionally, interfacial adsorption properties of proteins are of interest as important inputs for ocean climate modeling. Bovine serum albumin is used here as a model protein to investigate the dynamic surface behavior of proteins under several variable conditions including solution ionic strength, temperature, and the presence of a stearic acid (C17COOH) monolayer at the air-water interface. Key vibrational modes of bovine serum albumin are examined via infrared reflectance-absorbance spectroscopy, a specular reflection method that ratios out the solution phase and highlights the aqueous surface to determine, at a molecular level, the surface structural changes and factors affecting adsorption to the solution surface. Amide band reflection absorption intensities reveal the extent of protein adsorption under each set of conditions. Studies reveal the nuanced behavior of protein adsorption impacted by ocean-relevant sodium concentrations. Moreover, protein adsorption is most strongly affected by the synergistic effects of divalent cations and increased temperature.

Structural evolution of water-in-propylene carbonate mixtures revealed by polarized Raman spectroscopy and molecular dynamics.

The liquid structure of systems wherein water is limited in concentration or through geometry is of great interest in various fields such as biology, materials science, and electrochemistry. Here, we present a combined polarized Raman and molecular dynamics investigation of the structural changes that occur as water is added incrementally to propylene carbonate (PC), a polar, aprotic solvent that is important in lithium-ion batteries. Polarized Raman spectra of PC solutions were collected for water mole fractions 0.003 ≤ χwater ≤ 0.296, which encompasses the solubility range of water in PC. The novel approach taken herein provides additional hydrogen bond and solvation characterization of this system that has not been achievable in previous studies. Analysis of the polarized carbonyl Raman band in conjunction with simulations demonstrated that the bulk structure of the solvent remained unperturbed upon the addition of water. Experimental spectra in the O-H stretching region were decomposed through Gaussian fitting into sub-bands and comparison to studies of dilute HOD in D2O. With the aid of simulations, we identified these different bands as water arrangements having different degrees of hydrogen bonding. The observed water structure within PC indicates that water tends to self-aggregate, forming a hydrogen bond network that is distinctly different from the bulk and dependent on concentration. For example, at moderate concentrations, the most likely aggregate structures are chains of water molecules, each with two hydrogen bonds.

Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air-water interface.

We exploit gas-phase cluster ion techniques to provide insight into the local interactions underlying divalent metal ion-driven changes in the spectra of carboxylic acids at the air-water interface. This information clarifies the experimental findings that the CO stretching bands of long-chain acids appear at very similar energies when the head group is deprotonated by high subphase pH or exposed to relatively high concentrations of Ca2+ metal ions. To this end, we report the evolution of the vibrational spectra of size-selected [Ca2+·RCO2-]+·(H2O) n=0to12 and RCO2-·(H2O) n=0to14 cluster ions toward the features observed at the air-water interface. Surprisingly, not only does stepwise hydration of the RCO2- anion and the [Ca2+·RCO2-]+ contact ion pair yield solvatochromic responses in opposite directions, but in both cases, the responses of the 2 (symmetric and asymmetric stretching) CO bands to hydration are opposite to each other. The result is that both CO bands evolve toward their interfacial asymptotes from opposite directions. Simulations of the [Ca2+·RCO2-]+·(H2O) n clusters indicate that the metal ion remains directly bound to the head group in a contact ion pair motif as the asymmetric CO stretch converges at the interfacial value by n = 12. This establishes that direct metal complexation or deprotonation can account for the interfacial behavior. We discuss these effects in the context of a model that invokes the water network-dependent local electric field along the C-C bond that connects the head group to the hydrocarbon tail as the key microscopic parameter that is correlated with the observed trends.

Functional Group Identification for FTIR Spectra Using Image-Based Machine Learning Models.

Fourier transform infrared spectroscopy (FTIR) is a ubiquitous spectroscopic technique. Spectral interpretation is a time-consuming process, but it yields important information about functional groups present in compounds and in complex substances. We develop a generalizable model via a machine learning (ML) algorithm using convolutional neural networks (CNNs) to identify the presence of functional groups in gas-phase FTIR spectra. The ML models reduce the amount of time required to analyze functional groups and facilitate interpretation of FTIR spectra. Through web scraping, we acquire intensity-frequency data from 8728 gas-phase organic molecules within the NIST spectral database and transform the data into spectral images. We successfully train models for 15 of the most common organic functional groups, which we then determine via identification from previously untrained spectra. These models serve to expand the application of FTIR measurements for facile analysis of organic samples. Our approach was done such that we have broad functional group models that infer in tandem to provide full interpretation of a spectrum. We present the first implementation of ML using image-based CNNs for predicting functional groups from a spectroscopic method.

