A highly selective lead-sensitive electrode with solid contact based on ionic liquid

A new polyvinylchloride membrane sensor for Pb(2+) with solid contact based on ionic liquid has been prepared. The electrode shows a Nernstian response for lead ions over a wide concentration range (1×10(-8) to 1×10(-1) mol L(-1)) and the slope of 29.8 mV/decade. The limit of detection is 4.3×10(-9) mol L(-1). It has a fast response time of 5-7 s and can be used for 4 months without any divergence in potential. The proposed sensor is not pH sensitive in the range 3.5-7.3 and shows a very good discriminating ability towards Pb(2+) ion in comparison with some alkali, alkaline earth, transition and heavy metal ions. It was successfully applied as an indicator electrode in potentiometric titration of lead ions with K(2)CrO(4) and for direct determination of Pb(2+) ions in real sample solution.     

Characterization of an EDTA bonded conducting polymer modified electrode: its application for the simultaneous determination of heavy metal ions

An EDTA bonded conducting polymer modified electrode (EDTA-CPME) was fabricated by polymerization of 3',4'-diamino-2,2';5',2'-terthiophene monomer on a GCE, followed by the reaction with EDTA in the presence of catalyst. The surface of the resulting modified electrode was characterized with EQCM, ESCA, SEM, Auger electron spectroscopy, scanning Auger microscopy, and electrochemical methods. The amounts of polymer and EDTA attached on the polymer film were determined. Simple immersing of the EDTA-CPME into a sample solution led to the chemical deposition through the complexation with Pb2+, Cu2+, and Hg2+ ions, simultaniously. Various experimental parameters that affect the simultaneous analysis of the metal ions, e.g., EDTA amount, pH, deposition time, and deposition temperature, were optimized. Calibration plots for the EDTA-CPME with square wave voltammetry were obtained in the concentration range between 5.0 x 10(-10) and 1.0 x 10(-7) M for Cu(II) and between 7.5 x 10(-10) and 1.0 x 10(-7) M for Pb(II) and Hg(II). The detection limits for Pb(II), Cu(II), and Hg(II) ions were determined to be about 6.0 x 10(-10), 2.0 x 10(-10), and 5.0 x 10(-10) M, respectively. Interference effects from other metal ions were studied at various pHs and it was found that there was little or no effect on the simultaneous determination. The stability of the EDTA-CPME was remarkably improved by coating the surface with the Nafion film, and the electrode can be used for more than one month. Analytical availability of the EDTA-CPME was demonstrated by the application for the certified standard urine reference material and tap water.     

Preconcentration and Voltammetric Determination of Mercury(II) at a Chemically Modified Glassy Carbon Electrode

In this work, the organic compound 2-mercaptobenzimidazole was covalently bound on the surface of a glassy carbon rod, via silanization, yielding a material capable of selectively complexing Hg(2+) ions. This material was applied as an electrode for voltammetric determination of mercury(II) following its nonelectrolytic preconcentration. After exchanging the medium, the voltammetric measurements were carried out by anodic stripping in the differential pulse mode (pulse amplitude, 50 mV; scan rate, 1.25 mV s(-)(1)) using 10(-)(2) mol L(-)(1) NaSCN solution as supporting electrolyte. An anodic stripping peak was obtained at 0.06 V (vs SCE) by scanning the potential from -0.3 to +0.3 V. After a 5 min preconcentration period in a pH 4.0 Hg(2+) solution, this electrode shows increasing voltammetric response in the range 0.1-2.2 μg mL(-)(1), with a relative standard deviation of 5% and a practical detection limit of 0.1 μg mL(-)(1) (5.0 × 10(-)(7) mol dm(-)(3)). Compared with the conventional stripping approach, this chemically modified glassy carbon electrode procedure presented good discrimination against interference from Cu(II) in up to 10-fold molar excess.     

