Headgroup Hydration Research Articles

Structure of DPPC Monolayers at the Air/Buffer Interface: A Neutron Reflectometry and Ellipsometry Study

Langmuir monolayers of 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine, known as DPPC, at the air/water interface are extensively used as model systems of biomembranes and pulmonary surfactant. The properties of these monolayers have been mainly investigated by surface pressure–area isotherms coupled with different complementary techniques such as Brewster angle microscopy, for example. Several attempts using neutron reflectometry (NR) or ellipsometry have also appeared in the literature. Here, we report structural information obtained by using NR and ellipsometry on DPPC monolayers in the liquid condensed phase. On one side, NR can resolve the thickness of the aliphatic tails and the degree of hydration of the polar headgroups. On the other side, ellipsometry gives information on the refractive index and, therefore, on the physical state of the monolayer. The thickness and surface excess obtained by multiple-angle-of-incidence ellipsometry (MAIE) is compared with the results from NR measurements yielding a good agreement. Besides, a novel approach is reported to calculate the optical anisotropy of the DPPC monolayer that depends on the orientation of the aliphatic chains. The results from both NR and ellipsometry are also discussed in the context of the existing results for DPPC monolayers at the air/water interface. The differences observed are rationalized by the presence of buffer molecules interacting with phospholipids.

Improvement of Foaming Ability of Surfactant Solutions by Water-Soluble Polymers: Experiment and Molecular Dynamics Simulation.

Aqueous foam is widely used in fire extinguishing and dust suppression technologies. Improving the foaming ability is the key to reducing the added concentration of foaming agents as well as the economic cost. In this work, the effect of a water-soluble polymer (polyvinyl alcohol, PVA) on the foaming ability of anionic surfactant (sodium dodecyl ether sulfate, SDES) was studied by an experiment and molecular dynamics simulation. The experimental results showed that PVA greatly improves the foaming ability of SDES solutions when the surfactant concentration is less than 0.1%, which is attributed to the fact that the polymer can enhance the stability of bubble films and reduce the bubble rupture rate during the foam generation process. The simulation results indicate that PVA can enhance the hydration of surfactant head groups and contribute to the formation of a three-dimensional hydrogen bond network between surfactants, polymers, and water molecules, thus greatly improving the stability of bubble liquid films. The above results suggest that water-soluble polymers can be used to improve the foaming ability of surfactant solutions by enhancing the bubble film stability, which is beneficial as it reduces the added concentration of foaming agents in aqueous foam applications.

Temperature and concentration effects on decyltrimethylammonium micelles in water

Wide-angle neutron scattering experiments combined with Empirical Potential Structural Refinement modelling have been used to study the detailed structure of decyltrimethylammonium bromide (C10TAB) micelles at two different temperatures; 25°C and 50°C and two concentrations; 0.4 and 0.8 M in water. At higher temperature, the micelles become smaller, and fewer counterions bind to the micelle surfaces, however, the headgroup positions are more ordered, possibly due to crowding in the smaller micelles. At higher concentration, the models suggest the micelles become elongated, although the aggregations numbers are smaller than those at the lower concentration. The smaller micelles found in 0.8 M solutions have more hydrated headgroups and lower counterion binding than the ellipsoidal micelles found in 0.4 M C10TAB solutions.

1-nm-Wide Hydrated Dipole Arrays Regulate AuNW Assembly on Striped Monolayers in Nonpolar Solvent

Summary We show that striped phases of horizontally oriented phospholipids presenting 1-nm-wide orientable dipole arrays can order and straighten flexible 2-nm-diameter gold nanowires (AuNWs) with lengths (up to 1 μm) that greatly exceed the template pitch (∼7.5 nm). AuNW ordering can extend over areas > 100 μm2. Whereas wires bundle in solution, with contact between ligand shells, wires adsorbing to the template separate to much larger center-to-center distances (e.g., 12–30 nm) near multiples of the template pitch, consistent with repulsive interactions between wires emerging during interactions with dipole arrays in the template. AuNW assembly was carried out in cyclohexane, a nonpolar solvent. Interestingly, we found that wire ordering was contingent on the extent of phospholipid headgroup hydration and the presence of excess oleylamine, which assembled into hemicylindrical micelles around the hydrated headgroups. Together, these components generated a protected polar environment that enabled the phospholipid headgroups to function collectively to regulate AuNW assembly.

