Simulation of surfactant adsorption at liquid-liquid interface: What we may expect from soft-core models?

The present work attempts to systematically explore the surfactant sorption at liquid-liquid interfaces with coarse-grained models targeting thermodynamic properties of reference liquid solutions. We employ dissipative particle dynamics with soft-core forcefield tested against experimental data on micellization of surfactants in water, and the previous results are reproduced in this work. We consider three different nonionic surfactants: hexaethylene glycol monododecyl ether (C12E6), 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol) known as Triton X-100 (TX-100), and two alkyl glucoside surfactants (CnG1) with n-alkane tail fragments and a saccharide hydrophilic head at decane-water and toluene-water interfaces. For TX-100, we composed a model based on the literature forcefield and found good agreement with the experimental critical micelle concentrations (CMCs). The head-head interactions are of different origins for different surfactant groups: entropic repulsion between ethylene oxide chains of C12E6 and TX-100, and more chemically specific and complex interactions between the maltose heads of alkyl glucosides. We interpret our results with the Redlich-Peterson equation of monolayer adsorption in order to relate the adsorption to the bulk concentration of the surfactant and the interfacial tension. The densities of the adsorbed monolayer at CMC mostly agree with the experimental data, and a reasonable agreement was obtained for the interfacial tension at CMC. At the same time, we found significant discrepancies between the simulated and experimental adsorption isotherms. We explain them by the oversimplified forcefield: when the parameters are fitted to the free energies of bulk solutions, they may not correctly reproduce the interfacial free energies.

Interactions of Crosslinked Polyacrylic Acid Polyelectrolyte Gels with Nonionic and Ionic Surfactants.

The morphology and stability of surfactant-loaded polyelectrolyte gels are of great interest for a variety of personal care, cosmetic, and pharmaceutical products. However, the mechanisms of surfactant interactions with gel-forming polymers are poorly understood and experimentally challenging. The aim of this work is to explore in silico the specifics of surfactant absorption within polyelectrolyte gels drawing on the examples of typical non-ionic octaethylene glycol monooctyl ether (C8E8) and anionic sodium dodecyl sulfate (SDS) surfactants and polyacrylic acid modified with hydrophobic sidechains mimicking the practically important Carbopol polymer. Using the systematically parameterized coarse-grained dissipative particle dynamics models, we generate and characterize the equilibrium conformations and swelling of the polymer films in aqueous solutions with the surfactant concentrations varied up to the critical micelle concentration (cmc). We discover the striking difference in interactions of Carbopol-like polymers with nonionic and ionic surfactants under mildly acidic conditions. The sorption of C8E8 within the polymer film is found substantial. As the surfactant concentration increases, the polymer film swells and, close to cmc, becomes unstable due to the formation and growth of water pockets filled with surfactant micelles. Sorption of SDS at the same bulk concentrations is found much lower, with only about 1% of surfactant mass fraction achieved at cmc. As the SDS concentration increases further, a lamellae structure is formed within the film, which remains stable. Reduced swelling and higher stability indicate better prospects of using SDS-type surfactants with Carbopol-based gels in formulations for detergents and personal care products.

Stability of Lipid Coatings on Nanoparticle-Decorated Surfaces.

Lipid membranes supported on solid surfaces and nanoparticles find multiple applications in industrial and biomedical technologies. Here, we explore in silico the mechanisms of the interactions of lipid membranes with nanostructured surfaces with deposited nanoparticles and explain the characteristic particle size dependence of the uniformity and stability of lipid coatings observed in vitro. Simulations are performed to demonstrate the specifics of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid membrane adhesion to hydrophilic and hydrophobic nanoparticles ranging in size from 1.5 to 40 nm using an original coarse-grained molecular dynamics model with implicit solvent and large simulation boxes (scales up to 280 × 154 × 69 nm3). We find that one of the major factors that affects the uniformity and stability of lipid coatings is the disjoining pressure in the water hydration layer formed between the lipid membrane and hydrophilic solid surface. This effect is accounted for by introducing a special long-range lipid-solid interaction potential that mimics the effects of the disjoining pressure in thin water layers. Our simulations reveal the physical mechanisms of interactions of lipid bilayers with solid surfaces that are responsible for the experimentally observed nonmonotonic particle size dependence of the uniformity and stability of lipid coatings: particles smaller than the hydration layer thickness (<2-3 nm) or larger than ∼20 nm are partially or fully enfolded by a lipid bilayer, whereas particles of the intermediate size (5-20 nm) cause membrane perforation and pore formation. In contrast, hydrophobic nanoparticles, which repel the hydration layer, tend to be encapsulated within the hydrophobic interior of the membrane and coated by the lipid monolayer. The proposed model can be further extended and applied to a wide class of systems comprising nanoparticles and nanostructured substrates interacting with lipid and surfactant bilayers and monolayers.

