Molecular understanding of diffusion in confinement

We introduce a computational method to directly relate diffusivities to the microscopic behavior of the adsorbed molecules. We apply this method to gases in an MFI-type molecular sieve, the reference system in this field. Transitions in the number and nature of adsorption sites result in temporary local increases in the diffusion. This occurs at different loadings in each of the x, y, and z directions, giving rise to the complex loading behavior found experimentally. Our method can be applied to any adsorbent-adsorbate system, and provides a fundamental understanding of diffusion in confinement on a molecular level.     

Molecular mechanism of Peptide-induced pores in membranes

We suggest a physical mechanism by which antimicrobial peptides spontaneously induce stable pores in membranes. Peptide binding to a lipid bilayer causes an internal stress, or internal membrane tension, that can be sufficiently strong to create pores. Like detergents, peptides have a high affinity for the rim of the pore. Binding to the rims reduces the line tension and decreases the number of peptides causing the internal membrane tension. Consequently, the pore radius is stable. The pore formation resembles a phase transition.     

Molecular dynamics simulation of pervaporation in zeolite membranes

The pervaporation separation of liquid mixtures of water/ethanol and water/methanol using three zeolite (Silicalite, NaA and Chabazite) membranes has been examined using the method of molecular dynamics. The main goal of this study was to identify intermolecular interactions between water, methanol, ethanol and the membrane surface that play a critical role in the separations. This would then allow better membranes to be designed more efficiently and systematically than the trial-and-error procedures often being used. Our simulations correctly exhibited all the qualitative experimental observations for these systems, including the hydrophobic or hydrophilic behaviour of zeolite membranes. The simulations showed that, for Silicalite zeolite, the separation is strongly influenced by the selective adsorption of ethanol. The separation factor, as a consequence, increases almost exponentially as the ethanol composition decreases. For ethanol dehydration in NaA and Chabazite, pore size was found to play a very important role in the separation; very high separation factors were therefore possible. Simulations were also used to investigate the effect of pore structure, feed compositions and operating conditions on the pervaporation efficiency. Finally, our simulations also demonstrated that molecular simulations could serve as a useful screening tool to determine the suitability of a membrane for potential pervaporation separation applications. Simulations can cost only a small fraction of an experiment, and can therefore be used to design experiments most likely to be successful.     

Impacts of zeolite nanoparticles on substrate properties of thin film nanocomposite membranes for engineered osmosis

In this work, microporous substrates modified by zeolite nanoparticles were prepared and used for composite membrane making with the aim of reducing internal concentration polarization (ICP) effect of membranes during engineered osmosis applications. Nanocomposite substrates were fabricated via phase inversion technique by embedding nanostructured zeolite (clinoptilolite) in the range of 0–0.6 wt% into matrix of polyethersulfone (PES) substrate. Of all the substrates prepared, the PES0.4 substrate (with 0.4 wt% zeolite) exhibited unique characteristics, i.e., increased surface porosity, lower structural parameter (S) (from 0.78 to 0.48 mm), and enhanced water flux. The thin film nanocomposite (TFN) membrane made of this optimized substrate was also reported to exhibit higher water flux compared to the control composite membrane during forward osmosis (FO) and pressure-retarded osmosis (PRO) test, without compromising reverse solute flux. The water flux of such TFN membrane was 43% higher than the control TFC membrane (1.93 L/m² h bar) with salt rejection recorded at 94.7%. An increment in water flux is ascribed to the reduction in structural parameter, leading to reduced ICP effect.     

Polydisperse fluid in contact with a semipermeable membrane

Using density functional theory developed by Rosefeld, a model polydisperse fluid has been studied in contact with a membrane permeable to some components of the fluid. Calculations were carried out for three kinds of polydisperse fluid, each characterized by a different distribution of particle sizes. The structure of fluid has been evaluated on both sides of the membrane, plus the distribution of the particles in bulk fluid and in the surface layers. The adsorption and osmotic pressure in the system have been calculated.     

Molecular mobility and transport in polymer membranes and polyelectrolyte multilayers

Polyelectrolyte multilayers prepared by the layer-by-layer technique provide an efficient way to generate planar structures of tailored surface charge and hydrophobicity, which are used as membranes for pervaporation. The use of polyelectrolyte multilayers to form the membrane permits tailoring the surface charge of the membrane and, thus, selectivity; at the same time, it reduces fouling of the membrane by adsorption of organic matter. Pulsed field gradient (PFG) nuclear magnetic resonance has been used to investigate the diffusion of probe molecules into polymer systems. Evaluation of the apparent diffusion coefficient in porous poly(amide) results in a pore size of 4 microm, as found in electron micrographs. For the pore size obtained for polyelectrolyte multilayers, no equivalent pores could be found in microscopy. Propagators for the diffusion of propanol and propanol-water mixture into multilayers reveal that there might be selective interaction of probe molecules with the polyelectrolyte system.     

