Adsorption of impurities in vegetable oil: A molecular modelling study.

Here, the adsorption of impurity species from triglyceride solvent representing a model vegetable oil is studied using atomistic molecular dynamics simulations. We compare the adsorption of water, glycerol, oleic acid, monoolein, and two types of phospholipids on model silica adsorbents differing in their OH-group density, i.e. hydrogen bonding ability, quartz and cristobalite. We find that the species containing charged groups, phospholipids DOPC and DOPE, adsorb significantly stronger than the nonionic impurities. Secondary contribution to adsorption arises from hydrogen bonding capability of the impurity species, the silica surface, and also the triglyceride solvent: in general, more hydrogen bonding sites in impurity species leads to enhanced adsorption but hydrogen bonding with solvent competes for the available sites. Interestingly, adsorption is weaker on cristobalite even though it has a higher hydrogen bonding site density than quartz. This is because the hydrogen bonds can saturate each other on the adsorbent. The finding demonstrates that optimal adsorption response is obtained with intermediate adsorbent hydrogen bonding site densities. Additionally, we find that monoolein and oleic acid show a concentration driven adsorption response and reverse micelle like aggregate formation in bulk triglyceride solvent even in the absence of water. The findings offer insight into adsorption phenomena at inorganic adsorbent - apolar solvent interfaces and provide guidelines for enhanced design of adsorbent materials for example for vegetable oil purification.

Hybrid Atomistic and Coarse-Grained Model for Surfactants in Apolar Solvents.

Here, we develop and verify the performance of a hybrid molecular modeling approach that combines coarse-grained apolar solvent and atomistic solute or polar solvent description, for example, for description of reverse micellar systems. The coarse-grained solvent model is directly applicable to organic solvents encompassing alkane, alkene, and fatty acid ester functional groups and connects directly to both standard united-atom GROMOS 53A6 and all-atom CHARMM27 force fields, as well as the atomistic detail water models compatible with these force fields. The different levels of description are coupled via explicit, unscaled electrostatics, and scaled mixing rules for dispersive interactions. The hybrid model is in near-quantitative agreement with fully atomistic simulations when combined with the CHARMM27 model but underestimates modestly surfactant aggregation when using GROMOS 53A6 united-atom description. The use of truncated electrostatics affords up to a 9-fold increase in computational speed without significant loss of accuracy. However, long-range electrostatic calculations and load imbalance at high core counts can significantly degrade the performance. We demonstrate the usability of the hybrid model by assessing the reverse micelle formation of a homologous series of nonionic glycerolipids via large-scale self-assembly simulations. The presented model is demonstrated here for accurate description of surfactant systems in apolar solvents, with and without also polar solvent (water) in the system. The formulation can be expected to describe well also other solute species or interfaces with an apolar solvent in an apolar environment.

Phospholipid-Based Reverse Micelle Structures in Vegetable Oil Modified by Water Content, Free Fatty Acid, and Temperature.

Colloidal assemblies of phospholipids in oil are known to be highly sensitive to changes in system composition and temperature. Despite the fundamental biological and high industrial relevance of these aggregates, the mechanisms behind the structural changes, especially in real oils, are not well understood. In this work, small-angle X-ray scattering (SAXS) was combined with molecular dynamics simulations to characterize the effects of oleic acid, water, and temperature on self-assembled structures formed by lecithin in rapeseed oil. SAXS showed that adding water to the mixtures caused the precipitation of liquid-crystalline phases with lamellar or hexagonal geometry. The combination of SAXS and molecular dynamics simulations revealed that stable spherical reverse micelles in oil had a core radius of about 2 nm and consisted of approximately 60 phospholipids centered around a core containing water and sugars. The presence of oleic acid improved the stability of reverse micelles against precipitation due to the increase in the water concentration in oil by allowing the reverse micelle cores to expand and accommodate more water. The shape and size of the reverse micelles changed at high temperatures, and irreversible elongation was observed, especially in the presence of oleic acid. The findings show the interdependency of the structure of the reverse micellar aggregates on system composition, in particular, oleic acid and water, as well as temperature. The revealed characteristics of the self-assembled structures have significance in understanding and tuning the properties of vegetable oil-based emulsions, food products, oil purification, and drug delivery systems.

Aggregation response of triglyceride hydrolysis products in cyclohexane and triolein.

