Size Exclusion Membrane Research Articles

Scalable membrane-assisted ion exchange (MEM-IE) strategy for organic acid purification in biorefinery process

The transition towards a carbon-neutral society necessitates radical approaches in the bio-refinery pipeline, particularly in the production of organic acids. The current downstream process from a dilute fermentation broth is limited by the extensive use of acids and bases, along with heavy reliance on energy-intensive distillation. In this work, we propose an entirely membrane-based process to purify organic acids (e.g., gluconic acid) from a crude solution of catalytic dehydrogenation of glucose. To facilitate downstream purification, we introduce an innovative membrane-assisted ion exchange (MEM-IE) strategy, which is a scalable process that can protonate ionic compounds entirely in the solution phase. Instead of a solid ion exchange resin, a bulky yet soluble acidification agent is used to protonate the target compound, which can be easily separated via a size exclusion membrane. We selected non-toxic poly (4-styrene sulfonic acid) (H-PSS, 75 kDa) as the acidification agent to selectively protonate gluconate ions and to enable facile fractionation. The proposed MEM-IE strategy can overcome the scale-up limitation of traditional solid ion exchange resins and can be applied to many types of ionic compounds. The versatility of the proposed process was also demonstrated on formate and lactate compounds. A techno-economic evaluation using the Verberne cost model showed that the proposed process achieves an 80 % reduction in energy consumption compared to the fermentation-based process, and the return on investment (ROI) of a 330 ton-per-day plant was less than a year. The proposed membrane-based process for the purification of organic acids, particularly the MEM-IE strategy, offers a sustainable and energy-efficient downstream separation platform.

Identification and characterization of a new potent inhibitor targeting CtBP1/BARS in melanoma cells

BackgroundThe C-terminal-binding protein 1/brefeldin A ADP-ribosylation substrate (CtBP1/BARS) acts both as an oncogenic transcriptional co-repressor and as a fission inducing protein required for membrane trafficking and Golgi complex partitioning during mitosis, hence for mitotic entry. CtBP1/BARS overexpression, in multiple cancers, has pro-tumorigenic functions regulating gene networks associated with “cancer hallmarks” and malignant behavior including: increased cell survival, proliferation, migration/invasion, epithelial-mesenchymal transition (EMT).Structurally, CtBP1/BARS belongs to the hydroxyacid-dehydrogenase family and possesses a NAD(H)-binding Rossmann fold, which, depending on ligands bound, controls the oligomerization of CtBP1/BARS and, in turn, its cellular functions.Here, we proposed to target the CtBP1/BARS Rossmann fold with small molecules as selective inhibitors of mitotic entry and pro-tumoral transcriptional activities.MethodsStructured-based screening of drug databases at different development stages was applied to discover novel ligands targeting the Rossmann fold. Among these identified ligands, N-(3,4-dichlorophenyl)-4-{[(4-nitrophenyl)carbamoyl]amino}benzenesulfonamide, called Comp.11, was selected for further analysis. Fluorescence spectroscopy, isothermal calorimetry, computational modelling and site-directed mutagenesis were employed to define the binding of Comp.11 to the Rossmann fold. Effects of Comp.11 on the oligomerization state, protein partners binding and pro-tumoral activities were evaluated by size-exclusion chromatography, pull-down, membrane transport and mitotic entry assays, Flow cytometry, quantitative real-time PCR, motility/invasion, and colony assays in A375MM and B16F10 melanoma cell lines. Effects of Comp.11 on tumor growth in vivo were analyzed in mouse tumor model.ResultsWe identify Comp.11 as a new, potent and selective inhibitor of CtBP1/BARS (but not CtBP2). Comp.11 directly binds to the CtBP1/BARS Rossmann fold affecting the oligomerization state of the protein (unlike other known CtBPs inhibitors), which, in turn, hinders interactions with relevant partners, resulting in the inhibition of both CtBP1/BARS cellular functions: i) membrane fission, with block of mitotic entry and cellular secretion; and ii) transcriptional pro-tumoral effects with significantly hampered proliferation, EMT, migration/invasion, and colony-forming capabilities. The combination of these effects impairs melanoma tumor growth in mouse models. ConclusionsThis study identifies a potent and selective inhibitor of CtBP1/BARS active in cellular and melanoma animal models revealing new opportunities to study the role of CtBP1/BARS in tumor biology and to develop novel melanoma treatments.