Molecular imprinting and adsorption of metallothionein on nanocrystalline titania membranes

Metallothionein (MT) imprinted TiO₂ membrane was synthesized via surface sol-gel process, using MT as template and TiO₂ sol as imprinted matrix. Appropriate template cavities in the TiO₂ sol-gel membrane were formed after the template molecules were removed on treatment with 1% NaOH solution. In situ technique of quartz crystal microbalance (QCM) was employed to study the molecular imprinting behavior of MT on nanocrystalline titania membranes. The imprinted membrane showed selectivity recognition for MT as compared to the other proteins. The amount of adsorption increased with the increasing of MT concentration both on imprinted membrane and non-imprinted membrane. The adsorption amount increased with the increasing of pH on imprinted membrane.     

Lattice gas simulations of osmosis

An analysis of the phenomenon of osmosis within the lattice gas model is presented. The model considered is a two-species version of the Frisch-Hasslacher-Pomeau model with rest particles and a semipermeable membrane which is implemented as a boundary that blocks one species, but lets the other pass freely. In this way the equilibrium between a pure and a mixed subsystem can be studied. Analytic expressions for both the pressure difference and the fluctuations of this quantity are obtained from the entropy function for the lattice gas, and we find that these results are in good agreement with those obtained from simulation. The osmotic flow across the membrane is also studied. We characterize the concentration boundary layer, and an analytic expression for the osmotic permeability as a function of porosity is compared with results from simulations.     

Fluid in contact with semipermeable vesicle: second-order integral equation approach

Secondorder Ornstein–Zernike integral equations in conjunction with the Lovett–Mou–Buff–Wertheim equation for the density profile are used to investigate a mixture of hard spheres in contact with a semipermeable membrane of spherical symmetry. Theoretical predictions are compared with grand canonical Monte Carlo simulations for several parameters, and reasonable agreement has been found. The pair functions for the systems considered are also determined and discussed.     

Membrane-water structural interactions in reverse osmosis transport

Reverse-osmotic water permeabilities, equilibrium water sorption levels, and rates of approach to sorption equilibrium were measured for a series of polymers, including hydroxyethyl methacrylate (HEMA), copolymers of HEMA and ethyl methacrylate (EMA), cellulose acetate, cellulose nitrate, and poly(urethans). Pronounced equilibrium solvent clustering behavior was observed for these systems as vapor saturation was approached in sorption experiments. However, clustering tendency was not found to be a function of total membrane water content at saturation but rather appears to be a function of the chemical nature of the polymer in question. Moreover, clustering of water molecules in (relatively) hydrophobic membranes resulted in low effective diffusivities (reverse osmotic permeability divided by equilibrium water content) whereas clustering in hydrophilic membranes led to higher effective water diffusivities. Clustering tendency was not as strong in the case of the weakly interacting membranes (i.e., the cellulose acetates). These conclusions were supported by theoretical diffusivity calculations. Predictions were based on analyses of transient sorption data, employing a dual-mode sorption model, and considering ordinary Fickian diffusion with simultaneous first-order reversible penetrant localization at water-binding sites in the polymer matrices. Means were found for correcting these diffusivity predictions to those values obtained experimentally under reverse osmosis conditions by accounting for the nonideality of the water flux under the latter conditions.     

Ergodic properties of the multidimensional rayleigh gas with a semipermeable barrier

We consider a multidimensional system consisting of a particle of massM and radiusr (molecule), surrounded by an infinite ideal gas of point particles of massm (atoms). The molecule is confined to the unit ball and interacts with its boundary (barrier) via elastic collision, while the atoms are not affected by the boundary. We obtain convergence to equilibrium for the molecule from almost every initial distribution on its position and velocity. Furthermore, we prove that the infinite composite system of the molecule and the atoms is Bernoulli.     