Here, we examine the aggregation response of a series of triglyceride-based biosurfactants in cyclohexane and triglyceride solvents via all-atom molecular dynamics simulations and supporting experiments. The surfactant aggregation follows in all systems, with only minor deviations, a multiple equilibrium, i.e. open association, model. Monoglyceride aggregation in cyclohexane exhibits a critical micellization concentration, cmc, showing a cmc can exist even in a system following open association. However, the cmc is associated with a change in balance with oligomeric and larger aggregates in the solution, not an onset of aggregate formation. It is demonstrated that reverse micelles can form in the absence of water stabilized by intersurfactant hydrogen bonds alone, and that the polarity and hydrogen bonding capability of triolein systematically reduces surfactant aggregation in comparison to cyclohexane. A comparison between CHARMM27 and CHARMM36 simulation models reveals that while trends are preserved, the models differ in quantitative prediction. Finally, consolidation of the general aggregation response trends predicted by the modelling are obtained via 7,7,8,8-tetracyanoquinodimethane dye (TCNQ) solubilization experiments on the corresponding model plant oil systems. The findings provide guidelines for predicting and controlling surfactant aggregation response in organic solvents via tuning the solvent polarity and hydrogen bonding ability, and a critical assessment of simulation and aggregation models for surfactant systems in organic solvents.

Particulate Coatings via Evaporation-Induced Self-Assembly of Polydisperse Colloidal Lignin on Solid Interfaces.

Polydisperse smooth and spherical biocolloidal particles were suspended in aqueous media and allowed to consolidate via evaporation-induced self-assembly. The stratification of the particles at the solid-air interface was markedly influenced, but not monotonically, by the drying rate. Cross-sectional imaging via electron microscopy indicated a structured coating morphology that was distinctive from that obtained by using particles with a mono- or bimodal distribution. Segregation patterns were found to derive from the interplay of particle diffusion, interparticle forces, and settling dynamics. Supporting our experimental findings, computer simulations showed an optimal drying rate for achieving maximum segregation. Overall, stratified coatings comprising nano- and microparticles derived from lignin are expected to open opportunities for multifunctional structures that can be designed and predicted on the basis of experimental Péclet numbers and computational order.

Effects of 1-hexanol on C12E10 micelles: a molecular simulations and light scattering study.

The micelles of the non-ionic C12E10 surfactant and 1-hexanol as an aqueous solution additives are studied toward the purpose of understanding the role of alcohol additives in tuning the characteristics of alkyl-ethoxylate micellar systems. Our dynamic light scattering and cloud point experiments show that the addition of hexanol induces a response similar to an increase of temperature. We associate the change with increased attraction between the micelles at low to moderate hexanol loadings and a potential increase of the aggregate size at a high hexanol-to-surfactant ratio. Detailed molecular dynamic simulation characterization shows that hexanol solubilizes to a micelle palisade layer when the hexanol-to-C12E10 ratio is less than or equal to 0.5 while swollen micelles, in which a part of hexanol forms an oil core, are present when the ratio increases above approximately 1.5. The simulations indicate that the surface of the micelles is rough. Formation of reverse hexanol structures akin to those found in bulk octanol is observed in the oil core. Molecular simulations associate the increase in attraction between micelles observed via the experiments with decreased chain density in the headgroup region. This density decrease is caused by hexanol molecules solubilized between neighbouring surfactants. Altogether, these findings provide detailed physical characterization of the effect of an archetypal solution additive, hexanol, on an alkyl ethoxylate micelle system. These findings could bear a significance in designing micellar and emulsion based systems with desired solution characteristics or properties for e.g. drug delivery, catalysis, or platforms for green chemistry reactions.

Surfactant Interactions and Organization at the Gas-Water Interface (CTAB with Added Salt).

