Influence of lipophilic inert electrolytes on the selectivity of polymer membrane electrodes

Lipophilic inert electrolytes, i.e., salts without ion-exchange properties, may influence the selectivity of ionophore-based liquid membrane electrodes by affecting the activity coefficients in the organic phase. It is expected by a theoretical model that the addition of a lipophilic salt renders the ion-selective electrode more selective for divalent over monovalent ions. These predictions are confirmed with Ca(2+)-responsive membranes containing the ionophores ETH 2120, ETH 1001, and ETH 129. The effect is especially pronounced with nonpolar membrane phases containing a low concentration of charged species, where up to 2 orders of magnitude selectivity improvement is observed.     

Electric field-driven strategy for multiplexed detection of protein biomarkers using a disposable reagentless electrochemical immunosensor array

A fast, simple, sensitive, and low-cost method for electrochemical multianalyte immunoassay was developed by combining newly designed electric field-driven incubation with a screen-printed reagentless immunosensor array. The disposable array was prepared by immobilizing respectively horseradish peroxidase (HRP)-labeled antibodies modified gold nanoparticles in biopolymer/sol-gel modified electrodes to obtain direct electrochemical responses of HRP. Upon the formation of immunocomplexes, the responses decreased due to increasing spatial blocking and impedance. At a driving potential of 0.5 V, the incubation process could be accomplished within 2 min. Under optimal conditions, this method could simultaneously detect carbohydrate antigens 153, 125, and 199 and carcinoembryonic antigens ranging from 0.084 to 16, 0.11 to 13, and 0.16 to 15 U mL(-1) and 0.16 to 9.2 ng mL(-1) with a detection time of less than 5 min, and the detection limits corresponding to the signals of 3SD were 0.06, 0.03, and 0.10 U mL(-1) and 0.04 ng mL(-1), respectively. The disposable immunosensor array and simple detection system for fast measurement of panels of tumor markers show significant clinical value for application in cancer screening and provide great potential for convenient point-of-care testing and commercial application.     

Electric field-driven energy storage density and photo-catalytic temperament of Gd3+-BiFeO3 nano-ferrite

Journal of Materials Science: Materials in Electronics - The multiferroic nanoferrites have widespread potential applications in the resolution of the ecological and green energy issues. In this...     

Synergistic pseudo-hydroxide extraction: synergism and anion selectivity in sodium extraction using a crown ether and a series of weak lipophilic acids

The nature of the weak lipophilic acid used in synergistic combination with a model crown ether cation host was shown to have a strong effect on the strength and selectivity of sodium hydroxide separation from alkaline aqueous salt solutions. Sodium ion-pair extraction employing only cis-syn-cis-dicyclohexano-18-crown-6 (1) in nitrobenzene (NB) was correlated with the standard Gibbs energy (deltaG(p)o) of anion partitioning into NB and was notably weak and nonselective for the hydroxide ion, in accord with Hofmeister bias. The Hofmeister order can be selectively overcome for NaOH by utilization of acid-base chemistry coupled with complexation of sodium ion in the NB phase. Upon addition of a lipophilic organic acid into the solution of 1 in NB, sodium extraction was selectively enhanced due to the initiation of an exchange reaction between the aqueous sodium ion and the ionizable proton of the organic acid. A series of weak lipophilic hydroxy acids (HA) including fluorinated alcohols and phenols was tested. The resulting synergistic pseudo-hydroxide extraction correlates with the pKa of the employed HA; the most acidic cation exchangers provide the greatest synergism. The synergistic factor obtained using a fluorinated benzyl alcohol 7 was as high as 256. Ion-pair extraction of neutral sodium salts was not changed or only mildly enhanced by addition of HA into the NB solution of 1. This enhancement was explained by hydrogen bonding of HA with the anion as related to the hardness of the anion and the acidity of HA. In comparison with the synergism observed for NaOH, this enhancement was weak and unable to overcome the Hofmeister effect. Examination of extraction selectivity revealed that the combination of 1 and 7 preferentially extracted NaOH over all other sodium salts, including the normally preferred nitrate and perchlorate salts. Quantitative recovery of NaOH from the NB phase was demonstrated via hydrolysis of the organic acid upon a single contact of the loaded solvent with water.     

Electric field sensing with a hybrid polymer/glass fiber

We demonstrate the operation of an in-fiber electric field sensor. The sensor is fabricated with selective chemical etching of the core of a D-shaped optical fiber followed by the deposition of an electro-optic polymer (PMMA/DR1), which forms a hybrid core. The device demonstrates electromagnetic field sensitivity less than 100 V/m at a frequency of 2.9 GHz. Epi is estimated to be 60 MV/m with an insertion loss of 14.4 dB.     

