Membrane properties of trisulfonated hydrophilic and partially fluorinated hydrophobic multiblock copolymer
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Anomalities in water and aqueous systems, and temperature effects on membranes
Reverse osmosis (RO) is a compact process that has potential for the removal of ionic and organic pollutants for recycling space mission wastewater. Seven candidate RO membranes were compared using a batch stirred cell to determine the membrane flux and the solute rejection for synthetic space mission wastewaters. Even though the urea molecule is larger than ions such as Na+, Cl-, and NH4+, the rejection of urea is lower. This indicates that the chemical interaction between solutes and the membrane is more important than the size exclusion effect. Low pressure reverse osmosis (LPRO) membranes appear to be most desirable because of their high permeate flux and rejection. Solute rejection is dependent on the shear rate, indicating the importance of concentration polarization. A simple transport model based on the solution-diffusion model incorporating concentration polarization is used to interpret the experimental results and predict rejection over a range of operating conditions. Grant numbers: NAG 9-1053.
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With the growing need for chemical separation and chemical storage solutions, polymeric adsorbents have emerged as a promising class of candidate materials because of their potentially tunable sorption properties, membrane structure and relatively cost consciousness. Moreover, the developing field of polymeric membrane materials has shown particular success at integrating both experimental and computational studies. However, these material systems are known to suffer from varying degrees of induced membrane structural rearrangement upon adsorbate uptake, and thus many polymeric membrane performance metrics are often considered to degrade with an increasing number of ‘guest’ species. In this mini–review, we highlight methodology tradeoffs and provide insights into atomistic molecular simulations used to study adsorption with flexible frameworks, which have the potential to predict separation, storage or catalytic capabilities a priori to experimental efforts. Specifically, molecular simulation methods that have been applied to provide predictions of polymeric membrane properties that have included consideration for sorbate–induced polymer chain rearrangement, swelling and/or plasticization are reviewed. Here, the examples and methodologies described provide demonstrations of the applicability of simulations as an approach to understand adsorption–based phenomena at an atomistic/molecular level, and as a tool to carry out screening studies aimed at efficiently providing analysis for a diversity of polymeric adsorbent–adsorbate systems.
Membranes are synthesized from ethylene and nitrogen in RF plasma at low power, gas-flow rates, and pressure. Ethylene and nitrogen are used because flow rate and partial pressure of each gas can be independently controlled to produce optimum conditions for synthesizing membrane. Membrane is particularly useful in recycling and purifying water.
Phospholipids form structurally and compositionally diverse membranes. A less studied type of compositional diversity involves phospholipid tail variety. Some phospholipids contain two acyl tails which differ in length. These tail-asymmetric lipids are shown to contribute to temperature sensitivity, oxygen adaptability, and membrane fluidity. Membranes of a highly virulent intracellular bacterium, Francisella tularensis, contain highly tail-asymmetric 1-lignoceroyl-2-decanoyl-sn-glycero-3-phosphatidylethanolamine (XJPE) lipids which were previously shown to inhibit inflammatory responses in host cells. XJPE tails have unusually high asymmetry, and how they contribute to membrane properties on a molecular level is unknown. Here, we use small angle X-ray scattering and molecular dynamics simulations to investigate how varying XJPE ratios alters properties of simple membranes. Our results demonstrate that at high concentration they promote liquid-to-gel transition in otherwise liquid membranes, while at low concentration they are tolerated well, minimally altering membrane properties. In liquid membranes, XJPE lipids dynamically adopt two main conformations; with the long tail extended into the opposing leaflet or bent-back residing in its own leaflet. When added to both leaflets XJPE primarily adopts an extended confirmation, while asymmetric addition results in more bent-back orientations. The former increases tail ordering and the latter decreases it. XJPE tails adopt different conformations that induce composition- and leaflet-dependent bidirectional effect on membrane fluidity and this suggests that Francisella tularensis could use tail asymmetry to facilitate vesicle fusion and destabilize host cells. The effect of tail-asymmetric lipids on complex membranes should be further investigated to reveal the regulatory roles of high tail asymmetry.
Cost optimal design of osmotic membrane processes requires an accurate estimate of membrane transport parameters across their full operational range. However, standard approaches for estimating these parameters rely on empirical methods, the accuracy of which remains unquantified as a function of temperature, salinity, and measurement error. Herein, we present a systematic accuracy analysis of previously developed methods for estimation of membrane transport properties in reverse osmosis, high-pressure reverse osmosis, forward osmosis, pressure retarded reverse osmosis, and osmotically assisted reverse osmosis. We use a Monte Carlo approach to sample the full range of feasible membrane water permeabilities, salt permeabilities, structural parameters, and operating conditions for these processes. These material and process parameters are then incorporated into a physical transport model for each process. Our analysis shows that the statistical uncertainty of current empirical methods for estimating membrane parameters increases by 5 times from low-salinity to high-salinity conditions. Here, the result of this work demonstrates that empirical methods are inadequate for precisely estimating membrane transport properties at high salinity and highlight a critical need for the development of statistically validated higher accuracy methods.
Membrane-like properties of synthetic protenoid microparticulate systems, considering catalytic activities, size and ultrastructure
Modification of the gas permeation properties of ZIF-8 membranes using electron beam irradiation is reported. 3.8 and 3.2 fold enhancements in ideal selectivity for CO 2 /N 2 and CO 2 /CH 4 can be achieved with less than 1 min exposure time.