Insight into the Ionizing Surface Potential Method and Aqueous Sodium Halide Surfaces.

Complementing the microscopic picture of the surface structure of electrolyte solutions set out by previous theoretical and experimental studies, the ionizing surface potential technique offers a unique approach to quantifying the impact of aqueous inorganic ions upon the interfacial electric field of the air-aqueous interface. In this Feature Article, we review the vulnerability of theoretical and empirically derived χwater values as a normative reference for aqueous ion surface potentials. Instead, we recognize and evaluate aqueous ion surface potentials relative to well-known ionic surfactants cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). Additionally, we also explore factors that impact the magnitude of the measured surface potentials using the ionizing method, particularly in the type of reference electrode and ionizing gas environment. With potential measurements of sodium halide solutions, we show that iodide has a dominant effect on the air-aqueous electric field. Compared to chloride and bromide, iodide is directly observed with a net negatively charged surface electric field at all salt concentrations measured (0.2 to 3.0 mol/kg water). Also, above the 2 M region, bromide is observed with a net negatively charged surface. Although several scenarios contribute to this effect, it is most likely due to the surface enrichment of bromide and iodide. While the results of this study are pertinent to determining the specific interfacial reactivity of aqueous halides, these anions seldom transpire as single-halide systems in the natural environment. Therefore, we also provide an outlook on future research concerning surface potential methods and more complex aqueous electrolyte systems.

Calcium bridging drives polysaccharide co-adsorption to a proxy sea surface microlayer.

Saccharides comprise a significant mass fraction of organic carbon in sea spray aerosol (SSA), but the mechanisms through which saccharides are transferred from seawater to the ocean surface and eventually into SSA are unclear. It is hypothesized that saccharides cooperatively adsorb to other insoluble organic matter at the air/sea interface, known as the sea surface microlayer (SSML). Using a combination of surface-sensitive infrared reflection-absorption spectroscopy and all-atom molecular dynamics simulations, we demonstrate that the marine-relevant, anionic polysaccharide alginate co-adsorbs to an insoluble palmitic acid monolayer via divalent cationic bridging interactions. Ca2+ induces the greatest extent of alginate co-adsorption to the monolayer, evidenced by the ∼30% increase in surface coverage, whereas Mg2+ only facilitates one-third the extent of co-adsorption at seawater-relevant cation concentrations due to its strong hydration propensity. Na+ cations alone do not facilitate alginate co-adsorption, and palmitic acid protonation hinders the formation of divalent cationic bridges between the palmitate and alginate carboxylate moieties. Alginate co-adsorption is largely confined to the interfacial region beneath the monolayer headgroups, so surface pressure, and thus monolayer surface coverage, only changes the amount of alginate co-adsorption by less than 5%. Our results provide physical and molecular characterization of a potentially significant polysaccharide enrichment mechanism within the SSML.

Hydration and Hydrogen Bond Order of Octadecanoic Acid and Octadecanol Films on Water at 21 and 1 °C.

The temperature-dependent hydration structure of long-chain fatty acids and alcohols at air-water interfaces has great significance in the fundamental interactions underlying ice nucleation in the atmosphere. We present an integrated theoretical and experimental study of the temperature-dependent vibrational structure and electric field character of the immediate hydration shells of fatty alcohol and acid headgroups. We use a combination of surface-sensitive infrared reflection-absorption spectroscopy (IRRAS), surface potentiometry, and ab initio molecular dynamics simulations to elucidate detailed molecular structures of the octadecanoic acid and octadecanol (stearic acid and stearyl alcohol) headgroup hydration shells at room temperature and near freezing. In experiments, the alcohol at high surface concentration exhibits the largest surface potential; yet we observe a strengthening of the hydrogen-bonding for the solvating water molecules near freezing for both the alcohol and the fatty acid IRRAS experiments. Results reveal that the hydration shells for both compounds screen their polar headgroup dipole moments reducing the surface potential at low surface coverages; at higher surface coverage, the polar headgroups become dehydrated, which reduces the screening, correlating to higher observed surface potential values. Lowering the temperature promotes tighter chain packing and an increase in surface potential. IRRAS reveals that the intra- and intermolecular vibrational coupling mechanisms are highly sensitive to changes in temperature. We find that intramolecular coupling dominates the vibrational relaxation pathways for interfacial water determined by comparing the H2O and the HOD spectra. Using ab initio molecular dynamics (AIMD) calculations on cluster systems of propanol + 6H2O and propionic acid + 10H2O, a spectral decomposition scheme was used to correlate the OH stretching motion with the IRRAS spectral features, revealing the effects of intra- and intermolecular coupling on the spectra. Spectra calculated with AIMD reproduce the red shift and increase in intensity observed in experimental spectra corresponding to the OH stretching region of the first solvation shell. These findings suggest that intra- and intermolecular vibrational couplings strongly impact the OH stretching region at fatty acid and fatty alcohol water interfaces. Overall, results are consistent with ice templating behavior for both the fatty acid and the alcohol, yet the surface potential signature is strongest for the fatty alcohol. These findings develop a better understanding of the complex surface potential and spectral signatures involved in ice templating.