A new model for lipid monolayer and bilayers based on thermodynamics of irreversible processes.

Lipid monolayers are used as experimental model systems to study the physical chemical properties of biomembranes. With this purpose, surface pressure/area per molecule isotherms provide a way to obtain information on packing and compressibility properties of the lipids. These isotherms have been interpreted considering the monolayer as a two dimensional ideal or van der Waals gas without contact with the water phase. These modelistic approaches do not fit the experimental results. Based on Thermodynamics of Irreversible Processes (TIP), the expansion/compression process is interpreted in terms of coupled phenomena between area changes and water fluxes between a bidimensional solution of hydrated head groups in the monolayer and the bulk solution. The formalism obtained can reproduce satisfactorily the surface pressure/area per lipid isotherms of monolayer in different states and also can explain the area expansion and compression produced in particles enclosed by bilayers during osmotic fluxes. This novel approach gives relevance to the lipid-water interaction in restricted media near the membrane and provides a formalism to understand the thermodynamic and kinetic response of biointerphases to biological effectors.

Molecular Dynamics Simulation of Surfactant Flooding Driven Oil-Detachment in Nano-Silica Channels.

Recovery of crude oil in rock nanopores plays an important role in the petroleum industry. In this work, we carried out molecular dynamics (MD) simulations to study the process of ionic surfactant solution driven oil-detachment in model silica (SiO2) nanochannels. Our MD simulation results revealed that the oil-detachment induced by the ionic surfactant flooding can be described by a three-stage process including the formation and delivery of surfactant micelles, the surfactant micelle disintegration-spread and migration on the oil-aggregate surface, and oil molecular aggregate deformation-to-detachment. A flooding from rear (FFR) phenomenon is revealed that the surfactant molecules tend to migrate to the rear bottom of the oil molecular aggregate caused by the water flow effect and hydration of polar head groups of surfactants, which facilitate the penetration of water molecules into the oil-rock interface, and the oil molecule detachment occurs at the rear bottom of the oil molecular aggregate. The present MD simulation results also indicate that the dodecyl benzenesulfonate (SDBS) has higher oil-driven efficiency than that of dodecyl trimethylammonium bromide (DTAB). The difference of oil displacement efficiency between the two surfactants is attributed to the hydration property of the polar head groups. Compared with the -N(CH3)3+ headgroup in DTAB, the bare O atom in the -SO3- group has a stronger H bond interaction with the surrounding water molecules. The stronger interaction between the headgroup of SDBS and the adjacent water molecule results in the surfactant migrating to the rear bottom of the oil molecules more quickly, thus accelerating the detachment of oil molecules.

On the solvation of the phosphocholine headgroup in an aqueous propylene glycol solution.

The atomic-scale structure of the phosphocholine (PC) headgroup in 30 mol. % propylene glycol (PG) in an aqueous solution has been investigated using a combination of neutron diffraction with isotopic substitution experiments and computer simulation techniques-molecular dynamics and empirical potential structure refinement. Here, the hydration of the PC headgroup remains largely intact compared with the hydration of this group in a bilayer and in a bulk water solution, with the PG molecules showing limited interactions with the headgroup. When direct PG interactions with PC do occur, they are most likely to coordinate to the N(CH3)3+ motifs. Further, PG does not affect the bulk water structure and the addition of PC does not perturb the PG-solvent interactions. This suggests that the reason why PG is able to penetrate into membranes easily is that it does not form strong-hydrogen bonding or electrostatic interactions with the headgroup allowing it to easily move across the membrane barrier.