Polyeugenol-modified platinum electrode for selective detection of dopamine in the presence of ascorbic Acid

A platinum electrode was modified with electropolymerized films of 4-allyl-2-methoxyphenol (eugenol) by its oxidative polymerization from an alkaline solution by cyclic voltammetry. The modified electrode was than used to determine dopamine (DA) in an excess of ascorbic acid (AA) by differential pulse voltammetry. The peak positions as well as relative sensitivity DA/AA were affected by the potential window applied for the polymerization. For polymerization between 0 and 2.2 V, the peak potentials recorded in a phosphate buffer solution (pH 7.4) were -61 and +152 mV vs Ag/AgCl for AA and DA, respectively. After a 5-min equilibration, relative sensitivity DA/AA was 164 and the current sensitivity for DA was 7.9 nA μM(-)(1). The detection limit for S/N = 3 is 0.1 μM. The high selectivity and sensitivity for DA was found to be due to charge discrimination/analyte accumulation and an effect of catalytic mediation of redox sites. Chronocoulometric data reveal that DA is accumulated on the electrode as a monolayer. The electrode is stable, reversible, and free of fouling problems.     

Voltammetric determination of the synthetic pyrethroid insecticide tetramethrin in acetonitrile

The synthetic pyrethroid insecticide tetramethrin may be reduced reversibly (E°' = -1.650 V vs Ag/Ag(+)) in acetonitrile at hanging mercury drop electrodes (HMDE) and glassy carbon electrodes. On the voltammetric time scale, the initial electron-transfer process involves the reversible formation of a radical anion. Data obtained from electron paramagnetic resonance spectroscopy indicate that the unpaired electron of the radical is located within the phthalimide system of the molecule. The radical anion may be further reduced at very negative applied potentials with the number of processes being dependent on the nature of the voltammetric technique. The detection limit (3σ) for the determination of tetramethrin in acetonitrile at a glassy carbon electrode, using differential pulse voltammetry, was found to be 2.1 × 10(-6) M. At a HMDE the detection limit is lower, having a value of 9.6 × 10(-7) M. The limit of determination (10σ) at a glassy carbon electrode is 3.5 × 10(-6) M and at a HMDE is 3.0 × 10(-6) M. Tetramethrin was selectively determined in an insecticide formulation, at a glassy carbon electrode using differential pulse voltammetry, at a concentration (w/v) of 0.34 ± 0.02%. The determined concentration is in good agreement with the stated value of 0.350 ± 0.018% (w/v).     

Strontium-selective membrane electrodes based on some recently synthesized benzo-substituted macrocyclic diamides

Eight different recently synthesized macrocyclic diamides were studied to characterize their abilities as strontium ion carriers in PVC membrane electrodes. The electrode based on 1,13-diaza-2,3;11,12-dibenzo-4,7,10-trioxacyclopentadecane-14,15-dione exhibits a Nernstian response for Sr(2+) ions over a wide concentration range (1.0 × 10(-)(1)-3.2 × 10(-)(5) M) with a limit of detection of 8.0 × 10(-)(6) M (0.7 ppm). The response time of the sensor is ～10 s, and the membrane can be used for more than three months without observing any deviation. The electrode revealed comparatively good selectivities with respect to many alkali, alkaline earth, and transition metal ions. It was used as an indicator electrode in potentiometric titration of carbonate ions with a strontium ion solution.     

Metal ion (silver, cadmium and zinc ions) modified CdS quantum dots for ultrasensitive copper ion sensing

Metal ion (Ag(+), Cd(2+), Zn(2+)) modified CdS quantum dots (QDs) were synthesized and used for Cu(2+) sensing. Modification by these metal ions could enhance the PL intensity of CdS QDs with the extent of the PL enhancement being related to the concentration of the metal ions. Different metal ion (Ag(+), Cd(2+), Zn(2+)) modified CdS QDs also showed different analytical characteristics for Cu(2+) sensing. In particular, Ag( + ) modified CdS QDs showed greatly enhanced sensitivity for Cu(2+) determination than did the unmodified CdS QDs. A limit of detection (LOD) of 2.0 × 10(-10) M was obtained for Ag(+) modified CdS QDs, which is the lowest LOD obtained using QDs as fluorescence probes for Cu(2+) sensing. This study demonstrates the important role of surface state of QDs in fluorescence sensing.     

