Strontium(II) selective PVC membrane electrode based acetophenone semicarbazone (ACS) as an ionophore

A new PVC membrane based strontium(II) ion-selective electrode has been constructed using acetophenone semicarbazone as a neutral carrier. The sensor exhibits a Nerstian response for strontium(II) ion over a wide concentration range 1.0 × 10⁻²–1.0 × 10⁻⁷ M with the slope of 29.4 mV/per decade. The limit of detection was 2.7 × 10⁻⁸ M. It was relatively fast response time (<10 s for concentration ⩾1.0 × 10⁻³ and <15 s for concentration of ⩾1.0 × 10⁻⁶ M) and can be used for 8 months without any considerable divergence in potentials. The proposed sensor revealed relatively good selectivity and high sensitivity for strontium(II) over a mono, di, trivalent cation and can be used in a pH range of 2.5–10.5. It was also successfully used as an indicator electrode in potentiometer titration and in the analysis of concentration in various real samples.     

Asymmetric Schiff base as carrier in PVC membrane electrodes for manganese (II) ions

Manganese(II) complex of (E)-2-(hydroxyl-5-methoxybenzylideneamino) phenol was synthesized and used as a suitable Mn(II) – selective membrane in PVC matrix. The plasticized membrane sensor exhibits a nersian response for Mn(II) ions over a wide concentration range of 6 × 10^?6–2 × 10^?2 M with slope of 29 ± 1 mV per decade. It has a response time of <11 s and can be used for 2 months without any measurable divergence in potential. The response of the proposed sensor is independent of pH between 4 and 9.5. The proposed sensor shows a fairly good discriminating ability towards Mn(II) in comparison with some hard and soft metals. The electrode was used in the determination of Mn(II) in aqueous solutions and as an indicator electrode in potentiometer titration of manganese ions against EDTA.     

Magnetic nanoparticle-molecular imprinted polymer: A new impedimetric sensor for tributyltin detection

Recently, molecular imprinted polymers (MIPs) were extensively used for separation and identification of specific molecules, replacing expensive and unstable biological receptors. Nonetheless, their application in electrochemical sensors has not been sufficiently explored. Here we report the use of a MIP as a specific receptor in a new highly sensitive tributyltin (TBT) electrochemical sensor. The sensor combines the specificity, pre-concentration capability and robustness of molecular imprinted polymer attached onto magnetic nanoparticles with the quantitative outputs of impedimetric measurements. The proposed device detects TBT in a concentration range of 5 pM to 5 μM with a low limit of detection (5.37 pM), which is lower than the one recommended for TBT in sea water by the US Environmental Protection Agency (EPA). We believe that this new electrochemical sensor can play an important role in the monitoring of the quality of sea and fresh waters worldwide.     

High performance cholesterol sensor based on ZnO nanotubes grown on Si/Ag electrodes

Zinc oxide nanotube (ZNT) arrays were grown on Si/Ag substrate by one-step chemical process in an aqueous solution and further used as a working electrode to fabricate an enzyme-based cholesterol biosensor through immobilization of cholesterol oxidase (ChOx). The fabricated biosensors exhibit high and reproducible sensitivity of 79.40 μA/mM/cm², wide linear range from 1.0 μM to 13.0 mM, fast response time of ~ 2 s and ultra-low detection limit of 0.5 nM (S/N = 3) for cholesterol sensing. The anti-interference ability and long-term stability of the biosensor were also assessed. Finally, the biosensor was applied to analyze cholesterol concentration in human serum samples.     