Hyperbranched TEMPO-based polymers as catholytes for redox flow battery applications.

Application of redox-active polymers (RAPs) in redox flow batteries (RFBs) can potentially reduce the stack cost through substitution of costly ion-exchange membranes by cheap size-exclusion membranes. However, intermolecular interactions of polymer molecules, i.e., entanglements, particularly in concentrated solutions, result in relatively high electrolyte viscosities. Furthermore, the large size and limited mobility of polymers lead to slow diffusion and more sluggish heterogeneous electron transfer rates compared to quickly diffusing small molecules. Although a number of RAPs with varying electrolyte viscosities have been reported in the literature, the relation between the RAP structure and the hydrodynamic properties has not been thoroughly investigated. Herein, hyperbranched 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)-based polymers intended for application as low-viscosity catholytes for RFBs are presented and the influence of the structure and the molar mass distribution on the hydrodynamic properties is investigated. A new synthesis approach for TEMPO-based polymers is established based on step-growth polymerization of a TEMPO-containing monomer using an aza-Michael addition followed by a postpolymerization modification to improve solubility in aqueous solutions. The compact structure of hyperbranched polymers was demonstrated using size-exclusion chromatography (SEC) with viscometric detection and the optimum molar mass was found based on the results of viscometric and crossover investigations. The resulting RAP revealed a viscosity of around 21 mPas at a concentration corresponding to around 1 M TEMPO-containing units, according to the calculated mass of the repeating unit, showing potential for high capacity polymer-based catholytes for RFBs. Nevertheless, possible partial deactivation of TEMPO units lowered the active TEMPO concentration of the hyperbranched RAPs. A faster diffusion and higher charge transfer rate were observed for the hyperbranched polymer compared to the previously reported linear polymers. However, in RFB tests, a poor performance was observed, which is attributed to the side reactions of the oxidized TEMPO moieties. Finally, pathways for overcoming the main remaining challenges, i.e., high loss of material during dialysis as an indication of being prone to crossover, the partial deactivation of TEMPO moieties, and the subsequent side reactions under battery conditions, are suggested.

Solutions Are the Problem: Ordered Two-Dimensional Covalent Organic Framework Films by Chemical Vapor Deposition.

Covalent organic frameworks (COFs) are a promising class of crystalline polymer networks that are useful due to their high porosity, versatile functionality, and tunable architecture. Conventional solution-based methods of producing COFs are marred by slow reactions that produce powders that are difficult to process into adaptable form factors for functional applications, and there is a need for facile and fast synthesis techniques for making crystalline and ordered covalent organic framework (COF) thin films. In this work, we report a chemical vapor deposition (CVD) approach utilizing co-evaporation of two monomers onto a heated substrate to produce highly crystalline, defect-free COF films and coatings with hydrazone, imine, and ketoenamine COF linkages. This all-in-one synthesis technique produces highly crystalline, 40 nm-1 μm-thick COF films on Si/SiO2 substrates in less than 30 min. Crystallinity and alignment were proven by using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and transmission electron microscopy (TEM), and successful conversion of the monomers to produce the target COF was supported by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV-vis measurements. Additionally, we used atomic force microscopy (AFM) to investigate the growth mechanisms of these films, showing the coalescence of triangular crystallites into a smooth film. To show the wide applicability and scope of the CVD process, we also prepared crystalline ordered COF films with imine and ketoenamine linkages. These films show potential as high-quality size exclusion membranes, catalytic platforms, and organic transistors.