Adhesion, intake, and release of nanoparticles by lipid bilayers.

Understanding the interactions between nanoparticles (NP) and lipid bilayers (LB), which constitute the foundations of cell membranes, is important for emerging biomedical technologies, as well as for assessing health threats related to nanoparticle commercialization. Applying dissipative particle dynamic simulations, we explore adhesion, intake, and release of hydrophobic nanoparticles by DMPC bilayers. To replicate experimental conditions, we develop a novel simulation setup for modeling membranes at isotension conditions. NP-LB interactions are quantified by the free energy landscape calculated by the ghost tweezers method. NPs are studied z of diameter 2 nm (comparable with the LB hydrophobic core), 4 nm (comparable with the LB thickness) and 8 nm (exceeding the LB thickness). NPs are pre-covered by an adsorbed lipid monolayer. It is shown that NP translocation across LB includes (1) NP intake into the hydrophobic core via merging of the monolayer adsorbed on NP with the outer leaflet of bilayer (2) NP release via formation and rupture of a lipid junction connecting NP and LB. Both stages are associated with free energy barriers. The barrier for the intake stage increases with the NP size and becomes prohibitively high for 8 nm NP. The barriers for the release stage are significantly higher which implies that the release stage controls the translocation rate and dynamics. The release energy barrier of 4 nm NP is found smaller than those for 2 and 8 nm NPs which implies the existence of the optimal NP size for unforced trans-membrane transport. Based on the calculated free energy landscape, the dynamics of unforced transport of NP across LB is evaluated using the Fokker-Planck equation, which mimics NP diffusion along the free energy landscape with multiple attempts to reach the barrier. We found that the number of attempts required for successful translocation scales exponentially with the energy barrier.

Nanoparticle-Engendered Rupture of Lipid Membranes.

Tension-induced rupture of 1,2-dimyristoyl- sn-glycero-3-phosphocholine (DMPC) lipid membranes with encapsulated hydrophobic nanoparticles is elucidated using dissipative particle dynamics simulations. The dynamics of hole formation is studied, and a nanoparticle size-dependent relationship is established for the probability of membrane rupture within a given time as a function of the membrane tension. Two mechanisms of hole formation are explored: homogeneous nucleation and heterogeneous nucleation at the nanoparticle surface. While the kinetics of homogeneous nucleation in unloaded membranes complies with the predictions of the classical Deryagin-Gutop (DG) theory, the heterogeneous nucleation causes progressively lower lysis tensions as the particle size increases. The thermodynamics of heterogeneous nucleation is treated by introducing an effective contact angle at the three-phase, solvent-membrane-solid boundary into the DG theory. The proposed approach helps quantitatively interpret the simulation results and predict the membrane stability in real experiments with significantly larger (by many orders of magnitude) observation times and spatial scales.

Coarse-grained model of nanoscale segregation, water diffusion, and proton transport in Nafion membranes.

We present a coarse-grained model of the acid form of Nafion membrane that explicitly includes proton transport. This model is based on a soft-core bead representation of the polymer implemented into the dissipative particle dynamics (DPD) simulation framework. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with water beads. Morse bond formation and breakup artificially mimics the Grotthuss hopping mechanism of proton transport. The proposed DPD model is parameterized to account for the specifics of the conformations and flexibility of the Nafion backbone and sidechains; it treats electrostatic interactions in the smeared charge approximation. The simulation results qualitatively, and in many respects quantitatively, predict the specifics of nanoscale segregation in the hydrated Nafion membrane into hydrophobic and hydrophilic subphases, water diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from a collection of isolated water clusters to a 3D network of pores filled with water embedded in the hydrophobic matrix. The segregated morphology is characterized in terms of the pore size distribution with the average size growing with hydration from ∼1 to ∼4 nm. Comparison of the predicted water diffusivity with the experimental data taken from different sources shows good agreement at high and moderate hydration and substantial deviation at low hydration, around and below the percolation threshold. This discrepancy is attributed to the dynamic percolation effects of formation and rupture of merging bridges between the water clusters, which become progressively important at low hydration, when the coarse-grained model is unable to mimic the fine structure of water network that includes singe molecule bridges. Selected simulations of water diffusion are performed for the alkali metal substituted membrane which demonstrate the effects of the counter-ions on membrane self-assembly and transport. The hydration dependence of the proton diffusivity reproduces semi-qualitatively the trend of the diverse experimental data, showing a sharp decrease around the percolation threshold. Overall, the proposed model opens up an opportunity to study self-assembly and water and proton transport in polyelectrolytes using computationally efficient DPD simulations, and, with further refinement, it may become a practical tool for theory informed design and optimization of perm-selective and ion-conducting membranes with improved properties.