Molecular Stark effect spectroscopy of diflavonol and inhomogeneous broadening of its electronic spectra in erythrocyte membranes

Using spectroscopy of the molecular Stark effect and fluorescence spectroscopy, we study the characteristics of diflavonol 3,7-dihydroxy-2,8-di(4-dimethylaminophenyl)-4H,6H-pyrano[3,2-g]chromene-4,6-dione (DFME), which demonstrates intramolecular charge and proton phototransfer. In the ground state, this dye has only one form and, in the excited state, it has two forms, i.e., normal and phototautomeric. We found that, for the normal form of DFME, the transition dipole moment that is responsible for the absorption (m _a ), the dipole moment in the equilibrium ground state (μ _g ), and the change of the dipole moment upon transition of the molecule in the excited Franck-Condon state (Δ ^a μ) are parallel. In the ground equilibrium state, the dipole moments in 1,4-dioxane and cyclohexane are equal to μg = 12.2 × 10⁻³⁰ C m and μ _g = 11.0 × 10⁻³⁰ C m, respectively. Upon excitation, they increase by Δ ^a μ = 61 × 10⁻³⁰ C m and Δ ^a μ = 50.2 × 10⁻³⁰ C m in these solvents. We study the spectral characteristics of DFME in organic solvents and erythrocyte membranes. A spectral inhomogeneity of DFME in erythrocyte ghosts is found. The inhomogeneous broadening of fluorescence spectra is manifested as a long-wavelength shift of the band of the normal form of DFME by 1640 cm⁻¹ upon excitation at the red edge of the absorption spectrum.     

Molecular dynamics study of the shear strength and fracture behavior of nanoporous graphene membranes

We perform molecular dynamics (MD) simulations to study the structural response and fracture characteristics of nanoporous graphene (NPG) membranes subjected to shear loading. The effects of porosity, temperature, and shear velocity on the mechanical responses of NPG membranes are examined. The results show that the wrinkling of the membrane becomes more obvious with increasing strain. Fractures occur around holes on the long diagonal of the NPG parallelogram, and fracture stress in the NPG membrane decreases with increasing porosity. In addition, the effect of shear velocity on the shear modulus decreases with increasing porosity. The fracture strain of NPG membranes with different porosities obviously decreases with increasing temperature. The results enhance our understanding of the shear mechanical properties of NPG membranes and are helpful for the design and application of high-performance NPG membranes.     

Molecular simulations of phenol and ibuprofen removal from water using multilayered graphene oxide membranes

We present here non-equilibrium molecular dynamic simulations concerning the separation of phenol and ibuprofen as impurities compounds (ICs) in water by novel graphene oxide (GO) membranes. The coupling between water permeability and impurity rejection is studied as a function of membrane thickness and concentration, focusing on the underlying molecular phenomena. Results show that water permeability decreases as the number of layers increases. Moreover, molecular sieving can be achieved by tuning the number of GO layers and the surface chemistry of the sheet: water flow through layers is up to 20% faster than that in graphene layers, because of strong hydrogen bonded interactions with the oxygenated groups. Analysis of the simulation results suggests that upon adsorbing on the GO surface, the translational motion of ICs in water would be supressed. Nevertheless, hydrophilicity affects the permeability for membranes with high O/C ratio, owing to these strong hydrogen bonds. Furthermore, 100% rejection for the ICs can be obtained for most of the GO membranes with four layers. This study elucidates the important role of hydrophilic interactions in GO membranes to become ideal candidates for removal of organic pollutants from water, showing the applicability of molecular simulations to obtain molecular insights into this problem.     

渗透现象实验设计与研究

设计了一套渗透现象的定量观测实验装置用于大学基础物理实验教学.通过实验得到了渗透流量和渗透膜两侧溶液浓度差的线性关系,验证了渗透流量经验公式.此外,从物理学宏观和微观的角度给出了渗透现象的定性解释,并从基本的动力学理论出发引入了范托夫定律的理论推导.     

The use of ultrasound to reduce internal concentration polarization in forward osmosis

Unlike reverse osmosis (RO) that is dominated by the hydraulic pressure differential, forward osmosis (FO) uses the osmotic pressure gradient as the driving force between a dilute feed solution and a concentrated draw solution across a membrane. High pressure is not required in FO, which means that FO can be used as an alternative to RO as an energy-saving separation process in desalination technology. However, a major limiting factor of the FO process is the internal concentration polarization (ICP). Because of the stagnant environment inside the porous supporting layer of a FO membrane, it is difficult to mitigate the ICP by simply increasing the shear stress or promoting turbulence. In this study, the ICP is reduced by ultrasound. The effect of the ultrasound frequency and output power on the ICP coefficient is investigated in a flat-sheet FO membrane module with counter-current flow. The ultrasound frequency and output power are varied between 25, 45, and 72 kHz and over the range of 10–70 W, respectively. NaCl solution is used as both the feed and draw solution. The results illustrate that moderate ultrasonic irradiation is effective for reducing the ICP in a FO process. A modified solution–diffusion model based on film theory is used to assess the effect of ultrasound on the ICP in a FO process. The ICP coefficient is estimated using this model.