Exploring the Impact of Oligomerization on Redox Flow Cell Performance

The redox flow battery (RFB) is a promising stationary energy storage technology due to its inherent decoupling of energy and power, long service lifetime, and potential for low-cost manufacturing.1 While current embodiments are constrained by high upfront cost, nonaqueous RFBs may offer a pathway to cost-competitive energy storage systems through higher energy densities;2 however, this concept is at an early stage and several challenges must be overcome. In particular, the development of stable, high-voltage redox chemistries in conjunction with low-cost, selective membranes is needed to mitigate difficult-to-reverse capacity fade and reduced efficiencies. As such, a range of redox-active organic macrostructures, including oligomers (RAOs),3 polymers (RAPs),4 and colloids (RACs),5 have been described in the peer-reviewed literature. Of specific interest are RAOs, which, like the other macrostructures, can be paired with size-exclusion membranes but exhibit electrochemical and fluid dynamic properties that more closely align with monomers. While this proof-of-concept has been demonstrated,6,7 to our knowledge, few studies have systematically evaluated how the molecular properties of RAOs influence their performance in flow cells.In this presentation, we will describe our efforts to understand how the molecular properties of different oligomers influence their behavior in redox flow cells. To this end, we synthesize and characterize a set of model compounds, ranging from monomers to tetramers, that utilize TEMPO as the redox-active unit. We then assess the thermodynamic, kinetic, and transport properties of these compounds using a suite of voltammetric techniques. Subsequently, we characterize the performance and durability of these compounds in symmetric flow cells via electrochemical impedance spectroscopy, DC polarization, and durational cycling. We perform post-test characterization after the cycling experiments to disaggregate molecular- and cell-level sources of capacity fade. We find that, in general, oligomers with increased size exhibit lower diffusivities while maintaining the facile charge transfer characteristics afforded by the appended monomer. These size-dependent variations in mass transport rates directly translate to differences in cell polarization and cycling performance. Time-dependent capacity fade observed during cycling is confirmed by post-mortem analysis. Broadly, these results align with previously developed relationships between molecular size, electrochemical properties, and flow cell performance; we posit that the principles for functionalization and testing utilized here can be applied to other RAOs with improved stability. Acknowledgements This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. B.J.N gratefully acknowledges the NSF Graduate Research Fellowship Program under Grant Number 1122374. Any opinion, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. The authors thank Jeffrey Kowalski and Katharine Greco of the Brushett Group as well as Yu Cao and Jeffrey Moore of the Moore Group at the University of Illinois for their contributions to conceptualizing the framework and preliminary testing for this work.

Aqueous Colloid Flow Batteries Based on Redox-Reversible Polyoxometalate Clusters and Size-Exclusive Membranes

Aqueous redox flow batteries (ARFBs) exhibit great potential for large-scale energy storage, but the cross-contamination, limited ion conductivity, and high costs of ion-exchange membranes restrict the wide application of ARFBs. Herein, we report the construction of aqueous colloid flow batteries (ACFBs) based on redox-active polyoxometalate (POM) colloid electrolytes and size-exclusive membrane separators. The aqueous suspensions of POM clusters, such as [N(C3H7)4]4[H12(VO2)12(C6H5PO3)8]·xH2O and [N(C3H7)4]4[H12(VO2)12(4-FC6H4PO3)8]·xH2O, deliver good reversibility, high redox kinetics, and long cycling life. The nanoscale sizes of POM clusters make them compatible with cheap commercial dialysis membrane separators to replace expensive ion-exchange membranes, thus inhibiting the cross-contamination of active species via size exclusion. The ACFBs achieve a high energy efficiency of ∼90% and an ultralow capacity fade rate of 0.004% per cycle. This work highlights the great potential of ACFBs based on redox-reversible POM clusters and size-exclusion membrane separators toward grid-scale and sustainable energy storage applications.

