Fabrication of Ultrathin Membranes Using 2D-MOF Nanosheets for Tunable Gas Separation

Two-dimensional (2D) metal-organic frameworks (MOF) nanosheets have emerged as novel membrane materials for gas separation. However, the development of ultrathin MOF membranes with tunable separation performances is still a challenge. Herein, we developed a facile GO-assisted restacking method to fabricate defect-free membranes with monolayer Zr-BTB nanosheets. Obtained ultrathin membranes ranging from 130 nm to 320 nm show tunable separation performances and exceed the 2008 Robeson upper bound by changing the amount of nanolayers in vertical stacking direction. Furthermore, a heating filtration method was used to change the restacking process of nanosheets in the horizontal direction. As a result, H₂/CO₂ selectivity can be enhanced by two times with the same membrane thickness (130 nm) and H₂ permeance is almost maintained to be 7.0×10⁻⁷ mol m⁻² s⁻¹ pa⁻¹. This method may provide a possible way to efficiently tune the gas separation performances of MOF membranes.     

Cable-like carbon nanotubes decorated metal-organic framework derived ultrathin CoSe2/CNTs nanosheets for electrocatalytic overall water splitting

The high cost and low reserves of noble metals greatly hinder their practical applications in new energy production and conversion. The exploration of cost-effective alternative electrocatalysts with the ability to drive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is extremely significant to promote overall water splitting. Herein, ultrathin CoSe₂/CNTs nanocomposites have been synthesized by a facile two-step method, where the ultrathin Co-MOF (metal organic-framework) decorated with cable-like carbon nanotubes (CNTs) (Co-MOF/CNTs) was initially fabricated, and followed a low-temperature selenization process. The ultrathin CoSe₂ nanosheets as well as the superior conductivity of CNTs synergistically resulted in abundant active sites and enhanced conductivity to boost the electrocatalytic activity. The as-prepared CoSe₂/CNTs electrocatalysts exhibited an overpotential of 190 mV and 300 mV vs. reversible hydrogen electrode (RHE) at a current density of 10 mA/cm² for the HER and OER in alkaline solution, respectively, and demonstrated superior durability. Furthermore, the as-prepared bifunctional CoSe₂/CNTs electrocatalysts can act as cathode and anode in an electrolyzer, showing a cell voltage of 1.75 V at 10 mA/cm² for overall water splitting.     

Bi-ionic membrane potential across a liquid anion-exchange membrane containing triphenyltin chloride

Potentiometric selectivities of a liquid anion-exchange membrane containing triphenyltin chloride (TPTCl) to several inorganic anions were evaluated via measurements of the membrane potential of a bi-ionic system, also called bi-ionic membrane potential. Addition of TPTCl to the liquid anion-exchange membrane, based on the quaternary ammonium salt, gave rise to a quite different selectivity pattern from the so-called Hofmeister anion series observed for the liquid anion-exchange membrane. An additivity rule of the bi-ionic membrane potential was observed to hold for the liquid anion-exchange membrane containing TPTCl. Thus, the following multiple chain rule was derived for selectivity coefficients; k_1,n^pot = k_1,2^pot · k_2,3^pot … k_i,(i+1)^pot … k_n−1,n^pot where k_i,i+1^pot is the selectivity coefficient of the membrane for the (i + 1)th ion over the ith ion.     

Sub‐10 nm Polyamide Nanofiltration Membrane for Molecular Separation

To separate small molecules from the solvent with high permeability and selectivity, the membrane process is thought to be highly effective with much lower energy consumption when compared to the traditional thermal‐based separation process. To achieve high solvent permeance, a sub‐10 nm thick polyamide nanofiltration membrane was synthesized through interfacial polymerization of ethidium bromide (EtBr) and trimesoyl chloride (TMC). Thanks to the extremely low solubility of the EtBr monomer in the organic phase, the polymerization process was strictly limited at the interface of the water and hexane, leading to an ultrathin polyamide membrane with a thickness down to sub‐10 nm. When used in nanofiltration, these ultrathin membranes display ultrafast water permeation of 40 liter per square meter per hour per bar (L m^?2 h^?1 bar^?1), and a high Congo red rejection rate of 93 %. This work demonstrates a new route to synthesize ultrathin polyamide membranes by the traditional interfacial polymerization.     