We have studied adsorbed layers of cetyltrimethylammonium bromide (CTAB) at air-water interfaces in the presence of added electrolyte. Fast bubble compression/expansion measurements were used to obtain the surface equation of state, i.e., the surface tension vs CTAB surface concentration dependence. We show that while a simple model where the surfactant molecules are assumed to be noninteracting is insufficient to describe the measured response of the surfactant layer, a modified Frumkin equation where the local interactions between the molecular components depend on their surface concentration captures the response. The variation of the effective interactions in the surfactant layer in the model shows that the interactions in the surfactant layer change from effectively repulsive to attractive with increasing surface concentration. Molecular dynamics simulations are performed to probe the origins of the change in the interactions. The simulations indicate that already at low surface concentrations the surfactants aggregate as highly dynamic rafts with surfactant orientation parallel to the interface. Increasing the concentration leads to a change in the assembly morphology at the interface: the surfactant layer thickens and the surfactants sample a range of tilted orientations with respect to the interfacial plane. The change from transient raftlike assemblies to dynamical aggregates at the interface involves a clear increase in the degree of counterion binding: we speculate that the flip of the effective interaction parameter in the model used to interpret the experimental results could result from this. The work here presents basic steps toward a proper understanding of the molecular organization and interactions of surfactants at an air-water interface. This is crucially important in understanding macroscopic properties of surfactant-stabilized systems such as foams, emulsions, and colloidal dispersions.

Effect of temperature, water content and free fatty acid on reverse micelle formation of phospholipids in vegetable oil.

The self-assembly of phospholipids in oil, specifically lecithin in rapeseed oil, was investigated by combining experimental and computational methods The influence of temperature, water, and free fatty acids on the onset of lecithin aggregation in the rapeseed oil was determined using the 7,7,8,8 -tetracyanoquinodimethane dye (TCNQ) solubilization method and the size and shape of the self-assembled lecithin structures were investigated by small-angle X-ray scattering and cryogenic transmission electron microscopy. In the absence of excess water in the system (0.03wt-% water in oil), stable cylindrical lecithin reverse micelles were observed above the critical micelle concentration (CMC). Comparing the aggregation response in room temperature and at 70°C revealed that CMC decreased with increasing temperature. Furthermore, already a modest amount of added water (0.3wt-% water in oil) was sufficient to induce the formation of lamellar lecithin structures, that phase separated from the oil. In low water content, oleic acid suppressed the formation of lecithin reverse micelles whereas in the presence of more water, the oleic acid stabilized the reverse micelles. Consequently, more water was needed to induce phase separation in the presence of oleic acid. Molecular dynamics simulations indicated that the stabilizing effect of oleic acid resulted from oleic acid enhancing phospholipid solubilization in the oil by forming a solvating shell around the phosphate head group. The findings showed that the response of the mixed surfactant system is a delicate interplay of the different components and variables. The significance of the observations is that multiple parameters need to be controlled for desired system response, for example towards vegetable oil purification or phospholipid based microemulsions.

Controlling carbon-nanotube-phospholipid solubility by curvature-dependent self-assembly.

Control of aqueous dispersion is central in the processing and usage of nanoscale hydrophobic objects. However, selecting dispersive agents based on the size and form of the hydrophobic object and the role of coating morphology in dispersion efficiency remain important open questions. Here, the effect of the substrate and the dispersing molecule curvature, as well as, the influence of dispersant concentration on the adsorption morphology are examined by molecular simulations of graphene and carbon nanotube (CNT) substrates with phospholipids of varying curvature as the dispersing agents. Lipid spontaneous curvature is increased from close to zero (effectively cylindrical lipid) to highly positive (effectively conical lipid) by studying double tailed dipalmitoylphosphadidylcholine (DPPC) and single tailed lysophosphadidylcholine (LPC) which differ in the number of acyl chains but have identical headgroup. We find that lipids are good dispersion agents for both planar and curved nanoparticles and induce a dispersive barrier nonsize selectively. Differences in dispersion efficiency arise from lipid headgroup density and their extension from the hydrophobic substrate in the adsorption morphology. We map the packing morphology contributing factors and report that the aggregate morphologies depend on the competition of interactions rising from (1) hydrophobicity driven maximization of lipid-substrate contacts and lipid self-adhesion, (2) tail bending energy cost, (3) preferential alignment along the graphitic substrate principal axes, and (4) lipid headgroup preferential packing. Curved substrates adjust the morphology by changing the balance between the interaction strengths. Jointly, the findings show substrate curvature and dimensions are a way to tune lipid adsorption to desired, self-assembling patterns. Besides engineering dispersion efficiency, the findings could bear significance in designing materials with defined molecular scale, molecular coatings for orientation specific CNT assembly or lipid-based molecular masks and patterning on graphene.