The possibility that the amphiphilic compounds in carbonaceous meteorites whose physicochemical properties are presently studied may represent sources of lipidlike compounds which could have evolved as membrane components in primitive cells is investigated in samples of the Murchison CM2 chondrite. Surface properties and membrane formation are obtained for three fractions isolated by two-dimensional thin-layer chromatography. It is concluded that a small, undefined fraction of Murchison components exhibits amphiphilic properties which allow assembly into boundary membranes.
Conventional compressor-based cooling has undergone incremental changes over the past 100 years. Further improvements in efficiency require evermore complex systems, especially under humid conditions. Meso-porous membranes offer unique opportunities for efficient humidity control in buildings using an absorbent desiccant solution, but membranes are not designed or optimized for this purpose. This project will use molecular dynamic simulations to determine optimal membrane properties for these air conditioning applications, focusing on the membrane properties at the membrane/liquid/air interface. Optimal membrane designs will enable smaller, more durable, and less expensive designs of these membrane air conditioning systems.
As a core component of biological and synthetic membranes, lipid bilayers are key to compartmentalizing chemical processes. Bilayer morphology and mechanical properties are heavily influenced by electric fields such as those caused by biological ion concentration gradients. We present atomistic simulations exploring the effects of electric fields applied normally and laterally to lipid bilayers. We find that normal fields decrease membrane tension, while lateral fields increase it. Free energy perturbation calculations indicate the importance of dipole-dipole interactions to these tension changes, especially for lateral fields. We additionally show that membrane area compressibilities can be related to their cohesive energies, allowing us to estimate changes in membrane bending rigidity under applied fields. We find that normal fields decrease bending rigidity, while lateral fields increase it. Furthermore, these results point to the use of directed electric fields to locally control membrane stiffness, thereby modulating associated cellular processes.
Lipid membranes, the primary matrix of cell membranes, exhibit a hierarchy of dynamics from molecular motions to collective undulations, which control spatiotemporal membrane phenomena and regulate various cellular functions. Thus, understanding how various dynamic modes influence membrane behavior is crucial to uncovering the design rules of cell membranes and implementing them in future technologies. Previous membrane dynamics studies using neutron spin-echo spectroscopy (NSE) have shed light on the dependence of collective membrane fluctuations on viscoelastic membrane properties, demonstrating that thickness fluctuation modes (100ns) are dictated by membrane viscosity, which directly governs fast (ps) molecular diffusive motions. Here, we focus on phase-separating lipid membranes, composed of DMPC:DSPC mixtures, to understand the effect of domain formation/growth on hierarchical matrix dynamics using selective lipid deuteration and different neutron spectroscopy techniques. NSE measurements on DMPC:DSPC-d83 (70:30 mol%) show that bending rigidity of the DMPC-rich matrix graduallyincreases with decreasing temperature - as the fully-fluid membrane approaches the upper phase transition (i.e. with the formation of transient DSPC clusters) - and increases further in the phase coexistence region with the growth of DSPC domains. Comparatively, NSE measurements on DMPC-d54:DSPC-d83 vesicles show pronounced matrix thickness fluctuations in the fully-fluid phase and drastic suppression of this fluctuation mode in the gel-fluid coexistence phase, even when the DMPC-rich matrix is still in its fluid phase. This suppression in fluctuations suggests an increase in the matrix viscosity with the growth of gel DSPC domains, which is further investigated by selectively measuring lipid diffusion in the DMPC-rich matrix using neutron backscattering spectroscopy. Comparisons of the experimental results with coarse-grained MD simulationsillustrate the underlying coupling mechanisms. Overall, these observations indicate a clear mechanical and viscoelastic coupling betweenlipid domains and their host matrix, suggesting that domain formation influences membrane properties beyond local effects.
Membrane polymers are a promising technology for use in many challenging gas separation applications. Here, the techniques of computer-aided molecular design can be used to search through the massive molecular space of heteropolymers and develop a set of likely candidate repeat units matching specific physical property targets. However, reasonably accurate property prediction algorithms are needed, but these algorithms must be very fast in order to be combined with an optimization framework. Artificial neural networks (ANNs), a branch of machine learning, are applied in this work to predict the physical properties of polymers. All of the physical properties investigated were found to be predicted by ANNs with R 2 scores exceeding 0.82.
Here, we present a simple and robust method to simultaneously characterize the water and salt permeability (A, B) of reverse osmosis (RO) membranes and mass transfer coefficient (k) in membrane modules. The proposed methodology comprises a set of RO experiments performed at different operating pressures or stages. The measured water and salt fluxes in each stage are simultaneously fitted to the RO transport equations by performing a non-linear regression, using A, B, and k as regression parameters. We first perform a systematic accuracy analysis of the proposed method across the full operational range of RO. The assessment shows that the method accuracy is substantially higher than current methods and increases with number of experimental stages and driving forces. This assessment is used to inform the design of an experimental protocol that minimizes errors in estimated A, B, and k. We then evaluate two commercial RO membranes following the new protocol. For both membranes, A and B parameters decrease by 17% and 15% from the dilute solution to seawater concentrations, whereas the k parameter remains constant. Our study demonstrates that the proposed method, informed by data-driven experimental designs, provides a new approach for accurately characterizing transport phenomenon in membrane processes with feeds of less than 100 g/L total dissolved solids.