Structural Effects of Cation Binding to DPPC Monolayers.

Ions at the two sides of the plasma membrane maintain the transmembrane potential, participate in signaling, and affect the properties of the membrane itself. The extracellular leaflet is particularly enriched in phosphatidylcholine lipids and under the influence of Na+, Ca2+, and Cl- ions. In this work, we combined molecular dynamics simulations performed using state-of-the-art models with vibrational sum frequency generation (VSFG) spectroscopy to study the effects of these key ions on the structure of dipalmitoylphosphatidylcholine. We used lipid monolayers as a proxy for membranes, as this approach enabled a direct comparison between simulation and experiment. We find that the effects of Na+ are minor. Ca2+, on the other hand, strongly affects the lipid headgroup conformations and induces a tighter packing of lipids, thus promoting the liquid condensed phase. It does so by binding to both the phosphate and carbonyl oxygens via direct and water-mediated binding modes, the ratios of which depend on the monolayer packing. Clustering analysis performed on simulation data revealed that changes in area per lipid or CaCl2 concentration both affect the headgroup conformations, yet their effects are anticorrelated. Cations at the monolayer surface also attract Cl-, which at large CaCl2 concentrations penetrates deep to the monolayer. This phenomenon coincides with a radical change in the VSFG spectra of the phosphate group, thus indicating the emergence of a new binding mode.

One-Pot Aldol Cascade for the Preparation of Isospiropyrans, Flavylium Salts, and bis-Spiropyrans.

We probed tandem aldol condensations of sixteen o-hydroxyacetophenones, carrying electron-withdrawing and -donating groups at positions 4 and 5, using five molar equivalents of SiCl4 in anhydrous ethanol. Substrates carrying electron-withdrawing groups (EWGs) (0 < ∑σ > 0.63) populated the equilibria with isospiropyrans (12-74% yield), while those carrying electron-donating groups (EDGs) (∑σ < -0.31) gave flavylium salts (50-80%) or thermochromic bis-spiropyrans (73%). The results are of interest for developing novel organic materials possessing switchable photochromic and thermochromic characteristics.

Molecular Recognition and Hydration Energy Mismatch Combine To Inform Ion Binding Selectivity at Aqueous Interfaces.

There is a critical need for receptors that are designed to enhance anion binding selectivity at aqueous interfaces in light of the growing importance of separation technologies for environmental sustainability. Here, we conducted the first study of anion binding selectivity across a series of prevalent inorganic oxoanions and halides that bind to a positively charged guanidinium receptor anchored to an aqueous interface. Vibrational sum frequency generation spectroscopy and infrared reflection absorption spectroscopy studies at the water-air interface reveal that the guanidinium receptor binds to an oxoanion series in the order SO42- > H2PO4- > NO3- > NO2- while harboring very weak interactions with the halides in the order I- > Cl- ≈ Br-. In spite of large dehydration penalties for sulfate and phosphate, the more weakly hydrated guanidinium receptor was selective for these oxoanions in contradiction to predictions made from ion partitioning alone, like the Hofmeister series and Collins's rules. Instead, sulfate binding is likely favored by the suppression of dielectric screening at the interface that consequently boosts Coulombic attractions, and thus helps offset the costs of anion dehydration. Geometric factors also favor the oxoanions. Furthermore, the unique placement of iodide in our halide series ahead of the stronger hydrogen-bond acceptors (Cl-, Br-) suggests that the binding interaction also depends upon single-ion surface partitioning from bulk water to the interface. Knowledge of the anion binding preferences displayed by a guanidinium receptor sheds light on the receptor architectures needed within designer interfaces to control selectivity.

Thermodynamic Signatures of the Origin of Anti-Hofmeister Selectivity for Phosphate at Aqueous Interfaces.

