Palmitic Acid Monolayers Research Articles

Investigating Bénard-Marangoni migration at the air-water interface in the time domain using sum frequency generation (SFG) spectroscopy of palmitic acid monolayers.

Sum-frequency generation (SFG) spectroscopy is frequently used to investigate the structure of monolayer films of long-chain fatty acids at the air-water interface. Although labeled a non-invasive technique, introducing intense SFG lasers onto liquid interfaces has the potential to perturb them. In the present work, narrowband picosecond SFG is used to study the structural changes that occur in palmitic acid and per-deuterated palmitic acid monolayers at the air-water interface in response to the high field strengths inherent to SFG spectroscopy. In order to determine structural changes and identify measurement artifacts, the changes in specific resonance intensities were measured in real-time and over a broad range of surface concentrations from films spread onto a stationary Langmuir trough. Using narrowband instead of broadband SFG minimizes the overlap of the incident infrared beam in the lipid C-H stretching region with resonances from the water sub-phase. Nevertheless, narrowband SFG still generates a thermal gradient at the surface, which produces a significant decrease in local concentration in the area of the laser spot caused by Bérnard-Marangoni convection originating in the sub-phase. The decrease in concentration results in an increase in the conformational disorder and a decrease in the tilt angle of lipid tails. Crucially, it is shown that, even at the highest monolayer concentrations, this gives rise to a measurement effect, which manifests itself as a dependence on the spectral acquisition time. This effect should be taken into account when interpreting the structure of monolayer films on liquid surfaces deduced from their SFG spectra.

Spontaneous evolution of equilibrium morphology in phospholipid-cholesterol monolayers.

Competition between intradomain electrostatic repulsions and interdomain line tension leads to domain shape transitions in phase-separating lipid monolayers. The question remains if these morphologies are energy minima or are kinetically trapped metastable states. We show the reversible evolution of uniform width stripe domains from polydisperse semicircular domains in monolayers of dipalmitoylphosphatidylcholine (DPPC), hexadecanol (HD) or palmitic acid (PA), and dihydrocholesterol (DChol). The initial semicircular domains grow at a fixed 2:1 DPPC:HD (or PA) stoichiometry, depleting the liquid phase of HD, leaving behind a liquid enriched in DPPC and DChol. At higher surface pressures, the remaining DPPC precipitates onto existing domains, decreasing the ratio of line tension to the square of the dipole density difference, λ/μ2. Theory predicts that, as λ/μ2 decreases, circular domains reversibly transform to uniform width stripes as the minimum energy structure. Measuring the stripe width provides the first estimates of λ/μ2 at liquid condensed–liquid expanded phase coexistence.

Maze Pattern at Nanometer-Scale in a Mixed Langmuir Monolayer of Fatty Acids

Abstract We investigated the morphology of binary monolayers of palmitic acid and behenic acid using atomic force microscopic observations. The monolayers exhibited a phase-separated morphology composed of meandering domains with a width of nanometer order, which is probably due to fixation of the monolayer morphology at a stage on the way to phase separation.

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.

Energetics and structure of Langmuir monolayers of palmitic acid: a DFT study.

Langmuir monolayers are monomolecular wide films composed of amphiphilic molecules with a bi-dimensional structure typically formed at the air-water interface. They have been studied for many years because these monolayers have important applications in many research fields. Their phase diagrams present several condensed phases whose atomic structure is not yet completely known. We present a novel density functional study on palmitic acid dimers and monolayers. Our results reveal that dihydrogen contacts established among alkyl chains play a leading role in the final structure, regarding both dimers and for the arrangement of molecules in the monolayer. In addition, our calculations show that tilted phases at approx. 30° can be formed without significant loss of structure stability, a result that is in agreement with the experimental findings. Different structures for the high pressure phases, S and CS, are proposed here for the first time, being in good agreement with the diffraction data available. Furthermore, linear compressibility values also in accordance with previous experimental studies are presented for several structures.

Thermodynamicversusnon-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.

Let there be light: stability of palmitic acid monolayers at the air/salt water interface in the presence and absence of simulated solar light and a photosensitizer.