Adhesion and Separation of Nanoparticles on Polymer-Grafted Porous Substrates.

This work explores interactions of functionalized nanoparticles (NP) with polymer brushes (PB) in a binary mixture of good and poor solvents. NP-PB systems are used in multiple applications, and we are particularly interested in the problem of chromatographic separation of NPs on polymer-grafted porous columns. This process involves NP flow through the pore channels with walls covered by PBs. NP-PB adhesion is governed by adsorption of polymer chains to NP surface and entropic repulsion caused by the polymer chain confinement between NP and the channel wall. Both factors depend on the solvent composition, variation of which causes contraction or expansion of PB. Using dissipative particle dynamics simulations in conjunction with the ghost tweezers free energy calculation technique, we examine the free energy landscapes of functionalized NPs within PB-grafted channels depending on the solvent composition at different PB grafting densities and polymer-solvent affinities. The free energy landscape determines the probability of NP location at a given distance to the surface, positions of equilibrium adhesion states, and the Henry constant that characterizes adsorption equilibrium and NP partitioning between the stationary phase of PB and mobile phase of flowing solvent. We analyze NP transport through a polymer-grafted channel and calculate the mean velocity and retention time of NP depending on the NP size and solvent composition. We find that, with the increase of the bad (poor) solvent fraction and respective PB contraction, NP separation exhibits a transition from the hydrodynamic size exclusion regime with larger NPs having shorter retention time to the adsorption regime with smaller NPs having shorter retention time. The observed reversal of the sequence of elution is reminiscent of the critical condition in polymer chromatography at which the retention time is molecular weight independent. This finding suggests the possibility of the existence of an analogous special regime in nanoparticle chromatography at which NPs with like surface properties elute together regardless of their size. The latter has important practical implications: NPs can be separated by surface chemistry rather than by their size employing the gradient mode of elution with controlled variation of solvent composition.

Adhesion of Phospholipid Bilayers to Hydroxylated Silica: Existence of Nanometer-Thick Water Interlayers.

Lipid bilayers attached to solid surfaces play an important role in bioinspired materials and devices and serve as model systems for studies of interactions of cell membranes with particles and biomolecules. Despite active experimental and theoretical studies, the interactions of lipid membranes with solid substrates are still poorly understood. In this work, we explore, using atomistic molecular dynamics simulations, the equilibrium and stability of a phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine membrane supported on hydroxylated amorphous silica. We reveal two distinct types of thermodynamically stable states, characterized by different widths of the water layer between the membrane and the substrate. In α-states, the membrane is closely attached with the lipid head groups interacting directly with surface hydroxyls; however, because of the molecular level roughness of the amorphous silica surface, there exists an inhomogeneous water layer trapped between the substrate and the membrane. In ß-states, the membrane is separated from the silica surface by a water film of ∼2.5 nm in thickness. The thermodynamic equilibrium is quantified in terms of the disjoining pressure isotherm as a function of membrane-substrate separation, which has a double sigmoidal shape with two minima and one maximum, which correspond to the limits of stability of α- and ß-states. The thermodynamic properties and bilayer structure are compared with experimental findings and simulation results for relevant systems.

In Situ Growth and Characterization of Metal Oxide Nanoparticles within Polyelectrolyte Membranes.

This study describes a novel approach for the in situ synthesis of metal oxide-polyelectrolyte nanocomposites formed via impregnation of hydrated polyelectrolyte films with binary water/alcohol solutions of metal salts and consecutive reactions that convert metal cations into oxide nanoparticles embedded within the polymer matrix. The method is demonstrated drawing on the example of Nafion membranes and a variety of metal oxides with an emphasis placed on zinc oxide. The in situ formation of nanoparticles is controlled by changing the solvent composition and conditions of synthesis that for the first time allows one to tailor not only the size, but also the nanoparticle shape, giving a preference to growth of a particular crystal facet. The high-resolution TEM, SEM/EDX, UV-vis and XRD studies confirmed the homogeneous distribution of crystalline nanoparticles of circa 4 nm and their aggregates of 10-20 nm. The produced nanocomposite films are flexible, mechanically robust and have a potential to be employed in sensing, optoelectronics and catalysis.