Voltammetric study on the mechanism of ion transfer caused by weak acids in the bilayer lipid membrane

The mechanism has been investigated by cyclic voltammetry for the ion transfer from one aqueous phase (W1) to another (W2) across a bilayer lipid membrane (BLM) in the presence of a typical uncoupler, carbonylcyanide p-trifluoromethoxyphenylhydrazone (FCCP). Voltammograms for the ion transfer were in steady-state and showed rotated sigmoidal and symmetrical shape about the origin (0 V, 0 A). The magnitude of the ion transfer current at a given applied potential increased linearly with the concentration of FCCP in W2 up to 10⁻⁶ M and then became saturated. The ion transfer current also showed a bell-type dependence on pH centered around pH ≅ pK_a + 1, K_a being the dissociation constant of FCCP in aqueous phase. These properties have been well explained by our proposed model that the ion transfer current is attributable to the transfers of H⁺ and Na⁺ distributed in BLM. The hydrophilic counter ions, H⁺ and Na⁺, compensate the negative charge of the dissociated FCCP in BLM. The current intensity is predominantly governed by the concentration and the ion mobility of the counter cations.     

Tethered bilayer lipid membranes with giga-ohm resistances

The successful reconstitution of a tethered BLM on μ-electrodes ranging from 4000 μm to 8 μm is shown in this article. The increase in membrane resistance with decreasing electrode size and the dependency of the membrane capacitance on the electrode size was studied. Furthermore the functional incorporation of α-hemolysin from Staphylococcus aureus into a tBLM situated on μ-electrodes was achieved.     

Towards a minimally invasive device for beta-lactam monitoring in humans

Antimicrobial resistance is a leading patient safety issue. There is a need to develop novel mechanisms for monitoring and subsequently improving the precision of how we use antibiotics. A surface modified microneedle array was developed for monitoring beta-lactam antibiotic levels in human interstitial fluid. The sensor was fabricated by anodically electrodepositing iridium oxide (AEIROF) onto a platinum surface on the microneedle followed by fixation of beta-lactamase enzyme within a hydrogel. Calibration of the sensor was performed to penicillin-G in buffer solution (PBS) and artificial interstitial fluid (ISF). Further calibration of a platinum disc electrode was undertaken using amoxicillin and ceftriaxone. Open-circuit potentials were performed and data analysed using the Hill equation and log(concentration [M]) plots. The microneedle sensor demonstrated high reproducibility between penicillin-G runs in PBS with mean K_m (± 1SD) = 0.0044 ± 0.0013 M and mean slope function of log(concentration plots) 29 ± 1.80 mV/decade (r² = 0.933). Response was reproducible after 28 days storage at 4 °C. In artificial ISF, the sensors response was K_m (± 1SD) = 0.0077 ± 0.0187 M and a slope function of 34 ± 1.85 mv/decade (r² = 0.995). Our results suggest that microneedle array based beta-lactam sensing may be a future application of this AEIROF based enzymatic sensor.     

On the corrosion inhibition of iron in hydrochloric acid solutions,Part I: Electrochemical DC and AC studies

The inhibitive action of 4-methyl pyrazole (4MP) against the corrosion of iron (99.9999%) in solutions of hydrochloric acid has been studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). At inhibitor concentration range (10^?3–10^?2 M) in 1.0 M acid, the results showed that 4MP suppressed mainly the anodic processes of iron corrosion in 1.0 M HCl by adsorption on the iron surface according to Temkin adsorption isotherm. Both potentiodynamic and EIS measurements reveal that 4MP inhibits the iron corrosion in 1.0 M HCl and that the efficiency increases with increasing inhibitor concentration. Data obtained from EIS were analyzed to model the corrosion inhibition process through an equivalent circuit.     

Effect of the reference solution in the measurement of ion activity coefficients using cells with transference at T = 298.15 K

This work reports individual activity coefficients of ions at T = 298.15 K in aqueous solutions obtained from voltage values of the respective half-cell ion-selective-electrode and a single-junction Ag–AgCl reference electrode, filled with different reference solutions at different concentrations. For potassium and chloride ions in KCl aqueous solutions, reference solutions of KCl, NaCl, or CsCl were used. For sodium and chloride ions in aqueous NaCl solutions, reference solutions of CsCl were used. Experimental runs were performed at molalities (1, 2, and 3) m of the reference solution. The concentration of the sample solution was increased, starting from around 1 · 10^?3 m, up to the molality of the reference solution. The values of activity coefficients are calculated using the Henderson equation to estimate the liquid-junction potential. Results show that the ionic activity coefficients are independent of the nature and concentration of reference solution.     