Synthesis and Characterization of Polyelectrolyte Complex N-Succinylchitosan-chitosan for Proton Exchange Membranes

Synthesis of acid-base complex membrane is one of method to improve the proton conductivity in proton exchange membrane for fuel cell applications. In this study, acid-base complex membrane was synthesized based on N-succinylchitosan-chitosan complexes. The N-succinylchitosan was blended with chitosan in acetic acid at various substitution degree of N-succinylchitosan with weight ratio of N-succinylchitosan of 80% w/w. The acid-base complex membranes were cast from the polymer solution and dried by evaporation. The properties of the membranes such as water uptake, ion exchange capacity, proton conductivity, and mechanical strength were analyzed. It was observed that the increase of substitution degree of N-succinylchitosan tends to increase the proton conductivity. The optimum performance of membrane unit is attained by the substitution degree of N-succinylchitosan of 0.72, which is reflected by its ion exchange capacity of 3.45 meq/g and proton conductivity of 7.35 × 10^-2 S cm^-1, respectively. Blending of N-succinylchitosan and chitosan also improved the mechanical strength of the membranes. These results imply that this type of polyelectrolyte complex membrane is a good candidate for proton exchange membrane in fuel cell applications.     

Investigation of interaction between the drug and cell membrane by capillary electrophoresis

By introducing cell membrane into electrophoretic buffer as pseudo-stationary phase, a novel capillary electrophoresis method was established to explore the interaction between drugs and cell membrane, where the interaction between citalopram and rabbit red blood cell membrane was used as an example. A series of concentrations of cell membrane were suspended into the running buffer by peak-shift method. The binding constant of citalopram to rabbit red blood cell membrane of 0.977 g^?1·L was obtained after treatment of Scatchard plot. This method could provide not only a new way for the investigation on the interactions between drugs and cell membrane, but also a new approach for high throughput screening of the drug membrane permeability, biological activity, and evaluating drugs in vivo.     

Flow injection potentiometric detection of trimethylamine in seafood using tungsten oxide electrode

A simple flow injection gas/diffusion method for the determination of trimethylamine (TMA) in seafood with potentiometric detection using tungsten oxide electrode has been developed. The method is based on the diffusion of TMA through a PTFE membrane from a sodium hydroxide donor stream to a phosphate buffer acceptor stream. The TMA in the acceptor stream passes through an electrochemical flow cell containing a tungsten oxide wire and a silver/silver chloride electrode, where TMA was sensitively detected. The parameters affecting the sensitivity of the electrode such as sodium hydroxide concentration, buffer concentration, pH, flow rate and injected volume were studied in details. The electrode response was linear in the concentration range from 1 to 10 μg ml⁻¹ TMA with a correlation coefficient (R²) of 0.991 and a detection limit of 0.05 μg ml⁻¹ TMA. The intra- and inter-days precision (R.S.D.) was found to be, respectively, 1.20 and 1.6% (n=6). The method was applied to the determination of TMA in fish tissue and recoveries of 99-100% were obtained for fish extracts. Results were in close agreement with those obtained by the existing classical official method. Common interference from those species that can diffuse through the membrane were removed by the addition of formaldehyde to the seafood extract. The method is simple, feasible with satisfactory accuracy and precision and thus, could be used for monitoring seafood quality with a sampling rate of 20±2 sample h⁻¹.     