Ionic Effect on Electrochemical Behavior of Water-Soluble Radical Polyelectrolytes

Water-soluble redox-active polymers (RAPs) have emerged as attractive electroactive materials for aqueous redox flow batteries because these systems rely on readily available size-exclusion membranes rather than expensive ion-selective membranes. While incorporating ionic units is the most effective strategy for forming water-soluble redox polyelectrolytes, little is known about how charges dictate their electrochemical behavior. Here, we design a series of water-soluble TEMPO (2,2,6,6-tetramethylpiperidyl-1-oxy) radical polyelectrolytes with identical radical distribution but various ionic groups through a sequential postmodification method. Physical and electrochemical characterizations show disparate diffusion coefficients (D) and charge transfer kinetics (k0) of these radical polyelectrolytes at various pH. Particularly, pH exerts a strong impact on k0 of the negatively charged polymer (i.e., with carboxylic acid groups). The bimolecular reaction rate kex determined from redox-induced polymer films shows electrostatic interactions between charged segments can enhance the electron self-exchange reaction rate by ten folds. The results suggest that charge effects are of great importance when designing water-soluble redox polymers for electrochemical applications.

A Materials Science Perspective of Midstream Challenges in the Utilization of Heavy Crude Oil.

An increasing global population and a sharply upward trajectory of per capita energy consumption continue to drive the demand for fossil fuels, which remain integral to energy grids and the global transportation infrastructure. The oil and gas industry is increasingly reliant on unconventional deposits such as heavy crude oil and bitumen for reasons of accessibility, scale, and geopolitics. Unconventional deposits such as the Canadian Oil Sands in Northern Alberta contain more than one-third of the world’s viscous oil reserves and are vital linchpins to meet the energy needs of rapidly industrializing populations. Heavy oil is typically recovered from subsurface deposits using thermal recovery approaches such as steam-assisted gravity drainage (SAGD). In this perspective article, we discuss several aspects of materials science challenges in the utilization of heavy crude oil with an emphasis on the needs of the Canadian Oil Sands. In particular, we discuss surface modification and materials’ design approaches essential to operations under extreme environments of high temperatures and pressures and the presence of corrosive species. The demanding conditions for materials and surfaces are directly traceable to the high viscosity, low surface tension, and substantial sulfur content of heavy crude oil, which necessitates extensive energy-intensive thermal processes, warrants dilution/emulsification to ease the flow of rheologically challenging fluids, and engenders the need to protect corrodible components. Geopolitical reasons have further led to a considerable geographic separation between extraction sites and advanced refineries capable of processing heavy oils to a diverse slate of products, thus necessitating a massive midstream infrastructure for transportation of these rheologically challenging fluids. Innovations in fluid handling, bitumen processing, and midstream transportation are critical to the economic viability of heavy oil. Here, we discuss foundational principles, recent technological advancements, and unmet needs emphasizing candidate solutions for thermal insulation, membrane-assisted separations, corrosion protection, and midstream bitumen transportation. This perspective seeks to highlight illustrative materials’ technology developments spanning the range from nanocomposite coatings and cement sheaths for thermal insulation to the utilization of orthogonal wettability to engender separation of water–oil emulsions stabilized by endogenous surfactants extracted during SAGD, size-exclusion membranes for fractionation of bitumen, omniphobic coatings for drag reduction in pipelines and to ease oil handling in containers, solid prills obtained from partial bitumen solidification to enable solid-state transport with reduced risk of damage from spills, and nanocomposite coatings incorporating multiple modes of corrosion inhibition. Future outlooks for onsite partial upgradation are also described, which could potentially bypass the use of refineries for some fractions, enable access to a broader cross-section of refineries, and enable a new distributed chemical manufacturing paradigm.

