A fast response cadmium-selective polymeric membrane electrode based on N,N'-(4-methyl-1,2-phenylene)diquinoline-2-carboxamide as a new neutral carrier

A new polyvinylchloride membrane sensor for Cd(2+) ions based on N,N'-(4-methyl-1,2-phenylene)diquinoline-2-carboxamide (Mebqb) as a new and excellent neutral ionophore has been prepared. The sensor shows a Nernestian response for cadmium ions over a wide concentration range (1.0 x 10(-6) to 1.0 x 10(-1) M) with the determination coefficient of 0.9964 and slope of 29.9 +/- 0.5 mV decade(-1). The limit of detection is 8 x 10(-7) M. It has a fast response time of 3-8s and can be used for at least 8 weeks without any divergence in potential. The electrode can be used in the pH range from 4.0 to 9.0. The proposed sensor shows a very good discriminating ability towards Cd(2+) ion in comparison to some alkali, alkaline earth, transition and heavy metal ions. It was successfully applied for the direct determination of Cd(2+) in standard and real sample solutions.     

A fast response hafnium selective polymeric membrane electrode based on N,N'-bis(alpha-methyl-salicylidene)-dipropylenetriamine as a neutral carrier

In this study a new hafnium selective sensor was fabricated from polyvinylchloride (PVC) matrix membrane containing neutral carrier N,N'-bis(alpha-methyl-salicylidene)-dipropylenetriamine (Mesaldpt) as a new ionophore, sodium tetraphenyl borate (NaTPB) as anionic discriminator and dioctyl phthalate (DOP) as plasticizing solvent mediator in tetrahydrofuran solvent. The electrode exhibits Nernstian response for Hf(4+) (Hafnium(IV)) over a wide concentration range (2.0 x 10(-7) to 1.0 x 10(-1)M) with the determination coefficient of 0.9966 and slope of 15.1+/-0.1 mVdecades(-1). The limit of detection is 1.9 x 10(-7)M. The electrode has a fast response time of 18s and a working pH range of 4-8. The proposed membrane shows excellent discriminating ability towards Hf(4+) ion with regard to several alkali, alkaline earth transition and heavy metal ions. It can be used over a period of 1.5 months with good reproducibility. It is successfully applied for direct determination of Hf(4+) in solutions by standard addition method for real sample analysis.     

PVC membrane potentiometric sensor based on 5-pyridino-2,8-dithia[9](2,9)-1,10-phenanthroline-phane for selective determination of neodymium(III)

Spectrofluorometric studies on the binding properties of 5-pyridino-2,8-dithia[9](2,9)-1,10-phenanthrolinephane (L) toward La3+, Sm3+, Gd3+, Yb3+, and Nd3+ in methanol solution revealed the occurrence of both 1:1 and 2:1 (ligand/metal) complexation with a stability order of Nd3+ > Yb3+ > Gd3+ > Sm3+ > La3+. Consequently, L was used as a suitable neutral ionophore for the preparation of a novel polymeric membrane-selective electrode for Nd3+ ion. The electrode exhibited a Nernstian response over a wide concentration range (1.0 x 10(-6)-1.0 x 10(-2) M) with a low limit of detection of 7.9 x 10(-7) M. The electrode possesses a fast response time of <5 s and can be used for at least 9 weeks without observing any considerable deviation. The proposed electrode revealed a very good selectivity for Nd3+ over a wide variety of alkali, alkaline earth, transition, and heavy metal ions, including members of the lanthanide family other than Nd3+. The potentiometric response of the electrode is independent of the pH of test solution in the pH range 4.0-6.5. The proposed electrode was successfully applied to the recovery of Nd3+ ion from tap water samples and, also, as an indicator electrode, in potentiometric titration of neodymium(III) ions.     

