Os(bpy)2(PVP)10Cl]Cl polymer and Nafion dual-film modified graphite electrode for the amperometric determination of trace amounts of norepinephrine.

A chemically modified graphite electrode was prepared by using a dual film of [Os(bpy)2(PVP)10Cl]Cl polymer and Nafion. The modified electrode showed excellent electrocatalytical activity for the oxidation of norepinephrine (NE) and an ability to eliminate efficiently the interference of ascorbic acid and other anions. The catalytic peak currents obtained from the cyclic voltammograms increased linearly with increasing concentration of NE. A log-log plot of catalytic current versus NE concentration showed a dual-linear relationship in the ranges 1.8 x 10(-8)-4.4 x 10(-6) M and 4.4 x 10(-6)-2.9 x 10(-4) M with correlation coefficients of 0.990 and 0.999, respectively. The detection limit was about 18 nM (3 delta). At a potential of +500 mV the chronoamperometric response showed a linear relationship between the steady state current and NE concentration in the range 1.3-130 microM. With a further increase in NE concentration a Michaelis-Menten-shaped response was observed. The apparent Michaelis-Menten constant and the maximum current were 1.7 mM and 86 microA, respectively. The modified electrode showed excellent reproducibility, sensitivity and stability for the determination of NE at trace levels.     

Direct electrochemistry behavior of cytochrome c/L-cysteine modified electrode and its electrocatalytic oxidation to nitric oxide

Cytochrome c (Cyt c) was successfully immobilized on L-cysteine modified gold electrode by multicyclic voltammetry method. The electrochemical behavior of Cyt c on the L-cysteine modified electrode was explored. In 0.10 M, pH 7.0 phosphate buffer solution (PBS), Cyt c showed a quasi-reversible electrochemical redox behavior with E(pc)=0.180 V, E(pa)=0.208 V (versus Ag/AgCl). The Cyt c/L-cysteine modified electrode gave an excellent electrocatalytic activity towards the oxidation of nitric oxide, and the catalysis currents were proportional to the nitric oxide concentration in the range of 7.0 x 10(-7) to 1.0 x 10(-5) M, the linear regression equation is I (microA)=-0.124-0.003 C(NO) (microM), with a correlation coefficient 0.996, The detection limit was 3.0 x 10(-7) M (times the ratio of signal to noise, S/N=3).     

Simultaneous determination of dopamine, ascorbic acid and uric acid at poly (Evans Blue) modified glassy carbon electrode

A sensitive and selective electrochemical method for the determination of dopamine using an Evans Blue polymer film modified on glassy carbon electrode was developed. The Evans blue polymer film modified electrode shows excellent electrocatalytic activity toward the oxidation of dopamine in phosphate buffer solution (pH 4.5). The linear range of 1.0 x 10(-6)-3.0 x 10(-5) M and detection limit of 2.5 x 10(-7) M were observed in pH 4.5 phosphate buffer solutions. The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of ascorbic acid and uric acid. The separation of the oxidation peak potentials for dopamine-ascorbic acid and dopamine-uric acid were about 182 mV and 180 mV, respectively. The differences are large enough to determine AA, DA and UA individually and simultaneously. This work provides a simple and easy approach to selectively detect dopamine in the presence of ascorbic acid and uric acid in physiological samples.     

Determination of nitrite based on mediated oxidation at a carbon paste electrode modified with a ruthenium polymer

The use of carbon paste electrodes modified with [Ru(bpy)(2)(PVP)(10)Cl]Cl for the mediated detection of nitrite is described. This surface modifier substantially lowers the overpotential for nitrite oxidation, hence permitting its determination at a lower potential. Various electrode characteristics were optimized, including the modifier loading and the monitoring potential, using batch amperometry. Standard calibration curves yielded slopes of 0.30 microA/microM over the linear range 5 x 10(-8)-5 x 10(-4)M nitrite with a detection limit of 3 x 10(-8)M (1.38 ppb) nitrite. The modified electrode response was shown to be relatively stable over a period of 5 days with a signal diminution of 8%. Electrode-to-electrode precision was measured as 11.4%. Flow-injection studies indicated the suitability of this electrode as a detector in flowing streams.     

Design of a new dodecyl sulfate-selective electrode based on conductive polyaniline.