Amperometric determination of hydrazine at manganese hexacyanoferrate modified graphite-wax composite electrode

Fabrication, characterization and application of a manganese hexacyanoferrate (MnHCF) modified graphite-wax composite electrode are described. The MnHCF mixed with graphite powder was dispersed into molten paraffin wax to yield a conductive composite, which was used as electrode material to construct a renewable three-dimensional MnHCF modified electrode. The characterization of the modified electrode has been studied by electrochemical techniques. The cyclic voltammogram of the MnHCF modified graphite-wax composite electrode prepared under optimum composition, showed a well-defined redox couple due to Fe(CN)(6)(4-)/Fe(CN)(6)(3-) system. The electrocatalytic oxidation of hydrazine by MnHCF modified graphite-wax composite electrode has been investigated in an attempt to develop a new sensor for its determination. It was found that the mediator catalyzed the oxidation of hydrazine. The electrocatalytic oxidation of hydrazine was also studied under hydrodynamic and chronoamperometric conditions. The anodic current increases linearly with increase in the concentration of hydrazine in the range of 3.33x10(-5)M to 8.18x10(-3)M. The detection limit was found to be 6.65x10(-6)M (S/N=3). The modified electrode can also be used for on-line detection of hydrazine. The proposed method has also been applied for the determination of hydrazine in photographic developer solution.     

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.     

LC-Biosensor System for the Determination of the Neurotoxin β-N-Oxalyl-l-α,β-diaminopropionic Acid

An analysis system is described for the determination of the neurotoxin β-N-oxalyl-l-α,β-diaminopropionic acid (β-ODAP). The system is based on liquid chromatographic separation of β-ODAP from interfering amino acids on an anion exchange column coupled with an amperometric enzyme electrode for the registration of β-ODAP. The electrode is based on a graphite rod modified with an Os(2+/3+) redox polymer cross-linked with l-glutamate oxidase and horseradish peroxidase. This LC-bienzyme electrode analytical system enabled monitoring of as low as 4 μM β-ODAP (injection volume 100 μL). The β-ODAP content in real grass pea samples was measured to range between 3.3 and 5.2 g kg(-)(1) in dry grass pea.     

Lead (II) ion detection in surface water with pM sensitivity using aza-crown-ether-modified silver nanoparticles via dynamic light scattering

In this paper, we reported ultrasensitive lead ion detection in environmental water with pM sensitivity using aza-crown-ether-modified silver nanoparticles (ACE-Ag NPs) through dynamic light scattering (DLS). The colorimetric method based on ACE-Ag NPs is not capable of detecting Pb2+ ions over other metal ions (Fe3+, Co2+, Cu2+, Hg2+, Cd2+, Ag+, Li+, Na+, K+ and Cs+) with high sensitivity. But DLS has improved the selectivity and sensitivity of the Pb2+ detection system (50-fold or more) over colorimetric method, and its detection limit is 0.25 pM (1.03 ppt). The Pb2+ DLS assay can be applied to detect Pb2+ in the environmental water, such as in Yangtze and East Lake water samples with a detection limit of 0.20 and 0.22 pM, which is much lower than the maximum contamination level of 4.8×10(-8) M for lead in surface water defined by the national environmental quality standards of China (GB 3838-2002). Also, this method has a good performance in the determination of Pb2+ in drinking water, which is much lower than the maximum contamination level (MCL) of 72 nM for lead as defined by the US Environmental Protection Agency (EPA).     

Determination of Cu2+ using poly(2-aminothiazole)/ multi-walled carbon nanotubes composite film modified glassy carbon electrodes

2-Aminothiazole was electropolymerized by cyclic voltammetry (CV) on the multi-walled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE) surface. Poly(2-aminothiazole)/MWCNTs/GCE was used for determination of copper ions. The anodic peak currents of copper ions evaluated by differential pulse stripping voltammetry (DPSV) are linear with the concentrations in the range from 1.0 x 10(-7) M to 2.0 x 10(-5) M with a linear coefficiency of 0.9985. The detection limit is 2.0 x 10(-9) M calculated for a signal-to-noise ratio of 3 (S/N = 3). The proposed method was applied successfully to the determination of copper ions in drinking water, and the recovery was 96%.     