Biophysical Properties of Phosphtidylglucoside and Phosphatidylinositol: Specific Differences in Head Group Interaction

The size of the polar head group plays a key role in lipid biophysics, influencing membrane organization, phase behavior, including transition (melting) temperature, as well as lipid–lipid interactions, such as the umbrella effect. In general, small head groups are associated with high transition temperatures and tighter head group packing compared to lipids with large head groups. The head groups of phosphatidylglucoside (PtdGlc) and phosphatidylinositol (PtdIns) are configurational isomers with both featuring a six-membered ring and a similar number of hydroxy functions. Interestingly, their chemical stability and biophysical properties differ significantly, despite their high structural similarity, comparable chemical size and weight, and presumably analogous head group orientation relative to the plasma membrane normal. PtdIns is known to exhibit a low transition temperature, limited lipid–lipid head group interaction, a high degree of head group hydration and an intramolecular hydrogen-bond even under fully hydrated conditions. PtdGlc on the other hand exhibits a ~20 degree higher transition temperature, extensive lipid–lipid head group interactions, a low degree of head group hydration and no intramolecular hydrogen-bond. Consequently, head group size in terms of lipid biophysics, refers not only to the immediate chemical size, but also includes the primary hydration shell.

Hydration and Counterion Binding of [C12MIM] Micelles.

Surface-active ionic liquids based on imidazolium cations are promising targets for micellar catalysis in aqueous solution, yielding enhanced rate constants compared to surfactants based on n-alkyltrimethylammonium cations and exhibiting a pronounced counterion dependence ( Bica Chem. Commun. 2012 , 48 , 5013 - 5015 ; Cognigni Phys. Chem. Chem. Phys. 2016 , 18 , 13375 - 13384 ). Probably most relevant to these effects is the interplay between headgroup hydration and counterion binding. To obtain more detailed information on these effects, aqueous solutions of 1-dodecyl-3-methylimidazolium ([C12MIM]) bromide, iodide, and triflate (TfO-) were investigated at 45 °C using broadband dielectric spectroscopy, viscosity measurements, and small-angle X-ray scattering experiments. Effective hydration numbers were determined, and information on the locations and mobilities of the condensed counterions, X-, was derived. It was found that [C12MIM] halide micelles were less hydrated than the corresponding n-dodecyltrimethylammonium ([C12TA]X) aggregates. Together with their somewhat weaker counterion condensation, this difference probably explains their higher catalytic activity. Whereas [C12MIM]Br micelles remained roughly spherical in the studied concentration range, rodlike aggregates were formed at high concentrations of the iodide and, in particular, the triflate surfactants. It appears that the much lower mobility of condensed TfO- counterions is the reason for the very low catalytic activity of [C12MIM]TfO micelles.

Molecular dynamics simulation of the influence of polyacrylamide on the stability of sodium dodecyl sulfate foam

Molecular dynamics simulations were performed to investigate the effect of the concentration of polyacrylamide (PAM) and the hydrolysis degree of partially hydrolyzed polyacrylamide (HPAM) on the stability of sodium dodecyl sulfate (SDS) foams. The effect of polymer on the complex systems (PAM-SDS and HPAM-SDS) was investigated by analyzing the density distribution of SDS headgroups, the radial distribution function (RDF) of hydration of SDS headgroups, the mean square displacement (MSD) of hydrated water around the amide group. The results show that an increase of PAM concentration can enhance the interaction between PAM and SDS, increase the number of hydrated water molecules around SDS headgroups and weaken the mobility of the hydrated water molecules around PAM, which will be beneficial to improve the foam stability. It has been observed that the favorable structure of SDS monolayer for stable foam appears when the hydrolysis degree of HPAM is 20% in the four foam systems of our simulations. In all four foams, the numbers of water molecules around headgroups increase first with the increase of HPAM hydrolysis degree, reaching a maximum value at HPAM 20%, followed by a decrease with larger hydrolysis degrees. These observations indicate that the foam is the most stable when the hydrolysis degree of HPAM is within the range of 20–30%.

Chemical Composition and Properties of the Liquid-Vapor Interface of Aqueous C1 to C4 Monofunctional Acid and Alcohol Solutions.