New analysis of clopidogrel bisulfate in plavix tablet and human biological fluids utilizing chemically modified carbon paste sensor

The fabrication and the performance response characteristics of a sensitive, selective, simple, and rapid sensor for the determination of clopidogrel bisulfate (CLO-H₂SO₄) were described. The constructed carbon paste sensor comprised of an ion-pair based on clopidogrel with silicotungstate (CLO-ST) where this study included: composition, usable pH range, response time and temperature. The sensor exhibited a wide linear dynamic concentration ranging from 1.00 × 10⁻⁷ to 1.00 × 10⁻² and the usable pH ranges from 1.2 to 4.8 with the response time ranging from 5 to 8 s which is much faster compared to liquid ISEs with a detection limit equalling 0.34 nM. The selectivity of the sensor (CLO-H₂SO₄) was applied with respect to many of organic and inorganic cations, amino acids and sugars. The sensor had applications in bulk powder, tablets, humans (serum-urine) and in monitoring Plavix tablets’ dissolution rates. The obtained results were statistically analyzed for both accuracy and precision and were compared using the US pharmacopeial method where no significant difference was observed.     

Factors affecting membrane fouling reduction by surface modification and backpulsing

Several factors affecting microfiltration membrane fouling and cleaning, including backpulsing, crossflushing, backwashing, particle size, membrane surface chemistry, and ionic strength, were investigated with suspensions of latex beads. Approximately two-fold permeate volume enhancements over 1 h of filtration were obtained by using water or gas backpulsing, and 50% enhancement was obtained with crossflushing, for filtration of 1.0 μm diameter carboxylate modified latex (CML) particles using unmodified polypropylene (PP) membranes of 0.3 μm nominal pore diameter. When 0.2 μm diameter CML particles or mixtures of 1.0 and 0.2 μm CML particles were used, however, the average flux decreased 60% compared with using 1.0 μm CML particles for experiments with or without backpulsing.PP membranes were rendered hydrophilic with neutral or positively on negatively charged surfaces by grafting monomers of poly(ethylene glycol 200) monomethacrylate (PEG200MA), dimethyl aminoethyl methacrylate (DMAEMA), or acrylic acid (AA), respectively, to the base PP membranes. Filtration experiments show that fouling is not strongly dependent on membrane surface chemistry for filtration of 1.0 μm CML particles without backpulsing. With backpulsing, however, a 10% increase and a 20% decrease of permeate volumes collected in 1 h were observed when the CML particles and the membranes had like charges and opposite charges, respectively, compared to the permeate collected with the unmodified membrane. Using the PP membranes modified with AA, permeate volumes with backpulsing decreased 30 and 40% when NaCl concentrations of 0.01 and 0.1 M, respectively, were added to the feed. However, the permeate volumes did not vary significantly with changing ionic strength for filtration without backpulsing.     

Electrical conductance of ion-exchange textiles equilibrated with sodium chloride solutions

The aim of the work presented here is to develop a method for measuring the electric resistance of ion-exchange textiles which is a parameter unknown up to now. A special cell has been elaborated and conductimetry and impedance spectroscopy methods were compared at various NaCl concentrations. Different kinds of ion-exchange textiles were tested. A significant decrease in the electric resistance was obtained with a bipolar textile (85%) and an amphoteric textile (75%), at NaCl concentration of 6 mg l⁻¹. The results were analysed taking into account the two phases gel model used for ion-exchange membranes. The NaCl concentration corresponding to the isoconductance point could be determined and showed that textiles improve the solution conductivity at concentrations lower than 100 mg l⁻¹.     