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.     

A new Schiff's base ligand immobilized agarose membrane optical sensor for selective monitoring of mercury ion

A highly selective optical sensor was developed for the Hg(2+) determination by chemical immobilization of 2-[(2-sulfanylphenyl)ethanimidoyl]phenol (L), on an agarose membrane. Spectrophotometric studies of complex formation between the Schiff's base ligand L and Hg(2+), Sr(2+), Mn(2+), Cu(2+), Al(3+), Cd(2+), Zn(2+), Co(2+) and Ag(+) metal ions in methanol solution indicated a substantially larger stability constant for the mercury ion complex. Consequently, the Schiff's base L was used as an appropriate ionophore for the preparation of a selective Hg(2+) optical sensor, by its immobilization on a transparent agarose film. A distinct color change, from yellow to green-blue, was observed by contacting the sensing membrane with Hg(2+) ions at pH 4.5. The effects of pH, ionophore concentration, ionic strength and reaction time on the immobilization of L were studied. A linear relationship was observed between the membrane absorbance at 650 nm and Hg(2+) concentrations in a range from 1×10(-2) to 1×10(-5) mol L(-1) with a detection limit (3σ) of 1×10(-6) mol L(-1). No significant interference from 100 times concentrations of a number of potentially interfering ions was detected for the mercury ion determination. The optical sensor was successfully applied to the determination of mercury in amalgam alloy and spiked water samples.     

Electrochemical detection of peroxynitrite using a biosensor based on a conducting polymer-manganese ion complex

A peroxynitrite (ONOO(-)) biosensor has been developed through the preparation of a new manganese-[poly-2,5-di-(2-thienyl)-1H-pyrrole)-1-(p-benzoic acid)] (Mn-pDPB) complex. DPB monomer was first synthesized and polymerized for the purpose of providing a polymer backbone for complex formation with Mn(2+) ion. The Mn-pDPB complex was characterized via Magnetomotive Force (MMF) simulation, X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. The complex selectively enhanced the reduction process of ONOO(-) which was used as the analytical signal for chronoamperometric detection. A polyethyleneimmine (PEI) layer was coated on the complex surface to increase selectivity and stability. The chronoamperometric calibration plot showed the hydrodynamic range of 2.0 × 10(-8)-5.0 × 10(-7) M. The detection limit was determined to be 1.9 (±0.2) × 10(-9) M based on S/N = 3. The microbiosensor, fabricated on a 100 μm diameter Pt tip, was applied in a real rat plasma sample for the detection of spiked concentrations of ONOO(-). The reliability and long-term stability of the microbiosensor was also examined with YPEN-1 cells in vitro, and the results shown were promising.     

Metal-binding particles alleviate lead and zinc toxicity during seed germination of metallophyte grass Astrebla lappacea

Combining metal-binding particles and metal-tolerant plants (metallophytes) offers a promising new approach for rehabilitation of heavy metal contaminated sites. Three types of hydrogel metal-binding polymer particles were synthesized and their effects on metal concentrations tested in vitro using metal ion solutions. The most effective of the tested polymers was a micron-sized thiol functional cross-linked acrylamide polymer which reduced the available solution concentrations of Pb(2+) (9.65 mM), Cu(2+) (4mM) and Zn(2+) (10mM) by 86.5%, 75.5% and 63.8%, respectively, and was able to store water up to 608% of its dry mass. This polymer was not toxic to seed germination. In deionised water, it enhanced seed germination, and at otherwise phytotoxic Pb(2+) (9.65 mM) and Zn(2+) (10mM) concentrations, it allowed normal germination and root elongation of the metallophyte grass Astrebla lappacea. We conclude that the polymer has the potential to facilitate restoration of heavy metal contaminated lands by reducing the concentration of metal cations in the soil solution and improving germination rates through reduced toxicity and enhanced plant water relations.     