Poly(vinyl) chloride membrane copper-selective electrode based on 1-phenyl-2-(2-hydroxyphenylhydrazo)butane-1,3-dione

1-Phenyl-2-(2-hydroxyphenylhydrazo)butane-1,3-dione (H(2)L) was used as an effective ionophore for copper-selective poly(vinyl) chloride (PVC) membrane electrodes. Optimization of the composition of the membrane and of the conditions of the analysis was performed, and under the optimized conditions the electrode has a detection limit of 6.30×10(-7) M Cu(II) at pH 4.0 with response time 10s and displays a linear EMF versus log[Cu(2+)] response over the concentration range 2.0×10(-6) to 5.0×10(-3) M Cu(II) with a Nernstian slope of 28.80±0.11 mV/decade over the pH range of 3.0-8.0. The sensor is stable for 9 weeks and exhibits good selectivity with respect to alkali, alkali earth and transition metal ions (e.g. Na(+), K(+), Ba(2+), Ca(2+), Zn(2+), Cd(2+), Co(2+), Mn(2+), Ni(2+), Fe(2+), Al(3+)) in the 3.0-8.0 pH range. It was successfully applied for the direct determination of copper(II) in zinc, aluminum and nickel based alloys, in soils polluted by oil, and as an indicator electrode for potentiometric titration of copper ions with EDTA.     

Lead phthalocyanine as a selective carrier for preparation of a cysteine-selective electrode.

A novel cysteine-selective electrode based on lead phthalocyanine (PbPc) as ionophore is described. The electrode was prepared by incorporating PbPc into a plasticized poly(vinyl chloride) (PVC) membrane, which was directly coated on the surface of a graphite electrode. This electrode shows high selectivity for the response to cysteine, as compared with many common inorganic anions, salicylate, and other kinds of amino acids. The influence of membrane composition, pH, and the effect of lipophilic cationic and anionic additives on the response characteristics of the electrode were investigated. The resulting sensor demonstrates nernstian response over a wide linear range of cysteine concentration (1 x 10(-6) to 5 x 10(-2) M). The electrode has a fast response time, micromolar detection limit (approximately 1 x 10(-6) M), and good long-term stability (more than 1 month). The prepared electrode was used for determination of cysteine in a synthetic human serum sample, and very good recovery results were obtained over a wide concentration range of cysteine.     

Salicylate-selective electrodes based on AI(III) and Sn(IV) salophens

New salicylate-selective electrodes based on aluminum-(III) and tin(IV) salophens are described. The electrodes were prepared by incorporating the ionophores into plasticized poly(vinyl chloride) (PVC) membranes, which were directly coated on the surface of graphite electrodes. These novel electrodes display high selectivity for salicylate with respect to many common inorganic and organic anions. The influence of membrane composition and pH and the effect of lipophilic cationic and anionic additives on the response properties of the electrodes were investigated. The electrode based on aluminum salophen, with 32% PVC, 65.8% plasticizer, and 2.2% ionophore, shows the best potentiometric response characteristics and displays a linear log [Sal-] vs EMF response over the concentration range 1 x 10(-6) - 1 x 10(-1) M in phosphate buffer solutions of pH 7.0, with a Nernstian slope of -59.2 mV/decade of salicylate concentration. Highest selectivity was observed for the membrane incorporating 38.8% PVC, 57.3% plasticizer, 2.6% Sn(salophen), and 1.3% sodium tetraphenylborate. The electrodes exhibit fast response times and micromolar detection limits (approximately 1 x 10(-6) M salicylate) and could be used over a wide pH range of 3-8. Applications of the electrodes for determination of salicylate in pharmaceutical preparations and biological samples are reported.     