Low‐voltage efficient electroosmotic pumps with ultrathin silica nanoporous membrane

In this work, an efficient electroosmotic pump (EOP) based on the ultrathin silica nanoporous membrane (u‐SNM), which can drive the motion of fluid under the operating voltage as low as 0.2 V, has been fabricated. Thanks to the ultrathin thickness of u‐SNM (～75 nm), the effective electric field strength across u‐SNM could be as high as 8.27 × 10⁵ V m^?1 in 0.4 M KCl when 1.0 V of voltage was applied. The maximum normalized electroosmotic flow (EOF) rate was as high as 172.90 mL/min/cm²/V, which was larger than most of other nanoporous membrane based EOPs. In addition to the ultrathin thickness, the high porosity of this membrane (with a pore density of 4 × 10¹² cm^?2, corresponding to a porosity of 16.7%) also contribute to such a high EOF rate. Moreover, the EOF rate was found to be proportional to both the applied voltage and the electrolyte concentration. Because of small electrokinetic radius of u‐SNM arising from its ultrasmall pore size (ca. 2.3 nm in diameter), the EOF rate increased with increasing the electrolyte concentration and reached the maximum at a concentration of 0.4 M. This dependence was rationalized by the variations of both zeta potential and electrokinetic radius with the electrolyte concentration.     

Ultrasensitively sensing acephate using molecular imprinting techniques on a surface plasmon resonance sensor

An ultrathin molecularly imprinted polymer film was anchored on an Au surface for fabricating a surface plasmon resonance sensor sensitive to acephate by a surface-bound photo-radical initiator. The polymerization in the presence of acephate resulted in a molecular-imprinted matrix for the enhanced binding of acephate. Analysis of the SPR wavenumber changes in the presence of different concentrations of acephate gave a calibration curve that included the ultrasensitive detection of acephate by the imprinted sites in the composite, K_ass for the association of acephate to the imprinted sites, 7.7 × 10¹² M⁻¹. The imprinted ultrathin film revealed impressive selectivity. The selectivity efficiencies for acephate and other structurally related analogues were 1.0 and 0.11-0.37, respectively. Based on a signal to noise ratio of 3, the detection limits were 1.14 × 10⁻¹³ M for apple sample and 4.29 × 10⁻¹⁴ M for cole sample. The method showed good recoveries and precision for the apple and cole samples spiked with acephate solution. This suggests that a combination of SPR sensing with MIP film is a promising alternative method for the detection of organophosphate compounds.     

Isolation of a Potential Anchoring Motif Based on Proteome Analysis of Escherichia coli and Its Use for Cell Surface Display

For bacterial cell surface display, the target protein needs to be linked to an anchoring motif, and it is essential to choose an appropriate anchoring motif for efficient and stable display of the protein on the cell surface. To isolate a potential anchoring motif that would allow a stable and enhanced display of target proteins on the surface of an Escherichia coli host, we analyzed the outer membrane proteome of E. coli. On the basis of this proteomic analysis, the outer membrane protein X (OmpX), which has a small, monomeric β-barrel structure and is highly expressed, was selected as a potential anchoring motif. The role of OmpX as an anchoring motif for cell surface display was demonstrated using three important industrial enzymes: endoxylanase, lipase, and alkaline phosphatase. Two different positions (Lys¹²², Val¹⁶⁰) in the extracellular loops of OmpX were examined for C-terminal fusion, and the biological activities and localization of the displayed enzymes were analyzed. All three enzymes examined were efficiently displayed on the E. coli cell surface with high activity. These results reveal that the use of OmpX as an anchoring motif is an efficient method to display functional enzymes on the surface of an E. coli host.     

Dipicrylamine transport across an ultrathin phosphatidylethanolamine membrane

Admittance measurements at zero applied direct voltage are reported for solutions containing 10^?4 to 10^?7M dipicrylamine, in contact with a black phosphatidylethanolamine membrane. The experimental data can be interpreted quantitatively in terms of a model involving slow phase transfer and fast desorption—adsorption kinetics. The adsorption of dipicrylamine makes it possible to distinguish experimentally between ion transport across the membrane itself and that across the water/membrane interfaces.     