Preparation,characterization and thermal studies of polymer inclusion cellulose acetate membrane with calix[4]resorcinarenes as carriers

A polymer inclusion membrane (PIM) system with cellulose acetate polymer as support and calix[4]resorcinarenes as carriers has been developed. Special attention was paid to PIM characterization using scanning electron microscopy, Fourier-transform infra-red study, X-ray scattering and thermogravimetric analyses. The efficiency of the membrane transport was optimized as a function of pH, stirring speed, aqueous phases and membrane composition. The results suggested that the transport mechanism is a counter-transport of protons, the mechanism was mainly controlled by the diffusion of the complex formed in the membrane core. Analysis of lead(II) transport through these PIMs was performed. It was found that calix[4]resorcinarenes containing membranes were flexible, resistant and heterogeneous without plasticizer addition.     

Kinetic model of membrane extraction with a sorbent interface

Membrane extraction with a sorbent interface (MESI) is an unique sample preparation alternative for trace organic analysis. The main features of MESI include its solvent-free nature, the rugged and simple design with no moving parts for long-term reliable performance, the fact that it is a single-step process which ensures good precision, its easy automation, and its feasibility for on-site operation. Among the available membrane extraction modules designed for the MESI system, the headspace configuration has continued to show its superior durability and versatility in membrane applications. The headspace membrane extraction configuration effectively eliminates the need for a sampling pump and flow metering and hence prevents the extraction system from plugging and greatly simplifies the extraction process. The module can be used for extraction of VOCs from gaseous, aqueous, or solid samples. A mathematical model has been developed for headspace membrane extraction of an aqueous sample, based on the assumption that the aqueous phase is perfectly stirred. The model is in good agreement with the experimental benzene extraction results obtained with an efficient agitation method such as high-speed magnetic stirring or sonication. The model has also been used to study the effects of various extraction parameters with respect to the sensitivity and response time of the MESI system. Sample agitation facilities analyte mass transport and hence improves both the system sensitivity and the response time. The sensitivity of the extraction method also increases with an increase of the extraction temperature.     

Permeation of a fully ionized species across a polarized supported liquid membrane

An analytical technique for the detection of permeation of a fully ionized analyte across a lipophilic membrane is reported. The system, which is comprised of two aqueous compartments (donor and acceptor) separated by a supported liquid membrane, is based on the parallel artificial membrane permeation assay (PAMPA), widely used in the drug discovery process to estimate permeability in vivo. The in situ spectroelectrochemical method developed here employs mechanical stirring of the solution phases on either side of the membrane, external polarization of the membrane, and in situ detection of the analyte via UV-vis spectrophotometry. The flux of the crystal violet cation across the membrane is simultaneously measured via UV-vis spectrophotometry and voltammetry/chronoamperometry as a function of applied potential. The relative contribution of two permeation modes, i.e., that due to naked ions and ion-pairs, is thereby quantified. The open circuit potential difference between the two aqueous compartments and the cyclic voltammetric response are also recorded as a function of time and compared with the predicted values.     

Linear coupling of alignment with transport in a polymer electrolyte membrane

Polymer electrolyte membranes (PEMs) selectively transport ions and polar molecules in a robust yet formable solid support. Tailored PEMs allow for devices such as solid-state batteries,'artificial muscle' actuators and reverse-osmosis water purifiers. Understanding how PEM structure and morphology relate to mobile species transport presents a challenge for designing next-generation materials. Material length scales from subnanometre to 1 μm influence bulk properties such as ion conductivity and water transport. Here we employ multi-axis pulsed-field-gradient NMR to measure diffusion anisotropy, and (2)H NMR spectroscopy and synchrotron small-angle X-ray scattering to probe orientational order as a function of water content and of membrane stretching. Strikingly, transport anisotropy linearly depends on the degree of alignment, signifying that membrane stretching affects neither the nanometre-scale channel dimensions nor the defect structure,causing only domain reorientation. The observed reorientation of anisotropic domains without perturbation of the inherent nematic-like domain character parallels the behaviour of nematic elastomers, promises tailored membrane conduction and potentially allows understanding of tunable shape-memory effects in PEM materials. This quantitative understanding will drive PEM design efforts towards optimal membrane transport, thus enabling more efficient polymeric batteries, fuel cells, mechanical actuators and water purification.     