A Viologen Polymer and a Compact Ferrocene: Comparison of Solution Viscosities and Their Performance in a Redox Flow Battery with a Size Exclusion Membrane

AbstractIn this work, the synthesis and characterization of a compact, ferrocene tetramer and a linear viologen polymer is reported. The latter material is a new, 4,4′‐bipyridine containing, organo‐soluble polymer. As aimed for solubility in nonpolar solvents, a 2‐ethylhexyl‐moiety to promote organosolubility and 4‐vinylbenzyl serving as a polymerizable group are introduced to a 4,4′‐bipyridine. The halide anions of the monomer cation are exchanged to bis(trifluoromethansulfon)imide, which further enhances organosolubility. The monomer is subsequently copolymerized with styrene by free radical polymerization. In addition, a four‐ferrocene‐containing compact structure, based on pentaerythritol, is synthesized via the straightforward radical thiol‐ene reaction. The polymer solutions are thoroughly characterized hydrodynamically. Subsequently, propylene carbonate‐based solutions of both materials are prepared to allow an assessment for future energy storage applications. This is done by testing battery characteristics in a custom‐made flow‐cell with a simple dialysis membrane for physical separation of the active materials. The capability of energy storage is verified by leaving the charged materials in solution in an open circuit for 24 h. Here, more than 99% of the stored charges can be recovered. Cycling the battery for 100 times reveals the remarkable stability of the materials of only 0.2% capacity loss per day in the battery setup.

Specialized Plant Growth Chamber Designs to Study Complex Rhizosphere Interactions.

The rhizosphere is a dynamic ecosystem shaped by complex interactions between plant roots, soil, microbial communities and other micro- and macro-fauna. Although studied for decades, critical gaps exist in the study of plant roots, the rhizosphere microbiome and the soil system surrounding roots, partly due to the challenges associated with measuring and parsing these spatiotemporal interactions in complex heterogeneous systems such as soil. To overcome the challenges associated with in situ study of rhizosphere interactions, specialized plant growth chamber systems have been developed that mimic the natural growth environment. This review discusses the currently available lab-based systems ranging from widely known rhizotrons to other emerging devices designed to allow continuous monitoring and non-destructive sampling of the rhizosphere ecosystems in real-time throughout the developmental stages of a plant. We categorize them based on the major rhizosphere processes it addresses and identify their unique challenges as well as advantages. We find that while some design elements are shared among different systems (e.g., size exclusion membranes), most of the systems are bespoke and speaks to the intricacies and specialization involved in unraveling the details of rhizosphere processes. We also discuss what we describe as the next generation of growth chamber employing the latest technology as well as the current barriers they face. We conclude with a perspective on the current knowledge gaps in the rhizosphere which can be filled by innovative chamber designs.

Analysis of circulating breast cancer cell heterogeneity and interactions with peripheral blood mononuclear cells.

For solid tumors, extravasation of cancer cells and their survival in circulation represents a critical stage of the metastatic process that lacks complete understanding. Gaining insight into interactions between circulating tumor cells (CTCs) and other peripheral blood mononuclear cells (PBMCs) may provide valuable prognostic information. The purpose of this study was to use single-cell RNA-sequencing (scRNA-seq) of liquid biopsies from breast cancer patients to begin defining intravascular interactions. We captured CTCs from the peripheral blood of breast cancer patients using size-exclusion membranes followed by scRNA-seq of enriched CTCs and carry-over PBMCs. Transcriptome analysis identified two populations of CTCs: one enriched for transcripts indicative of estrogen responsiveness and increased proliferation and another enriched for transcripts characteristic of reduced proliferation and epithelial-mesenchymal transition (EMT). We applied interactome and pathway analysis to determine interactions between CTCs and other captured cells. Our analysis predicted for enhanced immune evasion in the CTC population with EMT characteristics. In addition, PD-1/PD-L1 pathway activation and T cell exhaustion were predicted in T cells isolated from breast cancer patients compared with normal T cells. We conclude that scRNA-seq of breast cancer CTCs generally stratifies them into two types based on their proliferative and epithelial state and differential potential to interact with PBMCs. Better understanding of CTC subtypes and their intravascular interactions may help design treatments directed against CTCs with high metastatic and immune-evasive competence.