PVC membrane and coated graphite potentiometric sensors based on Et4todit for selective determination of samarium(III)

Solution studies on the binding properties of 4,5,6,7-tetrathiocino[1,2-b:3,4-b']diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione (Et(4)todit) toward a number of cationic species including some lanthanide ions revealed the occurrence of a selective 1:1 complexation of the ligand with Sm(3+) ion. Consequently, Et(4)todit was used as a suitable neutral ionophore for the preparation of novel polymeric membrane (PME) and coated graphite (CGE) Sm(3+)-selective electrodes. The electrodes exhibit a Nernstian behavior for Sm(3+) ions over wide concentration ranges (1.0 x 10(-5)-1.0 x 10(-1) M for PME and 1.0 x 10(-7)-1.0 x 10(-1) M for CGE) and very low limits of detection (8.0 x 10(-6) M for PME and 1.6 x 10(-8) M for CGE). The proposed potentiometric sensors manifest advantages of relatively fast response, and, most importantly, good selectivities relative to wide variety of other cations, including other lanthanide ions. The selectivity behavior of the proposed Sm(3+)-selective electrodes revealed a great improvement compared to the best previously reported electrode for samarium(III) ion. The potentiometric responses of the electrodes are independent of the pH of the test solution in the pH range 4.0-6.5. The electrodes were successfully applied to the recovery of Sm(3+) ion from tap water samples and also, as an indicator electrode, in potentiometric titration of samarium(III) ions.     

Carbon nanotube composite coated platinum electrode for detection of Ga(III)

This study demonstrates the application of composite multi-walled carbon nanotube (MWCNT) polyvinylchloride (MWNT-PVC) based on 7-(2-hydroxy-5-methoxybenzyl)-5,6,7,8,9,10-hexahydro-2H benzo [b][1,4,7,10,13] dioxa triaza cyclopentadecine-3,11(4H,12H)-dione ionophore for gallium sensor. The sensor shows a good Nernstian slope of 19.68 ± 0.40 mV/decade in a wide linear range concentration of 7.9 × 10(-7) to 3.2 × 10(-2)M of Ga(NO(3))(3). The detection limit of this electrode is 5.2 × 10(-7)M of Ga(NO(3))(3). This proposed sensor is applicable in a pH range of 2.7-5.0. It has a short response time of about 10s and has a good selectivity over nineteen various metal ions. The practical analytical utility of this electrode is demonstrated by measurement of Ga(III) in river water.     

Chromium(III) porphyrin as a selective ionophore in a salicylate-selective membrane electrode

The construction, potentiometric response properties, and applications of a novel ion-selective electrode with high selectivity toward salicylate are described. Chromium(III) tetraphenylporphyrin chloride was used as ion carrier into plasticized PVC membrane. This ionophore is capable of serving as both a positively charged and neutral carrier, depending on the pH of the sample solution. The influence of several variables was investigated to optimize the potentiometric response and selectivity of the electrode. The resulting electrode demonstrates a near-Nernstian response over a wide range of salicylate concentration (10(-6)-10(-1) M). This electrode has a fast response time and micromolar detection limit and could be used over a wide pH range (3-9). The proposed electrode showed very high selectivity for salicylate over a number of common inorganic and organic anions. The specific interaction of salicylate with the central metal of porphyrin is described based on UV-visible absorption spectra. The electrode was successfully applied to the determination of salicylate in pharmaceutical preparations and clinical samples.     

Determination of serotonin on a glassy carbon electrode modified by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin and single walled carbon nanotubes

A chemically modified electrode [poly(TAPP)-SWNT/GCE] was prepared by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin (TAPP)-single walled carbon nanotubes (SWNT) on the surface of a glassy carbon electrode (GCE). This modified electrode was employed as an electrochemical biosensor for the determination of serotonin concentration and exhibited a typical enhance effect on the current response of serotonin and lower oxidation overpotential. The biosensor was very effective to determined 5-HT in a mixture. The linear response was in the range 2.0 x 10(-7) to 1.0 x 10(-5) M, with a correlation coefficient of 0.999 [i(p)(microA) = 3.406 C (microM)+0.132] on the anodic current, with a detection limit of 1 x 10(-9) M. Due to the relatively low currents and different potentials in the electrochemical responses to ascorbic acid and dopamine, the modified electrode is a useful and effective sensing device for the selective and sensitive serotonin determination in the presence of ascorbic acid and dopamine.     