Effects of the feed solution concentration on the separation degree in Donnan dialysis for binary systems of amino acids

The separations of amino acids by Donnan dialysis using an ion-exchange membrane were studied. Donnan dialytic experiments were carried out using an anion-exchange membrane, glutamic acid–phenylalanine or glutamic acid–alanine mixed solutions as the feeds, and sodium hydroxide solutions as the stripping ones. The initial concentrations of the two kinds of amino acids in the feed solutions were equal and in the range of 0.5–50 mol m⁻³. The amino acid fluxes were measured for each feed solution. Above the feed concentration of 10 mol m⁻³, the glutamic acid flux was over 100 times greater than that of the other amino acid, and it was found that the Donnan dialysis was applicable to the separation of the amino acids. On the other hand, below 10 mol m⁻³, the amino acid fluxes varied in a complicated manner with the concentration, and below 1 mol m⁻³ there was little difference between the fluxes of the two amino acids.Furthermore, after soaking the membrane in solutions having the same concentrations as the feed in the Donnan dialysis, uptake of the amino acids into the membrane was also measured. By comparing the experimental results of both the flux and uptake of the amino acids, the reason why the flux varied in a complicated manner with the concentration was discussed.     

Viscosity studies of (l-alanine-, l-proline,l-valine,l-leucine + aqueous KCl/KNO3) solutions at different temperatures

Viscosity coefficients of (l-alanine-, l-proline, l-valine, l-leucine + 2.0 M aqueous KCl/KNO₃) solutions have been determined as a function of amino acid concentration at different temperatures: (298.15, 303.15, 308.15, 313.15, 318.15, and 323.15) K. The trends of variation of viscosity values with increase in the concentration of l-alanine, l-proline, l-valine, and l-leucine in 2.0 M aqueous KCl and 2.0 M aqueous KNO₃ solutions, and temperature have been ascribed to the solute–solvent interactions operative in the solutions.     

Zirconium(IV) phosphosulphosalicylate-based ion selective membrane electrode for potentiometric determination of Pb(II) ions

Zirconium(IV) phosphosulphosalicylate, a cation exchanger was synthesized by mixing zirconium oxychloride to a mixture of 5-sulphosalicylic acid and phosphoric acid. The material showed good efficiency for the preparation of an ion-selective membrane electrode. The membrane was characterized affinity for Pb(II) ions. Due to its Pb(II) selective nature, the ion-exchanger was used as an electroactive by XRD and SEM analysis. The electrode responds to Pb(II) ions in a linear range from 1 × 10⁻⁵ to 1 × 10⁻¹ M with a slope of 43.8 mV per decade change in concentration with detection limit of 4.78 × 10⁻⁶ M. The life span of electrode was found to be 90 days. The proposed electrode showed satisfactory performance over a pH range of 4.0–6.5, with a fast response time of 15 s. The sensor has been applied to the determination of Pb(II) ions in water samples of different origins. It has also been used as indicator electrode in potentiometric titration of Pb(II) ion with EDTA.     

Photoelectrochemical determination of inorganic mercury ions based on energy transfer between CdS quantum dots and Au nanoparticles

A novel photoelectrochemical (PEC) sensor for mercury ions (Hg^2 +) was fabricated based on the energy transfer (ET) between CdS quantum dots (QDs) and Au nanoparticles (NPs) with the formation of T–Hg^2 +–T pairs. In the presence of Hg^2 + ions, a T-rich single-strand (ss) DNA labeled with Au NPs could hybridize with another T-rich ssDNA anchored on the CdS QDs modified electrode, through T–Hg^2 +–T interactions, rendering the Au NPs in close proximity with the CdS QDs and hence the photocurrent decrease due to the ET between the CdS QDs and the Au NPs. Under the optimal condition, the photocurrent decrease was proportional to the Hg^2 + concentration, ranging from 3.0 × 10^− 9 to 1.0 × 10^− 7 M, with the detection limit of 6.0 × 10^− 10 M.     