Parametrization of Chain Molecules in Dissipative Particle Dynamics.

This paper presents a consistent strategy for parametrization of coarse-grained models of chain molecules in dissipative particle dynamics (DPD), where the soft-core DPD interaction parameters are fitted to the activities in solutions of reference compounds that represent different fragments of target molecules. The intercomponent parameters are matched either to the infinite dilution activity coefficients in binary solutions or to the solvent activity in polymer solutions. The respective calibration relationships between activity and intercomponent interaction parameter are constructed from the results of Monte Carlo simulation of the coarse-grained solutions of reference compounds. The chain conformation is controlled by the near neighbor and second neighbor bond potentials, which are parametrized by fitting the intramolecular radial distribution functions of the coarse-grained chains to the respective atomistic molecular dynamics simulations. The consistency, accuracy, and transferability of the proposed parametrization strategy is demonstrated drawing on the example of nonionic surfactants of the poly(ethylene oxide) alkyl ether (CnEm) family. The lengths of tail and head sequences are varied (n = 8-12 and m = 3-9), so that the critical micelle concentration ranges from 10 to 0.1 mM. The surfactants are modeled at different coarse-graining levels using DPD beads of different diameters. We found consistent agreement with experimental data for the critical micelle concentration and aggregation number, especially for surfactants with relatively long hydrophilic segments. Depending on the system, we observed surfactant aggregation into spheroidal, elongated, or core-shell micelles, as well as into irregular agglomerates. Using the models at different coarse-graining levels for the same molecules, we found that the smaller the bead size the better is agreement with experimental data.

Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane.

Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

Modeling Proton Dissociation and Transfer Using Dissipative Particle Dynamics Simulation.

We suggest a coarse-grained model for dissipative particle dynamics (DPD) simulations of solutions with dissociated protons. The model uses standard short-range soft repulsion and smeared charge electrostatic potentials between the beads, representing solution components. The proton is introduced as a separate charged bead that forms dissociable bonds with proton receptor base beads, such as water or deprotonated acid anions. The proton-base bonds are described by Morse potentials. When the proton establishes the Morse bonds with two bases, they form an intermediate complex, and the proton is able to "hop" between the bases artificially mimicking the Grotthuss diffusion mechanism. By adjusting the Morse potential parameters, one can regulate the potential barrier associated with intermediate complex formation and breakup and control the hopping frequency. This makes the proposed model applicable to simulations of proton mobility and reaction equilibria between protonated and deprotonated acid forms in aqueous solutions. The proposed model provides quantitative agreement with experiments for the proton self-diffusion coefficient and hopping frequency, as well as for the degree of dissociation of benzenesulfonic acid.

Modeling Aggregation of Ionic Surfactants Using a Smeared Charge Approximation in Dissipative Particle Dynamics Simulations.

Using dissipative particle dynamics (DPD) simulations, we explore the specifics of micellization in the solutions of anionic and cationic surfactants and their mixtures. Anionic surfactant sodium dodecyl sulfate (SDS) and cationic surfactant cetyltrimethylammonium bromide (CTAB) are chosen as characteristic examples. Coarse-grained models of the surfactants are constructed and parameterized using a combination of atomistic molecular simulation and infinite dilution activity coefficient calibration. Electrostatic interactions of charged beads are treated using a smeared charge approximation: the surfactant heads and dissociated counterions are modeled as beads with charges distributed around the bead center in an implicit dielectric medium. The proposed models semiquantitatively describe self-assembly in solutions of SDS and CTAB at various surfactant concentrations and molarities of added electrolyte. In particular, the model predicts a decline in the free surfactant concentration with the increase of the total surfactant loading, as well as characteristic aggregation transitions in single-component surfactant solutions caused by the addition of salt. The calculated values of the critical micelle concentration reasonably agree with experimental observations. Modeling of catanionic SDS-CTAB mixtures show consecutive transitions to worm-like micelles and then to vesicles caused by the addition of CTAB to micellar solution of SDS.