A Schiff base complex of Zn(II) as a neutral carrier for highly selective PVC membrane sensors for the sulfate ion

Novel polymeric membrane (PME) and coated graphite (CGE) sulfate-selective electrodes based on a recently synthesized Schiff base complex of Zn(II) were prepared. The electrodes reveal a Nernstian behavior over wide SO4(2-) ion concentration ranges (5.0 x 10(-5)-1.0 x 10(-1) M for PME and 1.0 x 10(-7)-1.0 x 10(-1) M for CGE) and very low detection limits (2.8 x 10(-5) M for PME and 8.5 x 10(-8) M for CGE). The potentiometric response is independent of the pH of the solution in the pH range 3.0-7.0. The electrodes manifest advantages of low resistance, very fast response, and, most importantly, good selectivities relative to a wide variety of other anions. In fact, the selectivity behavior of the proposed SO4(2) ion-selective electrodes shows a great improvement compared to the previously reported electrodes for sulfate ion. The electrodes can be used for at least 3 months without any appreciable divergence in potentials. The electrodes were used as an indicator electrode in the potentiometric titration of sulfate and barium ions and in the determination of iron in ferrous sulfate tablets.     

Lanthanide Recognition: Monitoring of Praseodymium(III) by a Novel Praseodymium(III) Microsensor Based on N′-(Pyridin-2-Ylmethylene)Benzohydrazide

In this work, for the first time, we introduce a highly selective and sensitive praseodymium(III) microsensor. Npsila-(pyridin-2-ylmethylene)benzohydrazide (PBH) was used as a membrane-active component to prepare a highly sensitive Pr(III)-selective polymeric membrane microelectrode. The electrode exhibits a Nernstian response toward Pr(III) ions over a very wide concentration range (1.0 times 10^-3 -1.0 times 10^-8 M), with a detection limit of 7.0 times 10^-9 M (~1 ng/ml). It has a very fast response time in the whole concentration range (~10 s). The proposed microelectrode can be used for at least six weeks without any considerable divergence in potentials. The proposed membrane sensor revealed very good selectivity toward Pr(III) ions over a wide variety of other metal ions including common alkali, alkaline earth and, specially, lanthanide ions. It could be used in the pH range of 3.0-8.5. The Pr(III) microelectrode was used as an indicator electrode for the titration of 20 ml of a 1.0 times 10^-6 M Pr(III) ions with a 1.0 times 10^-4 M EDTA.     

PVC-based 1,3,5-trithiane sensor for cerium(III) ions

A PVC membrane sensor for cerium(III) ions based on 1,3,5-trithiane as membrane carrier was prepared. The sensor has a linear dynamic range of 1.0 x 10(-1)-5.0 x 10(-5) M, with a Nernstian slope of 19.4+/-0.4 mV decade(-1), and a detection limit 3.0 x 10(-5) M. It has a fast response time of < 15 s and can be used for at least 5 months without any considerable divergence in potentials. The proposed sensor revealed comparatively good selectivities with respect to alkali, alkaline earth, and some transition and heavy metal ions and could be used in a pH range of 5.0-8.0. It was used as an indicator electrode in potentiometric titration of oxalate and fluoride ions and in determination of F- ion in some mouth wash preparations.     

Copper(II) nanosensor based on a gold cysteamine self-assembled monolayer functionalized with salicylaldehyde