The selectivities and driving forces governing phosphate recognition by charged receptors at prevalent aqueous interfaces is unexplored relative to the many studies in homogeneous solutions. Here we report on electrostatic binding versus hydrogen-bond-assisted electrostatic binding of phosphate (H2PO4-) for two important receptor classes in the unique microenvironment of the air-water interface. We find that the methylated ammonium receptor (U-Ammo+) is dominated by electrostatic binding to phosphate anions and fails to be selective for phosphate binding over chloride, whereas the highly phosphate-selective guanidinium receptor (U-Guan+) provides synergistic hydrogen-bonding and electrostatic interactions. Apparent binding constants were evaluated in situ for U-Ammo+ and U-Guan+ using temperature-controlled infrared reflection-absorption spectroscopy with Langmuir-type fitting. Thermodynamic quantities showed enthalpically driven binding affinities of U-Guan+ and U-Ammo+ receptors (ΔH°b = -71 (±9) kJ/mol and ΔH°b = -155 (±13) kJ/mol, respectively). U-Guan+ revealed a nearly fourfold smaller entropic barrier to binding (ΔS°b = -132 (±34) J/mol K) than the U-Ammo+ receptor (ΔS°b = -440 (±45) J/mol K), attributed to hydration differences. The larger entropic penalty for the U-Ammo+ receptor is correlated with a molecular expansion shown in surface pressure-area isotherms, whereas the smaller entropic penalty of the U-Guan+ receptor conversely correlated with no expansion. The U-Guan+ receptor also revealed anti-Hofmeister selectivity for phosphate over chloride, while the non-hydrogen-bonding U-Ammo+ receptor followed Hofmeister selectivity. Our results indicate that hydrogen bonding is an integral chemical design element for achieving anti-Hofmeister selectivity for phosphate.

Relating Structure and Ice Nucleation of Mixed Surfactant Systems Relevant to Sea Spray Aerosol.

Ice nucleating particles (INPs) influence weather and climate by their effect on cloud phase state. Fatty alcohols present within aerosol particles confer a potentially important source of ice nucleation activity to sea spray aerosol produced in oceanic regions. However, their interactions with other aerosol components and the influence on freezing were previously largely unknown. Here, we report quantitative measurements of fatty alcohols in model sea spray aerosol and examine the relationships between the composition and structure of the surfactants and subphase in the context of these measurements. Deposited mixtures of surfactants retain the ability to nucleate ice, even in fatty acid-dominant compositions. Strong refreezing effects are also observed, where previously frozen water-surfactant samples nucleate more efficiently. Structural sources of refreezing behavior are identified as either kinetically trapped film states or three-dimensional (3D) solid surfactant particles. Salt effects are especially important for surfactant INPs, where high salt concentrations suppress freezing. A simple water uptake model suggests that surfactant-containing aerosol requires either very low salt content or kinetic trapping as solid particles to act as INPs in the atmosphere. These types of INPs could be identified through comparison of different INP instrument responses.

Iron(III) Speciation Observed at Aqueous and Glycerol Surfaces: Vibrational Sum Frequency and X-ray.

Aqueous solutions of FeCl3 have been widely studied to shed light on a number of processes from dissolution, mineralization, biology, electrocatalysis, corrosion, to microbial biomineralization. Yet there are little to no molecular level studies of the air-liquid FeCl3 interface. Here, both aqueous and glycerol FeCl3 solution surfaces are investigated with polarized vibrational sum frequency generation (SFG) spectroscopy. We also present the first ever extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy measurements of solvated ions and complexes at a solution interface, and observe with both X-ray photoelectron spectroscopy (XPS) and XUV-RA the existence of Fe(III) at the surface and in the near surface regions of glycerol FeCl3 solutions, where glycerol is used as a high vacuum compatible proxy for water. XPS showed Cl- and Fe(III) species with significant Fe(III) interfacial enrichment. In aqueous solutions, an electrical double layer (EDL) of Cl- and Fe(III) species at 0.5 m FeCl3 concentration is observed as evidenced from an enhancement of molecular ordering of water dipoles, consistent with the observed behavior at the glycerol surface. At higher concentrations in water, the EDL appears to be substantially repressed, indicative of further Fe(III) complex enrichment and dominance of a centrosymmetric Fe(III) species that is surface active. In addition, a significant vibrational red-shift of the dangling OH from the water molecules that straddle the air-water interface reveals that the second solvation shell of the surface active Fe(III) complex permeates the topmost layer of the aqueous interface.