Radiation stability of several polymeric supports used for radionuclide transport from nuclear wastes using liquid membranes

In an attempt to evaluate radiation stability of several polymeric materials used as the support in supported liquid membrane studies for the transport of radionuclides from nuclear waste, flat sheets made from polytetrafluoroethylene, polysulfone, polyether sulfone, polyacrylonitrile and polyvinylidenefluoride were irradiated to varying extents using a ⁶⁰Co gamma ray source and subsequently, the transport efficiency of the irradiated flat sheets were evaluated. The membrane integrity was assessed from the transport rates of Am³⁺ from a feed containing 3 M HNO₃ into a receiver phase containing 0.01 M HNO₃ as the strippant while 0.1 M TODGA (N,N,N′,N′-tetraoctyldiglycolamide) + 0.5 M DHOA (di-n-hexyloctanamide) in n-dodecane was used as the carrier extractant. The radiation stability of the membrane filters was evaluated after irradiating them up to 20 MRad absorbed dose in a gamma chamber.     

The effect of the Co-anion,SCN−, on macrocycle-facilitated selective transport of Cd (II) over Ag (I) in an emulsion membrane

Emulsion membrane systems consisting of (1) an aqueous source phase containing 0.001 M Cd (NO₃)₂ and/or 0.001 M AgNO₃ and varying concentrations of SCN⁻, (2) a toluene membrane containing dicyclohexano-18-crown-6 (DC18C6) (0.02 M) and the surfactant Span 80 (sorbitan monooleate) (3% v/v), and (3) an aqueous receiving phase containing MgS₂O₃ or Mg (NO₃)₂ were studied with respect to the disappearance of Cd (II) and/or Ag (I) from the source phase as a function of time. The transport rate of Cd (II) was highest when a maximum amount of the Cd(II) in the source phase was present as Cd(SCN)₂ ([SCN⁻] =0.4 M). Cadmium(II) was transported over Ag(I), which is present mainly as Ag(SCN)₄³⁻, by 5- and 55-fold in 5 minutes with 0.4 M SCN⁻ in the source phase and 0.3 M S₂O²⁻₃ and 0.3 M NO⁻₃, respectively, in the receiving phase. In these competitive experiments, the total percent of Cd (II) transported was 98 and 84, respectively. The results are explained using the various equilibrium constants for cation-DC18C6, cation-SCN⁻ and cation-S₂O²⁻₃ interactions. These results indicate that rapid transport occurs when a cation is present in the source phase as a neutral complex. Selectivity for neutral species can be designed into these membrane systems when other cations interact with the source-phase anion to form charged species. Emulsion systems like those above were studied with respect to the appearance of Li⁺ in the source phase as a measure of membrane breakage. Maximum membrane stability was obtained when the ionic strengths of the source and receiving phases were equal.     

The cell model of the electrolyte transport mechanisms for cultured human colonocytes. Electromotive forces of the cellular pathways

The purpose of this work was to explain the chloride secretory model of the human colonocytes in terms of the equivalent electromotive forces and the relative apical ionic permeabilities using a conventional micro-electrode technique and different ion-substitution experiments. Both equivalent electromotive forces (for apical and basolateral membranes: E_a=−47.7±5.1 mV and E_b=−65.2±2.9 mV, respectively) depend strongly on the external K⁺ concentration. The most important conclusion is that both cell membrane potentials are largely dominated by a K⁺ permeability. The apical membrane has low Na⁺ and Cl⁻ permeabilities in non-stimulated conditions (P_Na/P_K=0.06±0.01 and P_Cl/P_K=0.23±0.09). An interesting response was found for the basolateral Na⁺ substitutions. Lowering the basolateral Na⁺ concentration at 1 mM we have seen a slow, but large depolarisation of the cell membrane potential of about 30 mV. We think that this is mostly caused by the presence of the basolateral Na⁺/H⁺ exchanger mechanism for the intracellular pH regulation. The Na⁺/K⁺ pump has a significant contribution to the basolateral electromotive force. The basolateral membrane has also a Cl⁻ permeability in non-stimulated conditions, but the basolateral Na⁺ permeability is undetectable.     