Microscopic visualization of virus removal by dedicated filters used in biopharmaceutical processing: Impact of membrane structure and localization of captured virus particles.

Virus filtration with nanometer size exclusion membranes (“nanofiltration”) is effective for removing infectious agents from biopharmaceuticals. While the virus removal capability of virus removal filters is typically evaluated based on calculation of logarithmic reduction value (LRV) of virus infectivity, knowledge of the exact mechanism(s) of virus retention remains limited. Here, human parvovirus B19 (B19V), a small virus (18–26 nm), was spiked into therapeutic plasma protein solutions and filtered through Planova™ 15N and 20N filters in scaled‐down manufacturing processes. Observation of the gross structure of the Planova hollow fiber membranes by transmission electron microscopy (TEM) revealed Planova filter microporous membranes to have a rough inner, a dense middle and a rough outer layer. Of these three layers, the dense middle layer was clearly identified as the most functionally critical for effective capture of B19V. Planova filtration of protein solution containing B19V resulted in a distribution peak in the dense middle layer with an LRV >4, demonstrating effectiveness of the filtration step. This is the first report to simultaneously analyze the gross structure of a virus removal filter and visualize virus entrapment during a filtration process conducted under actual manufacturing conditions. The methodologies developed in this study demonstrate that the virus removal capability of the filtration process can be linked to the gross physical filter structure, contributing to better understanding of virus trapping mechanisms and helping the development of more reliable and robust virus filtration processes in the manufacture of biologicals.

Interleukin-1 causes CNS inflammatory cytokine expression via endothelia-microglia bi-cellular signaling

As a major producer of the inflammatory cytokine interleukin-1 (IL-1), peripheral macrophages can augment IL-1 expression via type 1 IL-1 receptor (IL-1R1) mediated autocrine self-amplification. In the CNS, microglial cells are the major producers of inflammatory cytokines, but express negligible levels of IL-1R1. In the present study, we showed CNS IL-1 induced microglial proinflammatory cytokine expression was mediated by endothelial, not microglial, IL-1R1. This paracrine mechanism was further dissected in vitro. IL-1 was unable to stimulate inflammatory cytokine expression directly from the microglial cell line BV-2, but it stimulated the brain endothelial cell line bEnd.3 to produce a factor(s) in the culture supernatant, which was capable of inducing inflammatory cytokine expression in BV-2. We termed this factor IL-1-induced microglial activation factors (IMAF). BV-2 cytokine expression was inducible by extracellular ATP, but IL-1 did not stimulate the release of ATP from bEnd.3 cells. Filtration of IMAF by size-exclusion membranes showed IMAF activity resided in molecules larger than 50 kd and incubation of IMAF at 95 °C for 5 min did not alter its activity. Microglial inhibitor minocycline was unable to block IMAF activity, even though it blocked LPS induced cytokine expression in BV-2 cells. Adding NF-κB inhibitor to the bEnd.3 cells abolished IL-1 induced cytokine expression in this bi-cellular system, but adding NF-κB inhibitor after IMAF is already produced failed to abrogate IMAF induced cytokine expression in BV-2 cells. RNA sequencing of IL-1 stimulated endothelial cells revealed increased expression of genes involved in the production and processing of hyaluronic acid (HA), suggesting HA as a candidate of IMAF. Inhibition of hyaluronidase by ascorbyl palmitate (AP) abolished IMAF-induced cytokine expression in BV-2 cells. AP administration in vivo also inhibited ICV IL-1-induced IL-1 expression in the hippocampus and hypothalamus. In vitro, either TLR2 or TLR4 inhibitors blocked IMAF induced BV-2 cytokine expression. In vivo, however, IL-1 induced cytokine expression persisted in either TLR2 or TLR4 knockouts. These results demonstrate IL-1 induced inflammatory cytokine expression in the CNS requires a bi-cellular system and HA could be a candidate for IMAF.