Adhesion of nanoparticles to polymer brushes studied with the ghost tweezers method.

Mechanisms of interactions between nanoparticles (NPs) and polymer brushes (PBs) are explored using dissipative particle dynamics simulations and an original "ghost tweezers" method that emulates lab experiments performed with optical or magnetic tweezers. The ghost tweezers method is employed to calculate the free energy of adhesion. Ghost tweezers represents a virtual harmonic potential, which tethers NP with a spring to a given anchor point. The average spring force represents the effective force of NP-PB interaction as a function of the NP coordinate. The free energy landscape of NP-PB interactions is calculated as the mechanical work needed to transfer NP from the solvent bulk to a particular distance from the substrate surface. With this technique, we explore the adhesion of bare and ligand-functionalized spherical NPs to polyisoprene natural rubber brush in acetone-benzene binary solvent. We examine two basic mechanisms of NP-PB interactions, NP adhesion at PB exterior and NP immersion into PB, which are governed by interplay between entropic repulsive forces and enthalpic attractive forces caused by polymer adsorption at the NP surface and ligand adsorption at the substrate. The relative free energies of the equilibrium adhesion states and the potential barriers separating these states are calculated at varying grafting density, NP size, and solvent composition.

Morphological transformations in polymer brushes in binary mixtures: DPD study.

Morphological transformations in polymer brushes in a binary mixture of good and bad solvents are studied using dissipative particle dynamics simulations drawing on a characteristic example of polyisoprene natural rubber in an acetone-benzene mixture. A coarse-grained DPD model of this system is built based on the experimental data in the literature. We focus on the transformation of dense, collapsed brush in bad solvent (acetone) to expanded brush solvated in good solvent (benzene) as the concentration of benzene increases. Compared to a sharp globule-to-coil transition observed in individual tethered chains, the collapsed-to-expanded transformation in brushes is found to be gradual without a prominent transition point. The transformation becomes more leveled as the brush density increases. At low densities, the collapsed brush is highly inhomogeneous and patterned into bunches composed of neighboring chains due to favorable polymer-polymer interaction. At high densities, the brush is expanded even in bad solvent due to steric restrictions. In addition, we considered a model system similar to the PINR-acetone-benzene system, but with the interactions between the solvent components worsened to the limit of miscibility. Enhanced contrast between good and bad solvents facilitates absorption of the good solvent by the brush, shifting the collapsed-to-expanded transformation to lower concentrations of good solvent. This effect is especially pronounced for higher brush densities.

Self-assembly in Nafion membranes upon hydration: water mobility and adsorption isotherms.

By means of dissipative particle dynamics (DPD) and Monte Carlo (MC) simulations, we explored geometrical, transport, and sorption properties of hydrated Nafion-type polyelectrolyte membranes. Composed of a perfluorinated backbone with sulfonate side chains, Nafion self-assembles upon hydration and segregates into interpenetrating hydrophilic and hydrophobic subphases. This segregated morphology determines the transport properties of Nafion membranes that are widely used as compartment separators in fuel cells and other electrochemical devices, as well as permselective diffusion barriers in protective fabrics. We introduced a coarse-grained model of Nafion, which accounts explicitly for polymer rigidity and electrostatic interactions between anionic side chains and hydrated metal cations. In a series of DPD simulations with increasing content of water, a classical percolation transition from a system of isolated water clusters to a 3D network of hydrophilic channels was observed. The hydrophilic subphase connectivity and water diffusion were studied by constructing digitized replicas of self-assembled morphologies and performing random walk simulations. A non-monotonic dependence of the tracer diffusivity on the water content was found. This unexpected behavior was explained by the formation of large and mostly isolated water domains detected at high water content and high equivalent polymer weight. Using MC simulations, we calculated the chemical potential of water in the hydrated polymer and constructed the water sorption isotherms, which extended to the oversaturated conditions. We determined that the maximum diffusivity and the onset of formation of large water domains corresponded to the saturation conditions at 100% humidity. The oversaturated membrane morphologies generated in the canonical ensemble DPD simulations correspond to the metastable and unstable states of Nafion membrane that are not realized in the experiments.

Oxygen incorporation in rubrene single crystals.