Fabrication of a micro-direct methanol fuel cell using microfluidics

A direct-methanol fuel cell containing three parts: microchannels, electrodes, and a proton exchange membrane (PEM), was investigated. Nafion resin (NR) and polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (PS) were used as PEMs. Preparation of PEMs, including compositing with other polymers and their solubility, was performed and their proton conductivity was measured by a four point probe. The results showed that the 5 % Nafion resin has lower conductivity than the 5 % PS solution. The micro-fuel cell contained two acrylic channels, PEM, and two platinum catalyst electrodes on a silicon wafer. The assembled micro-fuel cells used 2 M methanol at the flow rate of 1.5 mL min^?1 in the anode channel and 5 × 10^?3 M KMnO₄ at the flow rate of 1.5 mL min^?1 in the cathode channel. The micro-fuel cell with the electrode distance of 300 ??m provided the power density of 59.16 ??W cm^?2 and the current density of 125.60 ??A cm^?2 at 0.47 V.     

muelectrode studies in cultured epithelial cells

The present analysis was done to elucidate the electrical properties of an established mammalian epithelial cell line, i.e. the Madin Darby canine kidney (MDCK) cell. Rapid changes of the extracellular fluid were made to identify conductive pathways across the cell membrane. During control conditions mimicking in vivo extracellular fluid, the potential difference across the cell membrane (U_m) approached −51.0±0.5 mV (n = 122). With potassium-sensitive muelectrodes, a potential difference of +14,4 ± 1.4 mV (n = 5) was determined. Rapid increase of the extracellular potassium concentration from 5.4 to 20 mmol/dm³ depolarized U_m (dU_mK) by +17.0 ± 0.4 mV (n = 85). Accordingly, some 50% of the cell membrane conductance is due to potassium conductive pathways, i.e. the transference number for potassium (t_K) approaches 0.5. When 10 μmol/dm³ valinomycin was added to the extracellular fluid, U_m increased gradually to −74.7 ± 0.8 mV and t_K increased to 0.86. Barium at a concentration of 1 mmol/dm³ in the extracellular fluid depolarized U_m by +20.2 ± 0.4 mV and virtually abolished t_K. However, when extracellular potassium was increased from 5.4 to 35 mmol/dm³, further depolarization was observed, indicating that barium can be displaced by high potassium concentrations. Rapid reduction of the extracellular sodium concentration from 133 to 19 mmol/dm³ led to a significant sustained hyperpolarization (dU_mNa) of −13.5±0.6 mV (n =15). Additional experiments indicated that the hyperpolarization was at least partly due to opening of potassium conductive pathways.In conclusion, the cell membrane conductance of MDCK cells is partially due to a potassium conductance which can be blocked by barium and stimulated by the reduction of extracellular sodium. Intracellular potassium is higher than that for electrochemical equilibrium across the cell membrane, and thus potassium diffusion is directed from the cell to the extracellular fluid.     

Mediated amperometric biosensor for hypoxanthine based on a hydroxymethylferrocene-modified carbon paste electrode

An amperometric enzyme electrode for the determination of hypoxanthine in fish meat is described. The hypoxanthine sensor was prepared from xanthine oxidase immobilized by covalent binding to cellulose triacetate and a carbon paste electrode containing hydroxymethylferrocene. The xanthine oxidase membrane was retained behind a dialysis membrane at a carbon paste electrode. The sensor showed a current response to hypoxanthine due to the bioelectrocatalytic oxidation of hypoxanthine, in which hydroxymethyiferrocene served as an electron-transfer mediator. The limit of detection is 6 × 10^?7 M, the relative standard deviation is 2.8% (n=28) and the response is linear up to 7 × 10^?4 M. The sensor responded rapidly to a low hypoxanthine concentration (7 × 10^?4 M), the steady-state current response being achieved in less than 1 min, and was stable for more than 30 days at 5 ° C. Results for tuna samples showed good agreement with the value determined by the conventional method.     