The liquid-vapor interface is playing an important role in aerosol and cloud chemistry in cloud droplet activation by aerosol particles and potentially also in ice nucleation. We have employed the surface sensitive and chemically selective X-ray photoelectron spectroscopy (XPS) technique to examine the liquid-vapor interface for mixtures of water and small alcohols or small carboxylic acids (C1 to C4), abundant chemicals in the atmosphere in concentration ranges relevant for cloud chemistry or aerosol particles at the point of activation into a cloud droplet. A linear correlation was found between the headgroup carbon 1s core-level signal intensity and the surface excess derived from literature surface tension data with the offset being explained by the bulk contribution to the photoemission signal. The relative interfacial enhancement of the carboxylic acids over the carboxylates at the same bulk concentration was found to be highest (nearly 20) for propionic acid/propionate and still about 5 for formic acid/formate, also in fair agreement with surface tension measurements. This provides direct spectroscopic evidence for high carboxylic acid concentrations at aqueous solution-air interfaces that may be responsible for acid catalyzed chemistry under moderately acidic conditions with respect to their bulk aqueous phase acidity constant. By assessing the ratio of aliphatic to headgroup C 1s signal intensities XPS also provides information about the orientation of the molecules. The results indicate an increasing orientation of alcohols and neutral acids toward the surface normal as a function of chain length, along with increasing importance of lateral hydrophobic interactions at higher surface coverage. In turn, the carboxylate ions exhibit stronger orientation toward the surface normal than the corresponding neutral acids, likely caused by the stronger hydration of the charged headgroup.

Self-Assembly Mechanism of pH-Responsive Glycolipids: Micelles, Fibers, Vesicles, and Bilayers.

A set of four structurally related glycolipids are described: two of them have one glucose unit connected to either stearic or oleic acid, and two other ones have a diglucose headgroup (sophorose) similarly connected to either stearic or oleic acid. The self-assembly properties of these compounds, poorly known, are important to know due to their use in various fields of application from cleaning to cosmetics to medical. At basic pH, they all form mainly small micellar aggregates. At acidic pH, the oleic and stearic derivatives of the monoglucose form, respectively, vesicles and bilayer, while the same derivatives of the sophorose headgroup form micelles and twisted ribbons. We use pH-resolved in situ small angle X-ray scattering (SAXS) under synchrotron radiation to characterize the pH-dependent mechanism of evolution from micelles to the more complex aggregates at acidic pH. By pointing out the importance of the COO-/COOH ratio, the melting temperature, Tm, of the lipid moieties, hydration of the glycosidic headgroup, the packing parameter, membrane rigidity, and edge stabilization, we are now able to draw a precise picture of the full self-assembly mechanism. This work is a didactical illustration of the complexity of the self-assembly process of a stimuli-responsive amphiphile during which many concomitant parameters play a key role at different stages of the process.

DMSO-induced perturbation of thermotropic properties of cholesterol-containing DPPC liposomes

Dimethyl sulfoxide (DMSO) is a universal solvent widely used in many fields, from basic research to industrial applications. At low concentration, it is the most important cryoprotectant agent against cellular damage caused during a freeze-thaw cycle. Although the effects of this cosolvent on the physico-chemical properties of a lipid bilayer have been extensively studied with both in vitro and in vivo experiments, the molecular mechanism of cryopreservation is not completely understood. Cholesterol (Chol) represents one of the essential cell membrane component and is fundamental to maintain the integrity and fluidity of the membrane. Here we report a study on the effect of DMSO on the stability of Chol-containing model membranes.We investigated the effect of DMSO on thermal stability of model membranes formed by dipalmitoylphospatidylcholine (DPPC) and DPPC/Chol by means of Fourier Transform Infrared Spectroscopy (FT-IR) and Differential Scanning Calorimetry (DSC) measurements. It is well known that cholesterol reduces the thermal stability of DPPC vesicles and also the pre-transition is abolished. Our results show that DMSO induces a stabilization of the lipid bilayer of DPPC liposomes increasing both the pre- and main transition temperatures. In DPPC/Chol liposomes a similar thermal stabilization was observed for the main transition indicating that DMSO is capable to stabilize the lipid bilayer even in the presence of the sterol. Moreover, by direct inspection of the hydration degree of the lipid bilayers, we evidenced the role played by DMSO on the thermal stability of the membrane as connected to the hydration of the polar head groups.