Fabrication and electrochemical characterization of a novel nanosensor for determination of Cu2+ in subnanomolar concentrations is described. The sensor is based on gold cysteamine self-assembled monolayer functionalized with salicylaldehyde by means of Schiff's base formation. Cyclic voltammetry, Electrochemical impedance spectroscopy (EIS), and electrochemical quartz crystal microbalance were used to probe the fabrication and characterization of the modified electrode. The sensor was used for quantitative determination of Cu2+ by the EIS in the presence of parabenzoquinone in comparison with stripping Osteryoung square wave voltammetry (OSWV). The attractive ability of the sensor to efficiently preconcentrate trace amounts of Cu2+ allowed a simple and reproducible method for copper determination. A wide range linear calibration curve was observed, 5.0 x 10(-11)-5.0 x 10(-6) and 5.0 x 10(-10)-5.0 x 10(-6) M Cu2+, by using the EIS and OSWV, respectively. Moreover, the sensor presented excellent stability with lower than 10% change in the response, as tested for more than three months daily experiments, and a high repeatability with relative standard deviations of 6.1 and 4.6% obtained for a series of eight successive measurements in 5.0 x 10(-7) M Cu2+ solution, by the EIS and OSWV, respectively.     

Carbon-Pt nanoparticles modified TiO2 nanotubes for simultaneous detection of dopamine and uric acid

The present work describes sensing application of modified TiO2 nanotubes having carbon-Pt nanoparticles for simultaneous detection of dopamine and uric acid. The TiO2 nanotubes electrode was prepared using anodizing method, followed by electrodeposition of Pt nanoparticles onto the tubes. Carbon was deposited by decomposition of polyethylene glycol in a tube furnace to improve the conductivity. The C-Pt-TiO2 nanotubes modified electrode was characterized by cyclic voltammetry and differential pulse voltammetry methods. The modified electrode displayed high sensitivity towards the oxidation of dopamine and uric acid in a phosphate buffer solution (pH 7.00). The electro-oxidation currents of dopamine and uric acid were linearly related to the concentration over a wide range of 3.5 x 10(-8) M to 1 x 10(-5) M and 1 x 10(-7) M to 3 x 10(-5) M respectively. The limit of detection was determined as 2 x 10(-10) M for dopamine at signal-to-noise ratio of 3. The interference of uric acid was also investigated. Electro-oxidation currents of dopamine in the presence of fix amount of uric acid represented a linear behaviour towards successive addition of dopamine in range of 1 x 10(-7) M to 1 x 10(-5) M. Furthermore, in a solution containing dopamine, uric acid and ascorbic acid the overlapped oxidation peaks of dopamine and ascorbic acid could be easily separated by using C-Pt-TiO2 nanotubes modified electrode.     

Amperometric determination of hydrogen peroxide by functionalized carbon nanotubes through EDC/NHS coupling chemistry

The electrochemistry of the redox mediator Toluidine blue (TB) which was covalently linked to the carboxyl group of the multiwalled carbon nanotubes (MWNTs) by coupling reactions, in which N-hydroxysuccinimide was used to assist 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride catalyzed amidation reaction is described. The results from cyclic voltammetry (CV) and amperometry suggested that the redox mediator is linked to the surface of the MWNTs and the nanotubes showed an obvious promotion for the direct electron-transfer between the redox mediator and the electrode. A couple of well-defined redox peak of TB was observed in a phosphate buffer solution (pH 7.0). The redox mediator immobilized to MWNTs exhibits remarkable electrocatalytic activity for the reduction of hydrogen peroxide (H2O2). The analytical applicability of the modified electrode for the determination of hydrogen peroxide was examined. A linear response in the concentration range of 6.8 x 10(-7)-3.4 x 10(-2) M (r = 0.9958) was obtained with detection limit of 3.4 x 10(-7) M for the determination of hydrogen peroxide. The modified electrode has advantages of being highly stable, sensitive, ease of construction and use.     