Carbon black as successful screen-printed electrode modifier for phenolic compound detection

We report a miniaturized and disposable electrochemical sensor for phenolic compound detection. The sensor was constructed by modifying the working electrode surface of screen-printed electrode (SPE) with carbon black (CB) dispersion. This new probe showed higher sensitivity and better resistance to fouling than the bare SPE, displaying the suitability of CB as an excellent nanomodifier of SPE for phenolic compound detection. Catechol, gallic acid, caffeic acid, and tyrosol were detected by square wave voltammetry with a detection limit of 0.1 μM, 1 μM, 0.8 μM, and 2 μM, respectively. The sensor was able to selectively discriminate the mono-phenols and ortho-diphenols with rapid and easy measurement, paving the way to use a cost-effective device for quality control of foods and beverages containing phenolic compounds.     

Acrylamide production in an ultrafiltration-membrane bioreactor using cells of Brevibacterium imperialis CBS 489-74

Both differential and integral UF-membrane reactors were tested for the bioconversion of acrylonitrile into acrylamide. Use was made of the commercially available flat membrane cell Amicon Mod.52 and the UF-membranes FS81PP, GR81PP, and YM100. The enzymatic reaction was catalyzed by the nitrile hydratase (NHase) present in resting cells of Brevibacterium imperialis CBS 489-74. The system was operated at 4°C and 10°C. Acrylonitrile concentration ranged from 50 to 500 mM. The membrane resistance to chemicals was complete at acrylonitrile and acrylamide concentrations up to 800 mM and 2 M, respectively. No rejection of solute was determined. Membranes totally retained the resting cells and no fouling was observed working with 2 and 16 mg of biocatalyst in stirred systems. Membrane compaction was apparently responsible for roughly 35% flux loss during the first 3–4 h of operation. The laboratory scale membrane bioreactor, continuously operating, allowed to show the dependence of enzyme deactivation on acrylonitrile concentration and process time. Substrate concentration higher than 100 mM were highly detrimental for NHase stability. The acrylamide yield reached in the multi-cycle process operating with 5.6 g/l of resting cells was 93.7% and the product concentration during roughly 450 h of bioconversion attained 8.3% (w/v). Decay of specific membrane flux was 98% of the initial value.     

Zinc(II) selective poly(vinyl chloride) membrane ISE using a macrocyclic compound 1,12,14-triaza-5,8-dioxo-3(4),9(10)-dibenzoylcyclopentadeca-1,12,14-triene as neutral carrier

The potentiometric response characteristics of zinc ion selective PVC-based membrane electrode employing 1,12,14-triaza-5,8-dioxo-3(4),9(10)-dibenzoyl-1,12,14-triene as an inophore was investigated. The proposed electrode exhibits a Nernstian behavior with a slope of 29.2 ± 0.4 mV per decade with a working concentration range of 1.3 × 10^?7–1.0 × 10^?1 mol L^?1 and a detection limit of 1.0 × 10^?8 mol L^?1. The membrane having the composition as TDODBCPT:O-NPOE:PVC:OA; 7:57:30:6 wt.% exhibits the best results. It has a fast response time of 7 s and can be used for at least 100 days without any considerable divergence in potential. The proposed electrode show good discrimination of Zn²⁺ ion from diverse ions. The potential response remains constant over a pH range of 3.5–9.2. The electrode found well work under laboratory conditions. The proposed sensor directly used for determination of zinc ions in human hair sample, wastewater and an indicator electrode with EDTA titration.     

A novel sensitive biosensor for Ca2+ based on electropolymerized melatonin modified electrode

An electropolymerized melatonin modified glassy carbon electrode (EPMT/GCE) was prepared by electrochemically polymerizing of melatonin in a 0.04 mol l^?1 perchloric acid solution. In KCl solution, Ca²⁺ was found to perform a reversible complex reaction on the EPMT/GCE to produce a sharp complex adsorption wave. The configuration of the electropolymerized membrane was characterized by scanning electron microscope and various electrochemical techniques. Based on which, a novel sensitive Ca²⁺ electrochemical sensor was established. The peak current showed a linear relationship with Ca²⁺ concentration in range of 6.2 × 10^?7–1.0 × 10^?4 mol l^?1 with detection limit of 4.5 × 10^?7 mol l^?1. The developed electrochemical sensor has been used for determination of Ca²⁺ in body fluid.