Effect of cation enrichment on dipalmitoylphosphatidylcholine (DPPC) monolayers at the air-water interface

The effect of highly concentrated salt solutions of marine-relevant cations (Na+, K+, Mg2+, and Ca2+) on Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC) was investigated by means of surface pressure-area isotherms, Brewster angle microscopy (BAM), and infrared reflection-absorption spectroscopy (IRRAS). It was found that monovalent cations and Mg2+ have similar phase behavior, causing DPPC monolayers to expand, while Ca2+ induces condensation. All cations disrupted the surface morphology at high cation concentration, resulting in decreased reflectivity from the monolayer. Monolayer refractive index was calculated from BAM image intensity in the liquid condensed phase and decreased with increasing cation concentration, which suggests that orientation of the alkyl chains change. Monovalent ions increase ordering of the alkyl chains, more than divalents, yet have little interaction with the DPPC headgroup. Mg2+ induces gauche defects in the alkyl chain and increases headgroup hydration at low lipid coverage but increases chain ordering and dehydrates the headgroup at high lipid coverage. Ca2+ orders alkyl chains and dehydrates the phosphate moiety, independent of lipid phase. At the highest salt concentration investigated, significant narrowing of the asymmetric PO2− vibrational mode occurs and is attributed to considerable dehydration of the DPPC headgroup.

Comparative atomic-scale hydration of the ceramide and phosphocholine headgroup in solution and bilayer environments.

Previous studies have used neutron diffraction to elucidate the hydration of the ceramide and the phosphatidylcholine headgroup in solution. These solution studies provide bond-length resolution information on the system, but are limited to liquid samples. The work presented here investigates how the hydration of ceramide and phosphatidylcholine headgroups in a solution compares with that found in a lipid bilayer. This work shows that the hydration patterns seen in the solution samples provide valuable insight into the preferential location of hydrating water molecules in the bilayer. There are certain subtle differences in the distribution, which result from a combination of the lipid conformation and the lipid-lipid interactions within the bilayer environment. The lipid-lipid interactions in the bilayer will be dependent on the composition of the bilayer, whereas the restricted exploration of conformational space is likely to be applicable in all membrane environments. The generalized description of hydration gathered from the neutron diffraction studies thus provides good initial estimation for the hydration pattern, but this can be further refined for specific systems.

Small Mismatches in Fatty Acyl Tail Lengths Can Effect Non Steroidal Anti-Inflammatory Drug Induced Membrane Fusion.

Biological membranes are made up of a variety of lipids with diverse physicochemical properties. The lipid composition modulates different lipidic parameters, such as hydration, dynamics, lipid packing, curvature strain, etc. Changes in these parameters affect various membrane-mediated processes, such as membrane fusion which is an integral step in many biological processes. Packing defects, which originate either from mismatch in the headgroup region or in the hydrophobic acyl tail region, play a major role in modulating membrane dynamics. In this study, we demonstrate how even a small mismatch in the fatty acyl chain length, achieved by incorporation of low concentrations (up to 30 mol %) of dipalmitoylphosphatidylcholine (DPPC) into dimyristoylphosphatidylcholine (DMPC) small unilamellar vesicles (SUVs), alters several lipidic parameters like packing, dynamics, and headgroup hydration. This in turn affects non steroidal anti-inflammatory drug (NSAID) induced membrane fusion. Dynamic light scattering, differential scanning calorimetry, second-derivative absorption spectrophotometry, and steady-state and time-resolved fluorescence have been used to elucidate the effect of small mismatch in the tails in DMPC/DPPC mixed vesicles and how it modulates membrane fusion induced by the oxicam NSAIDs, meloxicam (Mx), piroxicam (Px), and tenoxicam (Tx). Fusion kinetics was monitored using fluorescence based fusion assays. At low DPPC concentration of 10 mol %, additional fluidization promotes lipid mixing to some extent for Mx, but at higher mol % of DPPC, subsequent increase in rigidity of membrane interior along with increase in headgroup hydration, synergistically inhibits fusion to various extents for the three different drugs, Mx, Px, and Tx.

Structure ⿿ membrane activity relationship in a family of peptide-based gemini amphiphiles: An insight from experimental and theoretical model systems

A study of the interaction between five gemini amphiphilic valine-based pseudopeptides (GAPs) differing by the length of the central aliphatic spacer linking two amino acid subunits, and a model bacterial membrane lipid, 1,2-dimyristoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DMPG), is here presented. Pure DMPG, pure GAPs and mixed GAPs/DMPG monolayers were formed at the air-water interface using Langmuir technique. The properties of the Langmuir films were investigated using surface pressure measurements, polarization modulation-infrared reflection-absorption spectroscopy, and Brewster angle microscopy. The atomic level information concerning the orientation of molecules in the monolayer and hydration of the polar headgroups was obtained from molecular dynamics simulations. It was demonstrated that the length of the central spacer in the GAPs structure is important for the properties of the mixed films; the disorganization of the membrane increases with the length of the spacer. The latter point is important for developing possible antimicrobial agents based on GAPs.