Long-chain fatty acid monolayers are known surfactants present at air/water interfaces. However, little is known about the stability of these long-chain fatty acid monolayers in the presence of solar radiation. Here we have investigated, for the first time, the stability of palmitic acid monolayers on salt water interfaces in the presence and absence of simulated solar light with and without a photosensitizer in the underlying salt subphase. Using surface sensitive probes to measure changes in the properties of these monolayers upon irradiation, we found that the monolayers become less stable in the presence of light and a photosensitizer, in this case humic acid, in the salt solution. The presence of the photosensitizer is essential in significantly reducing the stability of the monolayer upon irradiation. The mechanism for this loss of stability is due to interfacial photochemistry involving electronically excited humic acid and molecular oxygen reacting with palmitic acid at the interface to form more oxygenated and less surface-active species. These oxygenated species can then more readily partition into the underlying solution.

Sodium-carboxylate contact ion pair formation induces stabilization of palmitic acid monolayers at high pH.

Sea spray aerosols (SSA) are known to have an organic coating that is mainly composed of fatty acids. In this study, the effect of pH and salt on the stability and organization of a palmitic acid (PA) monolayer is investigated by surface vibrational spectroscopy and molecular dynamics simulations. Results indicate that alkyl chain packing becomes more disordered as the carboxylic headgroup becomes deprotonated. This is associated with packing mismatch of charged and neutral species as charged headgroups penetrate deeper into the solution phase. At pH 10.7, when the monolayer is ∼99% deprotonated, palmitate (PA-) molecules desorb and solubilize into the bulk solution where there is spectroscopic evidence for aggregate formation. Yet, addition of 100 mM NaCl to the bulk solution is found to drive PA- molecules to the aqueous surface. Free energy calculations show that PA- molecules become stabilized within the interface with increasing NaCl concentration. Formation of contact -COO-:Na+ pairs alters the hydration state of PA- headgroups, thus increasing the surface propensity. As salts are highly concentrated in SSA, these results suggest that deprotonated fatty acids may be found at the air-aqueous interface of aerosol particles due to sea salt's role in surface stabilization.

Effects of surface pressure on the properties of Langmuir monolayers and interfacial water at the air-water interface.

The effects of surface pressure on the physical properties of Langmuir monolayers of palmitic acid (PA) and dipalmitoylphosphatidic acid (DPPA) at the air/water interface are investigated through molecular dynamics simulations with atomistic force fields. The structure and dynamics of both monolayers and interfacial water are compared across the range of surface pressures at which stable monolayers can form. For PA monolayers at T = 300 K, the untilted condensed phase with a hexagonal lattice structure is found at high surface pressure, while the uniformly tilted condensed phase with a centered rectangular lattice structure is observed at low surface pressure, in agreement with the available experimental data. A state with uniform chain tilt but no periodic spatial ordering is observed for DPPA monolayers on a Na(+)/water subphase at both high and low surface pressures. The hydrophobic acyl chains of both monolayers pack efficiently at all surface pressures, resulting in a very small number of gauche defects. The analysis of the hydrogen-bonding structure/dynamics at the monolayer/water interface indicates that water molecules hydrogen-bonded to the DPPA head groups reorient more slowly than those hydrogen-bonded to the PA head groups, with the orientational dynamics becoming significantly slower at high surface pressure. Possible implications for physicochemical processes taking place on marine aerosols in the atmosphere are discussed.

Palmitic Acid on Salt Subphases and in Mixed Monolayers of Cerebrosides: Application to Atmospheric Aerosol Chemistry

Palmitic acid (PA) has been found to be a major constituent in marine aerosols, and is commonly used to investigate organic containing atmospheric aerosols, and is therefore used here as a proxy system. Surface pressure-area isotherms (π-A), Brewster angle microscopy (BAM), and vibrational sum frequency generation (VSFG) were used to observe a PA monolayer during film compression on subphases of ultrapure water, CaCl2 and MgCl2 aqueous solutions, and artificial seawater (ASW). π-A isotherms indicate that salt subphases alter the phase behavior of PA, and BAM further reveals that a condensation of the monolayer occurs when compared to pure water. VSFG spectra and BAM images show that Mg2+ and Ca2+ induce ordering of the PA acyl chains, and it was determined that the interaction of Mg2+ with the monolayer is weaker than Ca2+. π-A isotherms and BAM were also used to monitor mixed monolayers of PA and cerebroside, a simple glycolipid. Results reveal that PA also has a condensing effect on the cerebroside monolayer. Thermodynamic analysis indicates that attractive interactions between the two components exist; this may be due to hydrogen bonding of the galactose and carbonyl headgroups. BAM images of the collapse structures show that mixed monolayers of PA and cerebroside are miscible at all surface pressures. These results suggest that the surface morphology of organic-coated aerosols is influenced by the chemical composition of the aqueous core and the organic film itself.