Interfacial Supramolecular Structures of Amphiphilic Receptors Drive Aqueous Phosphate Recognition.

Phosphate remediation is important for preventing eutrophication in fresh waters and maintaining water quality. One approach for phosphate removal involves the utilization of molecular receptors. However, our understanding of anion recognition in aqueous solution and at aqueous interfaces is underdeveloped, and the rational design of surface-immobilized receptors is still largely unexplored. Herein, we evaluated the driving forces controlling phosphate binding to elementary amphiphilic receptors anchored at air-water interfaces. We designed biologically inspired receptors with neutral thiourea, positively charged guanidinium, and thiouronium units that all formed Langmuir monolayers. Phosphate binding was quantitatively examined using surface pressure-area isotherms and infrared reflection-absorption spectroscopy (IRRAS). The receptors within this homologous series differ in functional group, charge, and number of alkyl chains to help distinguish the fundamental components influencing anion recognition at aqueous interfaces. The two charged receptors bearing two alkyl chains each displayed strong phosphate affinities and 103- and 101-fold anti-Hofmeister selectivity over chloride, respectively. Neutral thiourea and the single-chain guanidinium receptor did not bind phosphate, revealing the importance of electrostatic interactions and supramolecular organization. Consistently, charge screening at high ionic strength weakens binding. Spectroscopic results confirmed phosphate binding to the double alkyl chain guanidinium receptor, whereas surface pressure isotherm results alone showed a minimal change, thus emphasizing the importance of interfacial spectroscopy. We found that the binding site identity, charged interface created by the electrical double layer, and supramolecular superstructure all affect interfacial binding. These detailed insights into phosphate recognition at aqueous interfaces provide a foundation to develop efficient receptors for phosphate capture.

An easily accessible isospiropyran switch.

In the presence of SiCl4, three molecules of 5'-bromo-2'-hydroxyacetophenone underwent an unexpected tandem aldol condensation to give a novel isospiropyran switch (69%), with X-ray crystallography confirming its structure. The strong Brønsted acid CH3SO3H turned the colorless isospiropyran into its protonated and open form possessing red color. This process was reversed using the Et3N base, with the acid/base toggling repeatable for at least six times (UV-Vis). When printed on a silica plate, however, the isospiropyran formed a blue-colored product due to, as posited, its stabilization by hydrogen bonding (HB) to silica. An exposure to HB-competing ethyl acetate temporarily "erased" the print only to be brought back by subjecting the plate to a higher temperature for evaporating the solvent. The isospiropyran described here is an easily accessible, chromic, modular and switchable compound that one can incorporate into dynamic materials or use for building chemosensors, molecular machines and organic electronic devices.

Hydration of ferric chloride and nitrate in aqueous solutions: water-mediated ion pairing revealed by Raman spectroscopy.

Iron is the most abundant transition metal in the earth's crust and is important for the proper functioning of many technological and natural processes. Despite the importance, a complete microscopic understanding of the hydration of ferric ions and water mediated ion pairing has not been realized. Hydrated Fe(iii) is difficult to study due to the process of complexation to the anion and hydrolysis of the hydrating water molecules leading to a heterogeneous solution with diverse speciation. Here, ferric chloride and nitrate aqueous solutions are studied using polarized Raman spectroscopy as a function of concentration and referenced to their respective sodium salt or mineral acid. Perturbed water spectra (PWS) were generated using multivariate curve resolution-alternating least squares (MCR-ALS) to show the residual spectral response uniquely attributable to the hydration of ferric speciation. The hydrogen bonding network associated with the hydrating water molecules in ferric chloride solutions are found to be more similar to hydrochloric acid solutions, whereas in ferric nitrate solutions, the network behaves more similar to sodium nitrate, despite increased acidity. Thus, in the FeNO3 and FeCl3 solutions, ion pairing and coordination, respectively, are significantly influencing the hydration spectra signature. These results further reveal concentration dependent changes to the hydrogen bonding network, hydrating water symmetry, and changes to the relative abundance of solvent shared ion pairs that are governed primarily by the ferric salt identity.

Effect of pH and Salt on Surface pKa of Phosphatidic Acid Monolayers.