A journey through the phase diagram of a pharmaceutically relevant microemulsion system

HypothesisThe phase behavior and the properties of water, oil, surfactant, and cosurfactant mixtures depend on the fine balance of different forces, among them the bending energy of the amphiphilic film. Thus, it should be possible to control the structural evolution of nonionic microemulsions by the cosurfactant content and the hydration of the surfactant headgroup. ExperimentsAn extensive investigation of the pseudoternary phase diagram of mixtures of water, isopropyl palmitate, polyoxyethylene (10) oleyl ether Brij 97 (C18E10), and butanol is presented for two different cosurfactant concentrations, thereby varying the hydrophilicity of the amphiphile. The studies were performed employing conductometric titrations, differential scanning calorimetry (DSC), and small-angle neutron scattering (SANS). FindingsA systematic growth of the domain sizes and correlation lengths is observed by increasing the water content in the initial oil/surfactant solution. The formation of a bicontinuous structure, as deduced from conductivity is directly related to the presence of free water unbound to the EO units of the surfactant, as determined by DSC. The experimental results, e.g., the extension of the different phase regions and the mesoscopic structure are discussed on a molecular level, therefore providing a direct link between the composition of the microemulsions and the resulting structure and properties.

Derivation of original RESP atomic partial charges for MD simulations of the LDAO surfactant with AMBER: applications to a model of micelle and a fragment of the lipid kinase PI4KA

In this paper, we describe the derivation and the validation of original RESP atomic partial charges for the N, N-dimethyl-dodecylamine oxide (LDAO) surfactant. These charges, designed to be fully compatible with all the AMBER force fields, are at first tested against molecular dynamics simulations of pure LDAO micelles and with a fragment of the lipid kinase PIK4A (DI) modeled with the QUARK molecular modeling server. To model the micelle, we used two distinct AMBER force fields (i.e. Amber99SB and Lipid14) and a variety of starting conditions. We find that the micelle structural properties (such as the shape, size, the LDAO headgroup hydration, and alkyl chain conformation) slightly depend on the force field but not on the starting conditions and more importantly are in good agreement with experiments and previous simulations. We also show that the Lipid14 force field should be used instead of the Amber99SB one to better reproduce the C(sp3)C(sp3)C(sp3)C(sp3) conformation in the surfactant alkyl chain. Concerning the simulations with LDAO-DI protein, we carried out different runs at two NaCl concentrations (i.e. 0 and 300 mM) to mimic, in the latter case, the experimental conditions. We notice a small dependence of the simulation results with the LDAO parameters and the salt concentration. However, we find that in the simulations, three out of four tryptophans of the DI protein are not accessible to water in agreement with our fluorescence spectroscopy experiments reported in the paper.

Intermolecular Headgroup Interaction and Hydration as Driving Forces for Lipid Transmembrane Asymmetry.

Variations between the inner and outer leaflets of cell membranes are crucial for cell functioning and signaling, drug-membrane interactions, and the formation of lipid domains. Transmembrane asymmetry can in principle be comprised of an asymmetric charge distribution, differences in hydration, specific headgroup/H-bonding interactions, or a difference in the number of lipids per leaflet. Here, we characterize the transmembrane asymmetry of small unilamellar liposomes consisting of zwitterionic and charged lipids in aqueous solution using vibrational sum frequency scattering and second harmonic scattering, label-free methods, specifically sensitive to lipid and water asymmetries. For single component liposomes, transmembrane asymmetry is present for the charge distribution and lipid hydration, but the leaflets are not detectably asymmetric in terms of the number of lipids per leaflet, even though geometrical packing arguments would predict so. Such a lipid transmembrane asymmetry can, however, be induced in binary lipid mixtures under conditions that enable H-bonding interactions between phosphate and amine groups. In this case, the measured asymmetry consists of a different number of lipids in the outer and inner leaflet, a difference in transmembrane headgroup hydration, and a different headgroup orientation for the interacting phosphate groups.