Influence of Salt Purity on Na+ and Palmitic Acid Interactions

The influence of salt purity on the interactions between Na(+) ions and the carboxylate (COO(-)) head group of palmitic acid (PA) monolayers is studied in the COO(-) and OH stretching regions using broad-band vibrational sum frequency generation (VSFG) spectroscopy. Ultrapure (UP) and ACS grade NaCl salts are used for aqueous solution preparation after proper pretreatment. The time evolution of VSFG spectra of PA monolayers on solutions made from these two grades of salts is different, which reveals that the salt purity has a significant impact on the interactions between Na(+) ions and the COO(-) group of PA. The trace metal impurities in ACS grade salt, which are more abundant than those in UP grade salt, are responsible for this difference due to their stronger affinity for the carboxylate group relative to Na(+) and further affects the interfacial water structure. These results suggest that the alkali salt grade even after pretreatment is critical in the studies of alkali cation-carboxylate interactions and comparison of relative binding affinities of different cations.

Mixed monolayers of DOPC and palmitic acid at the liquid–air interface

The interactions between 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and palmitic acid (PA) in mixed monolayers were investigated through surface pressure measurements, fluorescence microscopy (FM) and atomic force microscopy (AFM). The miscibility of two components and the interactions between DOPC and PA in the mixed monolayers were accessed by analyzing surface pressure (π)–area (A) isotherms. It was found that there were both positive deviations for excess molecular area and excess Gibbs energy, which suggests the interaction is repulsive in all case and the strongest repulsive occurs at XPA=0.5 ratio. The FM and AFM images showed that there were discernible phase separations at selected surface pressures. The increase of surface pressure and the phenomenon that the PA-enriched domains have been connected to form much larger platforms are in agreement with the thermodynamic results.

Properties and structure of interfacial layers formed by hydrophilic silica dispersions and palmitic acid

The properties and structure of different types of interfacial layers obtained from aqueous dispersions of nanometric silica and palmitic acid (PA) have been studied and characterized by different diagnostics and measurements. The investigations concern PA monolayers spread on the silica dispersions, dispersions in contact with PA solutions in oil and silica dispersions containing PA, aiming at elucidating the role of the PA interaction with the particles and investigating the surface-activity of the originated silica-PA complexes. Drop shape tensiometry was utilized to measure the dynamic surface and interfacial tension while a Langmuir trough apparatus was used to obtain compression isotherms of the spread PA layers and to measure the dilational viscoelasticity according to the oscillating barrier method. Brewster angle microscopy and ellipsometry were utilized to investigate the lateral and vertical structure of the interfacial layers. From this multifold approach emerges a complex picture of the features of these interfacial layers that can be rationalized on the basis of the adsorption of PA on the particle surface. The results evidence a threshold in PA adsorption above which particles change from hydrophilic to partially hydrophobic, promoting their incorporation into the interfacial layer.

Interfacial Water Structure and Effects of Mg2+and Ca2+Binding to the COOH Headgroup of a Palmitic Acid Monolayer Studied by Sum Frequency Spectroscopy

The interfacial hydrogen-bonding network that uniquely exists in between a palmitic acid (PA) monolayer and the underneath surface water molecules was studied using vibrational sum frequency generation (VSFG) spectroscopy. Perturbations due to cation binding of Mg(2+) and Ca(2+) were identified. The polar ordering of the interfacial water molecules under the influence of the surface field of dissociated PA headgroups was observed. Only a fraction of PA molecules are deprotonated at the air/water interface with a neat water subphase, yet the submonolayer concentration of negatively charged PA headgroups induces considerable polar ordering on the interfacial water molecules relative to the neat water surface without the PA film. Upon addition of calcium and magnesium chloride salts to the subphase of the PA monolayer, the extent of polar ordering of the interfacial water molecules was reduced. Ca(2+) was observed to have the greater impact on the interfacial hydrogen-bonding network relative to Mg(2+), consistent with the greater binding affinity of Ca(2+) toward the carboxylate group relative to Mg(2+) and thereby modifying the interfacial charge. At high-salt concentrations, the already disrupted hydrogen-bonding network reorganizes and reverts to its original hydrogen-bonding structure as that which appeared at the neat salt solution surface without a PA monolayer.