Investigation of virus retention by size exclusion membranes under different flow regimes.

Virus removal by filter membranes is regarded as a robust and efficient unit operation, which is frequently applied in the downstream processing of biopharmaceuticals. The retention of viruses by virus filtration membranes is predominantly based on size exclusion. However, recent results using model membranes and bacteriophage PP7 point to the fact that virus retention can also significantly be influenced by adsorptive interactions between virus, product molecules, and membranes. Furthermore, the impact of flow rate and flow interruptions on virus retention have been studied and responsible mechanisms discussed. The aim of this investigation was to gain a holistic understanding of the underlying mechanisms for virus retention in size exclusion membranes as a function of membrane structure and membrane surface properties, as well as flow and solution conditions. The results of this study contribute to the differentiation between size exclusion and adsorptive effects during virus filtration and broaden the current understanding of mechanisms related to virus breakthroughs after temporary flow interruptions. Within the frame of a Design of Experiments approach it was found that the level of retention of virus filtration membranes was mostly influenced by the membrane structure during typical process-related flow conditions. The retention performance after a flow interruption was also significantly influenced by membrane surface properties and solution conditions. While size exclusion was confirmed as main retention mechanism, the analysis of all results suggests that especially after a flow interruption virus retention can be influenced by adsorptive effects between the virus and the membrane surface. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 35: e2747, 2019.

Surface-Engineered Inorganic Nanoporous Membranes for Vapor and Pervaporative Separations of Water⁻Ethanol Mixtures.

Surface wettability-tailored porous ceramic/metallic membranes (in the tubular and planar disc form) were prepared and studied for both vapor-phase separation and liquid pervaporative separations of water-ethanol mixtures. Superhydrophobic nanoceramic membranes demonstrated more selective permeation of ethanol (relative to water) by cross-flow pervaporation of liquid ethanol–water mixture (10 wt % ethanol feed at 80 °C). In addition, both superhydrophilic and superhydrophobic membranes were tested for the vapor-phase separations of water–ethanol mixtures. Porous inorganic membranes having relatively large nanopores (up to 8-nm) demonstrated good separation selectivity with higher permeation flux through a non-molecular-sieving mechanism. Due to surface-enhanced separation selectivity, larger nanopore-sized membranes (~5–100 nm) can be employed for both pervaporation and vapor phase separations to obtain higher selectivity (e.g., permselectivity for ethanol of 13.9 during pervaporation and a vapor phase separation factor of 1.6), with higher flux due to larger nanopores than the traditional size-exclusion membranes (e.g., inorganic zeolite-based membranes having sub-nanometer pores). The prepared superhydrophobic porous inorganic membranes in this work showed good thermal stability (i.e., the large contact angle remains the same after 300 °C for 4 h) and chemical stability to ethanol, while the silica-textured superhydrophilic surfaced membranes can tolerate even higher temperatures. These surface-engineered metallic/ceramic nanoporous membranes should have better high-temperature tolerance for hot vapor processing than those reported for polymeric membranes.

Latest advances in degumming feedstock oils for large‐scale biodiesel production

The removal of gummy or mucilaginous substances from vegetable oils, commonly known as degumming, is required for the use of crude vegetable oils as the feedstock for biodiesel production. These gums reduce the rate of transesterification reactions by deactivation of the catalyst and they hinder the separation of the glycerol phase from the biodiesel. They also cause the deposition of carbon particles within engine machinery and affect performance. To take care of these issues, gums should be separated from the oils to make the oils suitable for use as fuel. Chemical treatment, membrane separation, and biological separation processes have been reported in the literature for this purpose. In the chemical treatment process aqueous solutions of chemicals like acids, bases, ethylenediaminetetraacetic acid (EDTA), and water are used for separating gums. The membrane separation process is based on size exclusion, and polymeric, ceramic, and inorganic membranes are used to separate gums from oil. In biological degumming, phospholipase groups of enzymes are used. These enzymes hydrolyze gums into fatty acids and lipophilic substances. Enzyme degumming also enhances oil‐phase yield. This paper reviews the chemical nature of gums and presents a comprehensive critical summary of different degumming technologies, their specific features, effecting parameters, advantages and disadvantages, and industrial uses. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd.