Properties of new inorganic membranes prepared by metal alkoxide methods Part II: New inorganic-organic anion-exchange membranes prepared by the modified metal alkoxide methods with silane coupling agents

Four types of inorganic-organic anion exchangeable membranes were prepared on a microporous alumina substrate by dipcoating with solution containing Si(OC₂H₅)₄, C₂H₅OH, H₂O, CH₃COOH, two silane coupling agents in molar ratio 1:6.8:2:0.03:0.02, and on a silica membrane by liquid-phase coupling method with two solutions containing C₆H₅CH₃, H₂O, 2-(trimethoxysilyl)ethyl-2-pyridine in molar ratio 11:0.06:0.04 or C₂H₅OH, H₂O, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride in molar ratio 21:0.06:0.06. The alumina substrate and silica membrane showed cation exchangeability, but membranes dip-coated and liquid-phase coupled showed anion exchangeability and their ion-exchange capacity per unit area of membrane surface were in the range 4–9 × 10⁻³ meq. cm⁻². The static transport number for liquid-phase coupled membranes was in the range of 0.6–0.9, but for dip-coated membranes it was 0.5.     

High performance nitrile copolymers for polymer electrolyte membrane fuel cells

This paper reports the fuel cells (DMFC and PEMFC) performance using sulfonated poly(arylene ether ether nitrile) (SPAEEN) copolymers containing sulfonic acid group arranged in structurally different ways. The membrane electrode assembly (MEA) fabricated from SPAEEN containing 60 mol% of angled naphthalenesulfonic acid group (m-SPAEEN-60) had superior performance over those derived from pendent naphthalenesulfonic acid group (p-SPAEEN) or sulfonated hydroquinone (HQ-SPAEEN) in H₂/air and/or DMFC conditions. For example, the current density of the MEA using m-SPAEEN-60 at 0.5 V and 2.0 M methanol was 250 mA/cm², whereas the current densities of the MEAs using p-SPAEEN-50 and HQ-SPAEEN-56 were 185 and 190 mA/cm², respectively. In addition, compared with the sulfonated polysulfone (BPSH-35) and Nafion membranes, the copolymer containing nitrile group showed the improved cell performance. For example, the power density of the MEA using m-SPAEEN-60 at 250 mA/cm² and 2.0 M methanol was 125 mW/cm², whereas the power densities of the MEAs using sulfonated polysulfone (BPSH-35) and Nafion were 115 and 113 mW/cm², respectively. m-SPAEEN-60 showed stable cell performance during extended operation (>100 h).     

Poly(arylene ether) ionomers containing sulfofluorenyl groups: Effect of electron-withdrawing groups on the properties

For polymer electrolyte membrane fuel membrane cell (PEMFC) applications, the effect of electron-withdrawing groups on the properties of sulfonated poly(arylene ether) (SPE) ionomer membranes was investigated. A series of poly(arylene ether)s containing fluorenyl groups and electron-withdrawing groups (sulfone, nitrile, or fluorine) was synthesized, which were sulfonated with chlorosulfonic acid using a flow reactor to obtain the title ionomers. The ionomers had high molecular weight (M_n > 77 kDa, M_w > 238 kDa) and gave tough, ductile membranes by solution casting. The ion exchange capacity (IEC) of the membranes ranged from 1.6 to 3.5 mequiv/g as determined by titration. The electron-withdrawing groups did not appear to affect the thermal properties (decomposition temperature higher than 200 °C). The presence of nitrile groups, especially at positions meta to the ether linkages, improved the oxidative stability of the SPE membranes, while it led to a deterioration of the hydrolytic stability. The perfluorinated biphenylene groups were effective in providing high mechanical strength with reasonable dimensional change, probably due to a somewhat decreased water absorbability. The SPE membrane containing sulfone groups showed the highest proton conductivity (10⁻³-10⁻¹ S/cm) at 20-93% RH (relative humidity) and 80 °C. The nitrile-containing SPE membrane showed smaller apparent activation energies for oxygen and hydrogen permeability and is thus considered to be a possible candidate for applications in PEMFCs.