The pH-induced surface speciation of organic surfactants such as fatty acids and phospholipids in monolayers and coatings is considered to be an important factor controlling their interfacial organization and properties. Yet, correctly predicting the surface speciation requires the determination of the surface dissociation constants (surface pKa) of the protic functional group(s) present. Here, we use three independent methods-compression isotherms, surface tension pH titration, and infrared reflection-absorption spectroscopy (IRRAS)-to study the protonation state of dipalmitoylphosphatidic acid (DPPA) monolayers on water and NaCl solutions. By examining the molecular area expansion at basic pH, the pKa to remove the second proton of DPPA (surface pKa2) at the aqueous interface is estimated. In addition, utilizing IRRAS combined with density functional theory calculations, the vibrational modes of the phosphate headgroup were directly probed and assigned to understand DPPA charge speciation with increasing pH. We find that all three experimental techniques give consistent surface pKa2 values in good agreement with each other. Results show that a condensed DPPA monolayer has a surface pKa2 of 11.5, a value higher than previously reported (∼7.9-8.5). This surface pKa2 was further altered by the presence of Na+ cations in the aqueous subphase, which reduced the surface pKa2 from 11.5 to 10.5. It was also found that the surface pKa2 value of DPPA is modulated by the packing density (i.e., the surface charge density) of the monolayer, with a surface pKa2 as low as 9.2 for DPPA monolayers in the two-dimensional gaseous phase over NaCl solutions. The experimentally determined surface pKa2 values are also found to be in agreement with those predicted by Gouy-Chapman theory, validating these methods and proving that surface charge density is the driving factor behind changes to the surface pKa2.

Presence and persistence of a highly ordered lipid phase state in the avian stratum corneum.

To survive high temperatures in a terrestrial environment, animals must effectively balance evaporative heat loss and water conservation. In passerine birds, cutaneous water loss (CWL) is the primary avenue of water loss at thermoneutral temperatures and increases slightly as ambient temperature increases, indicating a change in the permeability of the skin. In the stratum corneum (SC), the outermost layer of the skin, lipids arranged in layers called lamellae serve as the primary barrier to CWL in birds. The permeability of these lamellae depends in large part on the ability of lipid molecules to pack closely together in an ordered orthorhombic phase state. However, as temperature increases, lipids of the SC become more disordered, and may pack in more permeable hexagonal or liquid crystalline phase states. In this study, we used Fourier transform infrared spectroscopy to monitor the phase state of lipids in the SC of house sparrows (Passer domesticus) at skin temperatures ranging from 25 to 50°C. As temperature increased, lipids became slightly more disordered, but remained predominantly in the orthorhombic phase, consistent with the small increase in CWL observed in house sparrows as ambient temperature increases. These results differ considerably from studies on mammalian SC, which find a predominantly hexagonal arrangement of lipids at temperatures above 37°C, and the increased order in avian SC may be explained by longer lipid chain length, scarcity of cholesterol and the presence of cerebrosides. Our results lend further insight into the arrangement and packing of individual lipid molecules in avian SC.

Thermodynamic versus non-equilibrium stability of palmitic acid monolayers in calcium-enriched sea spray aerosol proxy systems.

Of the major cations in seawater (Na+, Mg2+, Ca2+, K+), Ca2+ is found to be the most enriched in fine sea spray aerosols (SSA). In this work, we investigate the binding of Ca2+ to the carboxylic acid headgroup of palmitic acid (PA), a marine-abundant fatty acid, and the impact such binding has on the stability of PA monolayers in both equilibrium and non-equilibrium systems. A range of Ca2+ conditions from 10 µM to 300 mM was utilized to represent the relative concentration of Ca2+ in high and low relative humidity aerosol environments. The CO2- stretching modes of PA detected by surface-sensitive infrared reflection-absorption spectroscopy (IRRAS) reveal ionic binding motifs of the Ca2+ ion to the carboxylate group with varying degrees of hydration. Surface tensiometry was used to determine the thermodynamic equilibrium spreading pressure (ESP) of PA on the various aqueous CaCl2 subphases. Up to concentrations of 1 mM Ca2+, each system reached equilibrium, and Ca2+:PA surface complexation gave rise to a lower energy state revealed by elevated surface pressures relative to water. We show that PA films are not thermodynamically stable at marine aerosol-relevant Ca2+ concentrations ([Ca2+] ≥ 10 mM). IRRAS and vibrational sum frequency generation (VSFG) spectroscopy were used to investigate the surface presence of PA on high concentration Ca2+ aqueous subphases. Non-equilibrium relaxation (NER) experiments were also conducted and monitored by Brewster angle microscopy (BAM) to determine the effect of the Ca2+ ions on PA stability. At high surface pressures, the relaxation mechanisms of PA varied among the systems and were dependent on Ca2+ concentration.