Stress analysis near the tip of a curvilinear interfacial crack between a rigid spherical inclusion and a polymer matrix

Craze and shear band formation at poorly adhering glass spheres in matrices of glassy polymers are known to be preceded by the formation of a curvilinear interfacial crack between sphere and matrix. In this study the axisymmetric finite element method has been used to analyse the stress situation near the tip of a curvilinear interfacial crack formed between a rigid spherical inclusion and a polymer matrix upon an applied uniaxial tension. Important factors that determine the stress state near the crack tip were found to be the crack length, the orientation of the crack tip with regard to the tension direction and the extent of interfacial slip between the inclusion and matrix. The results of the analyses were compared with the physical reality of craze and shear band formation at poorly adhering glass spheres. Reasonable agreement was found with respect to both the maximum interfacial crack length that can be reached until a craze or shear band forms at the crack tip and the planar orientation of craze growth perpendicular to the direction of the major principal stress.     

新型磁性聚合物膜材料研究进展

按磁性来源可将磁性聚合物膜材料分为无机磁粉 -聚合物膜和磁性高分子 -聚合物膜 ;本文综述了近年来无机磁粉 -聚合物膜材料的新型制备技术及应用进展 ,对获得磁性高分子 -聚合物膜的可能途径进行了展望     

Self-organizing structure in platinum films on a Nafion type polymer membrane

The morphology of platinum films deposited onto a polymer membrane material of the Nafion type has been studied. The films with thicknesses above ∼20 nm exhibit a specific structure (morphology) that is related to the process of self-organization. The observed phenomenon is interpreted and it is established that the main mechanism responsible for the self-organization is related to the dipole interaction between clusters of the deposited catalytic metal.     

Simple fabrication of a Pd-P film on a polymer membrane and its catalytic applications

Composites were prepared by a surface activation by aerosol deposition of Pd nanoparticles (Pd nano seeds) on a poly(tetrafluoroethylene) membrane and subsequent Pd-P film formation by electroless deposition. Activation of the membrane processed by an ambient Pd spark discharge and subsequent fixation of the spark produced Pd nano seeds. Characterizations for electroless Pd-P films indicated that P entered into the crystal lattice of Pd and formed an alloy. The fabricated composites were applied to catalytic applications of formic acid oxidation (FAO) and toluene conversion (TC). The composite catalysts from the simple activation had more stable performances of FAO and TC than those from the conventional Sn-Pd activation, and their better performances might have originated from better purity due to the simple activation that only introduced pure Pd nano seeds.     

Near-infrared imaging of water in a polymer electrolyte membrane during a fuel cell operation

A novel technique of spectroscopic imaging using a near-infrared (NIR) laser sheet beam was developed for visualization of liquid water in a proton-exchange membrane (PEM) sandwiched between two opaque electrodes set in a polymer electrolyte fuel cell (PEFC). In-plane two-dimensional distribution of water in the thin membrane was clearly visualized during the fuel cell operation. Under the condition of fuel feeding into the PEFC without humidification, water was generated by the fuel cell reaction in the whole electrode area. In contrast, under the condition of fuel feeding with humidification, the PEM got wet in the vicinity of a gas flow field locally.     

Electric fields within cells as a function of membrane resistivity--a model study

Externally applied electric fields play an important role in many therapeutic modalities, but the fields they produce inside cells remain largely unknown. This study makes use of a three-dimensional model to determine the electric field that exists in the intracellular domain of a 10-/spl mu/m spherical cell exposed to an applied field of 100 V/cm. The transmembrane potential resulting from the applied field was also determined and its change was compared to those of the intracellular field. The intracellular field increased as the membrane resistance decreased over a wide range of values. The results showed that the intracellular electric field was about 1.1 mV/cm for R/sub m/ of 10 000 /spl Omega//spl middot/cm/sup 2/, increasing to about 111 mV/cm as R/sub m/ decreased to 100 /spl Omega//spl middot/cm/sup 2/. Over this range of R/sub m/ the transmembrane potential was nearly constant. The transmembrane potential declined only as R/sub m/ decreased below 1 /spl Omega//spl middot/cm/sup 2/. The simulation results suggest that intracellular electric field depends on R/sub m/ in its physiologic range, and may not be negligible in understanding some mechanisms of electric field-mediated therapies.     

Calibration of membrane extraction for air analysis

Calibration methods based on the recently developed mathematical model are proposed for air monitoring by membrane extraction. In membrane extraction, analytes permeate through the membrane at a constant rate controlled by the distribution constant and the diffusion coefficient. The principle of the proposed calibration approach is based on either theoretical or experimental determination of both constants at the extraction conditions. A group of selected compounds was employed for the experimental testing, and the results indicated practical feasibility of the approach. On-line determination of partition coefficients and distribution constants was proposed and investigated, producing very promising results. Both approaches to calibration facilitate quantitative monitoring.