A reduced graphene oxide based electrochemical biosensor for tyrosine detection

In this paper, a 'green' and safe hydrothermal method has been used to reduce graphene oxide and produce hemin modified graphene nanosheet (HGN) based electrochemical biosensors for the determination of l-tyrosine levels. The as-fabricated HGN biosensors were characterized by UV-visible absorption spectra, fluorescence spectra, Fourier transform infrared spectroscopy (FTIR) spectra and thermogravimetric analysis (TGA). The experimental results indicated that hemin was successfully immobilized on the reduced graphene oxide nanosheet (rGO) through π-π interaction. TEM images and EDX results further confirmed the attachment of hemin on the rGO nanosheet. Cyclic voltammetry tests were carried out for the bare glass carbon electrode (GCE), the rGO electrode (rGO/GCE), and the hemin-rGO electrode (HGN/GCE). The HGN/GCE based biosensor exhibits a tyrosine detection linear range from 5?×?10(-7)?M to 2?×?10(-5)?M with a detection limitation of 7.5?×?10(-8)?M at a signal-to-noise ratio of 3. The sensitivity of this biosensor is 133 times higher than that of the bare GCE. In comparison with other works, electroactive biosensors are easily fabricated, easily controlled and cost-effective. Moreover, the hemin-rGO based biosensors demonstrate higher stability, a broader detection linear range and better detection sensitivity. Study of the oxidation scheme reveals that the rGO enhances the electron transfer between the electrode and the hemin, and the existence of hemin groups effectively electrocatalyzes the oxidation of tyrosine. This study contributes to a widespread clinical application of nanomaterial based biosensor devices with a broader detection linear range, improved stability, enhanced sensitivity and reduced costs.     

Ferrocenylethyl phosphate: an improved substrate for the detection of alkaline phosphatase by cathodic stripping ion-exchange voltammetry. Application to the electrochemical enzyme affinity assay of avidin

The ferrocenylethyl phosphate disodium salt was synthesized and used as a new substrate for alkaline phosphatase (AP). The enzyme-generated ferroceneethanol was selectively and sensitively detected at a Nafion film-coated electrode by anodic preconcentration of the ferricinium salt, followed by cyclic voltammetry. The accumulated ferricinium units could be expelled from the polymer film in their neutral form by cathodic stripping, and so the Nafion-modified electrode could be reused for more than 10 measurements with a standard deviation less than 3%. Values of 0.75 mM for the Michaelis constant and 1.42 μmol s(-)(1) (mg of protein)(-)(1) for the maximal velocity were found. The regenerable Nafion-coated electrode was employed for the indirect detection of AP down to 2 × 10(-)(12) M and for the noncompetitive heterogeneous enzyme assay of avidin, whose detection limit was 5 × 10(-)(12) M.     

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.     

Impedimetric and potentiometric investigation of a sulfate anion-selective electrode: experiment and simulation

A new anion-selective polyvinyl chloride (PVC) membrane electrode based on {6,6'-diethoxy-2,2'-[2,2-dimethylpropane-1,3-diylbis(nitrilomethylidyne)]diphenolato}nickel(II)monohydrate as a carrier for the sulfate anion is reported. In this work, a new strategy for optimizing membrane components by electrochemical impedance spectroscopy (EIS) is presented. The performance of this electrode was investigated using potentiometric and EIS techniques. The potentiometric results indicated that the prepared electrode had a Nernstian slope of -28.9 ± 0.1 mV in a linear concentrations range of 1.0 × 10(-6) to 3.0 × 10(-1) M, a detection limit of 6.3 × 10(-7) M, an applied pH range of 4.0-9.0, and a response time of less than 15 s; while using the EIS technique, the linear concentrations range was 1.0 × 10(-9) to 1.0 × 10(-1) M and the pH range increased to 4.0-10.0. Finally, the impedance spectra were simulated using the Maple 13 software. A comparison of the experimental data and information obtained from the simulation confirmed the accuracy of the impedance measurement of this electrode.