Effect of Phospholipase A2 Hydrolysis Products on Calcium Oxalate Precipitation at Lipid Interfaces

Urinary stones are commonly composed of an inorganic component, calcium oxalate, or calcium phosphate and an organic matrix of lipids, carbohydrates, and proteinaceous matter. Of interest is the role that the organic matrix elements may play as catalysts for the heterogeneous nucleation of the calcium salts, and a number of studies have examined the role of lipids in calcium oxalate monohydrate (COM) formation. In this study, products of lipid hydrolysis from phospholipase A(2) (PLA(2)) are examined for their effect on COM formation using Langmuir monolayers as model lipid membrane assemblies. The enzyme PLA(2) hydrolyzes DPPC monolayers in the presence of a supersaturated calcium oxalate subphase, inducing the rapid and plentiful nucleation of calcium oxalate at the lipid interface. To investigate the cause of increased crystal formation in the presence of the enzyme, Langmuir monolayers modeling the hydrolysis products were investigated. Calcium oxalate crystal growth at a ternary monolayer of dipalmitoylphosphatidylcholine (DPPC), palmitic acid (PA), and a 22-carbon chain lysophospholipid (22:0 Lyso PC) dramatically increases relative to monolayers of just DPPC. Binary monolayers of DPPC with either PA or the 22:0 Lyso PC and single-component monolayers of PA were also studied. It is demonstrated that the fatty acid generated during lipid hydrolysis causes a significant increase in the extent of heterogeneous nucleation of calcium oxalate from supersaturated solutions. The results imply a possible link between increased phospholipase activity, which is associated with hyperoxaluria, and calcium oxalate precipitation.

Characterizing Internally Mixed Insoluble Organic Inclusions in Aqueous Aerosol Droplets and Their Influence on Light Absorption

A strategy is developed for characterizing the properties and microphysical structure of a mixed phase aerosol droplet consisting of an aqueous sodium chloride host and an insoluble organic inclusion using aerosol optical tweezers and Raman spectroscopy. In particular, palmitic acid (PA), solvated in ethanol and nebulized to produce a flow of aerosol, is coalesced with an optically trapped sodium chloride droplet. Once the ethanol solvent has evaporated, a hydrated crystalline organic phase is formed. Two distinct classes of mixed phase structure are observed. The observation of a PA aggregate formed immediately on coalescence at the surface of the host droplet is consistent with the hydrophobicity of the organic component; this is the dominant structure observed. However, PA inclusions are also observed within the droplet bulk following the evaporation of the ethanol solvent. This may be attributable to the interplay of the optical forces exerted on the inclusion and the lowering of the surface tension of the aqueous droplet by the presence of a monolayer of PA, or through direct incorporation of a PA inclusion by impaction. In this latter class of structure, an autocorrelation analysis of the Raman signatures suggests that the inclusion diffuses throughout the entire droplet volume. Finally, the coupling of nonresonant and resonant heating of the droplet, arising from motion of the PA inclusion within the droplet, is contrasted with observations of the lowering of equilibrium droplet size that accompanies the presence of a weakly absorbing inclusion, a polystyrene bead, within the droplet core.

Ionic Binding of Na+ versus K+ to the Carboxylic Acid Headgroup of Palmitic Acid Monolayers Studied by Vibrational Sum Frequency Generation Spectroscopy

Ionic binding of alkali ions Na(+) and K(+) to the carboxylic acid headgroups of fatty acid monolayers is studied as a proxy toward understanding the fundamental chemistry in cell biology. In this study, we used broad-bandwidth sum frequency generation (BBSFG) vibrational spectroscopy to investigate the ionic binding event that leads to deprotonation and complex formation of fatty acid headgroups. Palmitic acid (C(15)H(31)COOH) exists as a monolayer on aqueous surfaces. Surface vibrational stretch modes of palmitic acid from 1400 cm(-1) to 3700 cm(-1) were observed (nu(s)-COO(-), nu-C horizontal lineO, nu-C-H, nu-O-H of -COOH, free OH). Palmitic acid is mostly protonated at the aqueous surface at neutral pH (approximately 6). However, various degrees of deprotonation are initiated by the introduction of Na(+) and K(+) that results in the complexation of K(+):COO(-) and solvent separated Na(+):COO(-). Evidence in several spectral regions indicates that K(+) exhibits stronger ionic binding affinity to the carboxylate anion relative to Na(+).