Effect of Formulation Additives on Drug Transport through Size-Exclusion Membranes.

The aim of this research was to investigate the driving force of membrane transport through size-exclusion membranes and to provide a concentration-based mathematical description of it to evaluate whether it can be an alternative for lipophilic membranes in the formulation development of amorphous solid dispersions. Carvedilol, an antihypertensive drug, was chosen and formulated using solvent-based electrospinning to overcome the poor water solubility of the drug. Vinylpyrrolidone-vinyl acetate copolymer (PVPVA64) and Soluplus were used to create two different amorphous solid dispersions of the API. The load-dependent effect of the additives on dissolution and permeation through regenerated cellulose membrane was observed by a side-by-side diffusion cell, μFLUX. The solubilizing effect of the polymers was studied by carrying out thermodynamic solubility assays. The supersaturation ratio (SSR, defined as the ratio of dissolved amount of the drug to its thermodynamic solubility measured in exactly the same medium) was found to be the driving force of membrane transport in the case of size-exclusion membranes. Although the transport through lipophilic and size-exclusion membranes is mechanistically different, in both cases, the driving force of membrane transport in the presence of polymer additives was found to be the same. This finding may enable the use of size-exclusion membranes as an alternative to lipid membranes in formulation development of amorphous solid dispersions.

High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries.

Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. These studies provide a template for the future design of other redox-active oligomers for this application.

Retention of Acholeplasma laidlawii by Sterile Filtration Membranes: Effect of Cultivation Medium and Filtration Temperature.

ALCM: A. laidlawii culture medium; ASTM: American Society for Testing and Materials; ATCC: American Type Culture Collection; CFU/mL: colony-forming units per milliliter; DLS: Dynamic light scattering; LRV: Log reduction value; PES: Polyethersulfone; PFU/mL: Plaque-forming units per milliliter; PSD: Particle size distribution; PVP: Polyvinylpyrrolidone; SDS: Sodium dodecyl sulfate; SEM: Scanning electron microscopy; SLB: Saline lactose broth; TMP: Transmembrane pressure; TSB: Tryptic soy broth.

Development and optimisation of a novel three-way extraction technique based on a combination of Soxhlet extraction, membrane assisted solvent extraction and a molecularly imprinted polymer using sludge polycyclic aromatic hydrocarbons as model compounds.

A novel technique that integrates extraction and clean-up into a single step format is reported as part of the search for new sample preparation techniques in the analysis of persistent organic pollutants from complex samples. This was achieved by combining the extraction efficiency of the Soxhlet extractor, the selectivity of a size exclusion membrane and the specificity of a molecularly imprinted polymer for the extraction of polycyclic aromatic hydrocarbons from wastewater sludge followed by quantitation using gas chromatography with time-of-flight mass spectrometry. The approach is described as the Soxhlet extraction membrane-assisted solvent extraction molecularly imprinted polymer technique. This technique was optimised for various parameters such as extraction solvent, reflux time and membrane acceptor phase. The applicability of the developed technique was optimised using a wastewater sludge certified reference material and then tested on real wastewater sludge samples. The method detection limits ranged from 0.14 to 12.86ng/g with relative standard deviation values for the extraction of the 16 US-EPA priority polycyclic aromatic hydrocarbons from wastewater sludge samples ranging from 0.78 to 18%. The extraction process was therefore reproducible and showed remarkable selectivity. The developed technique is a promising prospect that can be applied in the analysis of organic pollutants from complex solid samples.