Single crystal rubrene is a model organic electronic material showing high carrier mobility and long exciton lifetime. These properties are detrimentally affected when rubrene is exposed to intense light under ambient conditions for prolonged periods of time, possibly due to oxygen up-take. Using photoelectron, scanning probe and ion-based methods, combined with an isotopic oxygen exposure, we present direct evidence of the light-induced reaction of molecular oxygen with single crystal rubrene. Without a significant exposure to light, there is no reaction of oxygen with rubrene for periods of greater than a year; the crystal's surface (and bulk) morphology and chemical composition remain essentially oxygen-free. Grand canonical Monte Carlo computations show no sorbtion of gases into the bulk of rubrene crystal. A mechanism for photo-induced oxygen inclusion is proposed.

Calculations of critical micelle concentration by dissipative particle dynamics simulations: the role of chain rigidity.

Micelle formation in surfactant solutions is a self-assembly process governed by complex interplay of solvent-mediated interactions between hydrophilic and hydrophobic groups, which are commonly called heads and tails. However, the head-tail repulsion is not the only factor affecting the micelle formation. For the first time, we present a systematic study of the effect of chain rigidity on critical micelle concentration and micelle size, which is performed with the dissipative particle dynamics simulation method. Rigidity of the coarse-grained surfactant molecule was controlled by the harmonic bonds set between the second-neighbor beads. Compared to flexible molecules with the nearest-neighbor bonds being the only type of bonded interactions, rigid molecules exhibited a lower critical micelle concentration and formed larger and better-defined micelles. By varying the strength of head-tail repulsion and the chain rigidity, we constructed two-dimensional diagrams presenting how the critical micelle concentration and aggregation number depend on these parameters. We found that the solutions of flexible and rigid molecules that exhibited approximately the same critical micelle concentration could differ substantially in the micelle size and shape depending on the chain rigidity. With the increase of surfactant concentration, primary micelles of more rigid molecules were found less keen to agglomeration and formation of nonspherical aggregates characteristic of flexible molecules.

Polymer translocation through a nanopore: DPD study.

Translocation of a polymer chain through a narrow pore is explored using 3D explicit solvent dissipative particle dynamics simulation. We study the dependence of the translocation dynamics and translocation time τ on the chain length N, driving force magnitude E, and solvent quality. Two types of driving forces are considered: uniform hydrostatic force, which is applied equally to the chain and solvent particles, and uniform electrostatic force, which is applied selectively to the charged particles in the chain and oppositely charged counterions in the solvent. We concluded that the scaling correlations τ ~ E(-ξ) and τ ~ N(ß) are valid only for coil-like chains. For globular chains, the exponents ξ and ß could not be identified with a reasonable accuracy. While the found value of ξ agrees with published experimental results and does not depend on the driving force type, the exponent ß depends on the driving force and solvent quality. This is explained by nonequilibrium effects, as in the systems considered, the time of translocation is comparable with the time of chain relaxation. These effects, manifested in the changes of chain conformation in the process of translocation, were analyzed on the basis of the variation of the gyration radii of cis and trans segments of the chain in normal and lateral directions. A prominent chain expansion was observed for coils and was insignificant for globules. This work demonstrates the feasibility of the 3D dissipative particle dynamics modeling of translocation phenomena and accounting for the electrostatic interactions with explicit counterions, as well as for the solvent quality, in a computationally efficient manner.

Interactions of sarin with polyelectrolyte membranes: a molecular dynamics simulation study.

Nanostructured polyelectrolyte membranes (PEMs), which are widely used as permselective diffusion barriers in fuel cell technologies and electrochemical processing, are considered as protective membranes suitable for blocking warfare toxins, including water-soluble nerve agents such as sarin. In this article, we examine the mechanisms of sorption and diffusion of sarin in hydrated PEMs by means of atomistic molecular dynamics simulations. Three PEMs are considered: Nafion, sulfonated polystyrene (sPS) that forms the hydrophilic subphase of segregated sPS-polyolefin block copolymers, and random sPS-polyethylene copolymer. We found that sarin concentrates at the interface between the hydrophilic and hydrophobic subphases of hydrated Nafion acting as a surfactant. In hydrated sPS, where the scale of water-polymer segregation is much smaller (1-2 nm), sarin also interacts favorably with hydrophobic and hydrophilic components. Water diffusion slows as the sarin content increases despite the overall increase in solvent content, which suggests that sarin and water have somewhat different pathways through the segregated membrane. Upon replacement of counterions of monovalent potassium with those of divalent calcium, sarin diffusion slows but remains substantial in all ionomers considered, especially at high sarin concentrations. The behavior of sarin is similar to that of its common simulant, dimethyl methylphosphonate.