Electrical Detection of Amine Ligation to a Metalloporphyrin via a Hybrid SOI-MOSFET

A close-packed monolayer of zinc 5,10,15,20-tetrakis(3-carboxyphenyl)porphyrin has been prepared and deposited on the thin native oxide covering the surface of an SOI-MOSFET (silicon-on-insulator metal-oxide-semiconductor field effect transistor) using Langmuir-Blodgett techniques. When the device is exposed to amine vapors in a nitrogen atmosphere, the amine coordinates to the zinc atom. The resulting change in electron distribution within the porphyrin leads to a large change in the drain current of the transistor, biased via a back gate. This change is sensitive to both the amount of amine present and the base strength of the amine. Only very small changes in drain current were observed with a monolayer of free base porphyrin or palmitic acid. After exposure to high pyridine concentrations, the device response saturates, but partially recovers after overnight exposure to flowing nitrogen gas. Interestingly, the device response is instantaneously reset by exposure to visible light, suggesting that photode-ligation occurs. An electrical model for the hybrid device that describes its response to ligand binding in terms of a change in the work function of the porphyrin monolayer has been developed. A transistor response to a few hundred attomoles of bound pyridine can be readily detected. This extreme sensitivity, coupled with the ability to reset the device using light, suggests that such systems might be useful as sensors.

Competition between Atmospherically Relevant Fatty Acid Monolayers at the Air/Water Interface

Competition and oxidation of fatty acids spread at the air/water interface were investigated using surface-specific, broad-bandwidth, sum frequency generation spectroscopy. At the air/water interface, a monolayer of oleic acid replaced a monolayer of deuterated palmitic acid at equilibrium spreading pressure. Subsequent oxidation of the oleic acid monolayer with ozone resulted in products more water soluble than the palmitic acid; therefore, the palmitic acid monolayer reformed at the surface. Results indicate that the surfactants on the surface of fat-coated tropospheric aerosols will only possess oxidized acyl chains after all less soluble species in the aqueous subphase have been removed through the processes of replacement at the surface and atmospheric oxidation.

Effects of albumin and erythrocyte membranes on spread monolayers of lung surfactant lipids

Dipalmitoyl phosphatidylcholine (DPPC), one of the main constituents of lung surfactant is mainly responsible for reduction of surface tension to near 0 mN/m during expiration, resisting alveolar collapse. Other unsaturated phospholipids like palmitoyloleoyl phosphatidylglycerol (PG), palmitoyloleoyl phosphatidylcholine (POPC) and neutral lipids help in adsorption of lung surfactant to the air–aqueous interface. Lung surfactant lipids may interact with plasma proteins and hematological agents flooding the alveoli in diseased states. In this study, we evaluated the effects of albumin and erythrocyte membranes on spread films of DPPC alone and mixtures of DPPC with each of PG, POPC, palmitoyloleoyl phosphatidylethanolamine (PE), cholesterol (CHOL) and palmitic acid (PA) in 9:1 molar ratios. Surface tension–area isotherms were recorded using a Langmuir–Blodgett (LB) trough at 37 °C with 0.9% saline as the sub-phase. In the presence of erythrocyte membranes, DPPC and DPPC + PA monolayers reached minimum surface tensions of 7.3 ± 0.9 and 9.6 ± 1.4 mN/m, respectively. Other lipid combinations reached significantly higher minimum surface tensions >18 mN/m in presence of membranes (Newman Keul's test, p < 0.05). The relative susceptibility to membrane inhibition was [(DPPC + PG, 7:3) = (DPPC + PG, 9:1) = (DPPC + POPC) = (DPPC + PE) = (DPPC + CHOL)] > [(DPPC + PA) = (DPPC)]. The differential response was more pronounced in case of albumin with DPPC and DPPC + PA monolayers reaching minimum surface tensions less than 2.4 mN/m in presence of albumin, whereas DPPC + PG and DPPC + POPC reached minimum surface tensions of around 20 mN/m in presence of albumin. Descending order of susceptibility of the spread monolayers of lipid mixtures to albumin destabilization was as follows: [(DPPC + PG, 7:3) = (DPPC + PG, 9:1) = (DPPC + POPC)] > [(DPPC + PE) = (DPPC + CHOL)] > [(DPPC + PA) = (DPPC)] The increase in minimum surface tension in presence of albumin and erythrocyte membranes was accompanied by sudden increases in compressibility at surface tensions of 15–30 mN/m. This suggests a monolayer destabilization and could be indicative of phase transitions in the mixed lipid films due to the presence of the hydrophobic constituents of erythrocyte membranes.