Electrocatalytic detection of NADH and glycerol by NAD(+)-modified carbon electrodes

The electrochemical oxidation of the adenine moiety in NAD+ and other adenine nucleotides at carbon paste electrodes gives rise to redox-active products which strongly adsorb on the electrode surface. Carbon paste electrodes modified with the oxidation products of NAD+ show excellent electrocatalytic activity toward NADH oxidation, reducing its overpotential by about 400 mV. The rate constant for the catalytic oxidation of NADH, determined by rotating disk electrode measurements and extrapolation to zero concentration of NADH, was found to be 2.5 x 10(5) M-1 s-1. The catalytic oxidation current allows the amperometric detection of NADH at an applied potential of +50 mV (Ag/AgCl) with a detection limit of 4.0 x 10(-7) M and linear response up to 1.0 x 10(-5) M NADH. These modified electrodes can be used as amperometric transducers in the design of biosensors based on coupled dehydrogenase enzymes and, in fact, we have designed an amperometric biosensor for glycerol based on the glycerol dehydrogenase (GlDH) system. The enzyme GlDH and its cofactor NAD+ were co-immobilized in a carbon paste electrode using an electropolymerized layer of nonconducting poly(o-phenylenediamine) (PPD). After partial oxidation of the immobilized NAD+, the modified electrode allows the amperometric detection of the NADH enzymatically obtained at applied potential above 0 V (Ag/AgCl). The resulting biosensor shows a fast and linear response to glycerol within the concentration range of 1.0 x 10(-6)-1.0 x 10(-4) M with a detection limit of 4.3 x 10(-7) M. The amperometric response remains stable for at least 3 days. The biosensor was applied to the determination of glycerol in a plant-extract syrup, with results in good agreement with those for the standard spectrophotometric method.     

Amperometric biosensor for glutamate using prussian blue-based "artificial peroxidase" as a transducer for hydrogen peroxide

The specially deposited Prussian Blue denoted as "artificial peroxidase" was used as a transducer for hydrogen peroxide. The electrocatalyst was stable, highly active, and selective to hydrogen peroxide reduction in the presence of oxygen, which allowed sensing of H2O2 around 0.0 V (Ag/AgCl). Glutamate oxidase was immobilized on the surface of the Prussian Blue-modified electrode in a Nafion layer using a nonaqueous enzymology approach. The calibration range for glutamate in flow injection system was 1 x 10(-7)-1 x 10(-4) M. The lowest concentration of glutamate detected (1 x 10(-7) M) and the highest sensitivity in the linear range of 0.21 A M-1 cm-2 were achieved. The influence of reductants was practically avoided using the low potential of an indicator electrode (0.0 V Ag/AgCl). The attractive performance characteristics of the glutamate biosensor illustrate the advantages of Prussian Blue-based "artificial peroxidase" as transducer for hydrogen peroxide detection.     

高氯酸盐离子新电极的建立

通过变性化学硅胶1,4-二氮杂双环[2,2,2]辛烷、环氧聚合物和碳混合,建立了高氯酸盐阴离子的电位响应。     

Electrogenerated chemiluminescence from a CdSe nanocrystal film and its sensing application in aqueous solution

Electrogenerated chemiluminescence (ECL) of semiconductor quantum dots in aqueous solutions and its first sensing application were studied by depositing CdSe nanocrystals (NCs) on a paraffin-impregnated graphite electrode (PIGE). The CdSe nanocrystal thin film exhibited two ECL peaks at -1.20 (ECL-1) and -1.50 V (ECL-2) in pH 9.3, 0.1 M PBS during the cyclic sweep between 0 and -1.8 V at 20 mV s(-1). The electron-transfer reaction between individual electrochemically reduced nanocrystal species and oxidant coreactants such as H(2)O(2) and reduced dissolved oxygen led to ECL-1. When mass NCs packed densely in the film were reduced electrochemically, assembly of reduced nanocrystal species could react with coreactants to produce another ECL signal, ECL-2. ECL-1 showed higher sensitivity to the concentration of oxidant coreactants than ECL-2 and thus was used for ECL detection of coreactant, H(2)O(2). A linear response of ECL-1 to H(2)O(2) was observed in the concentration range of 2.5 x 10(-7)-6 x 10(-5) M with a detection limit of 1.0 x10(-7) M. The fabrication of 10 CdSe nanocrystal thin-film modified PIGEs displayed an acceptable reproducibility with a RSD of 1.18% obtained at H(2)O(2) level of 10 microM.