A new, simple, sensitive, low cost and rapid potentiometric method for direct determination of ultra trace amounts of sodium dodecyl sulfate (SDS) with a new DS(-)-selective electrode is reported. The electrode was prepared by electropolymerization of aniline in acidified DS- ion on the surface of a Pt electrode. The cyclic voltammetry (CV) was used for electropolymerization of polyaniline (PA) in the potential range of -200 to +1000 mV vs. Ag/AgCl. This sensor showed a Nernstian behavior (59.0 +/- 2.3 mV/decade) over a very wide linear range (1.0 x 10(-9)-3.0 x 10(-6) M) with a detection limit of 1.0 x 10(-9) M. The response time of the electrode was 15 s for 1.0 x 10(-7) M of analyte; the electrode can be used for 4 weeks without any major deviation. This electrode can be used in the pH range of 3.5-9.8. The selectivity of electrode to DS- over some organic, inorganic and anionic surfactants was investigated with the fixed primary ion method. The results show that the electrode is highly selective to DS- ion over other ions. The proposed electrode was applied to the determination of DS- in real samples.     

Covalent attachment of glucose oxidase to an Au electrode modified with gold nanoparticles for use as glucose biosensor

A feasible method to fabricate glucose biosensor was developed by covalent attachment of glucose oxidase (GOx) to a gold nanoparticle monolayer modified Au electrode. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) of ferrocyanide followed and confirmed the assemble process of biosensor, and indicated that the gold nanoparticles in the biosensing interface efficiently improved the electron transfer between analyte and electrode surface. CV performed in the presence of excess glucose and artificial redox mediator, ferrocenemethanol, allowed to quantify the surface concentration of electrically wired enzyme (Gamma(E)(0)) on the basis of kinetic models reported in literature. The Gamma(E)(0) on proposed electrode was high to 4.1 x 10(-12) mol.cm(-2), which was more than four times of that on electrode direct immobilization of enzyme by cystamine without intermediate layer of gold nanoparticles and 2.4 times of a saturated monolayer of GOx on electrode surface. The analytical performance of this biosensor was investigated by amperometry. The sensor provided a linear response to glucose over the concentration range of 2.0 x 10(-5)-5.7 x 10(-3) M with a sensitivity of 8.8 microA.mM(-1).cm(-2) and a detection limit of 8.2 microM. The apparent Michaelis-Menten constant (K(m)(app)) for the sensor was found to be 4.3 mM. In addition, the sensor has good reproducibility, and can remain stable over 30 days.     

Silver Doped Poly(L‐valine) Modified Glassy Carbon Electrode for the Simultaneous Determination of Uric Acid,Ascorbic Acid and Dopamine

In this paper, a silver doped poly(L ‐valine) (Ag‐PLV) modified glassy carbon electrode (GCE) was fabricated through electrochemical immobilization and was used to electrochemically detect uric acid (UA), dopamine (DA) and ascorbic acid (AA) by linear sweep voltammetry. In pH 4.0 PBS, at a scan rate of 100 mV/s, the modified electrode gave three separated oxidation peaks at 591 mV, 399 mV and 161 mV for UA, DA and AA, respectively. The peak potential differences were 238 mV and 192 mV. The electrochemical behaviors of them at the modified electrode were explored in detail with cyclic voltammetry. Under the optimum conditions, the linear ranges were 3.0×10^?7 to 1.0×10^?5 M for UA, 5.0×10^?7 to 1.0×10^?5 M for DA and 1.0×10^?5 to 1.0×10^?3 M for AA, respectively. The method was successfully applied for simultaneous determination of UA, DA and AA in human urine samples.     

Fabrication of a multilayer film electrode containing porphyrin and its application as a potentiometric sensor of iodide ion

A novel iodide ion-selective electrode has been produced based on a molecular deposition technique in which water-soluble porphyrin was alternatively deposited with water-soluble polypyrrole on a 2-aminoethanethiol modified silver electrode. The potentiometric response is independent of pH of the solution between pH 1 and 7, while it is dependent on the nature of the medium. The electrode has a linear dynamic range between 1.6x10(-6) and 0.1 M with a Nernstian slope of 59 mV/decade and a detection limit of 1.0x10(-6) M in acetate buffer (0.1 M, pH 4.6). The electrode has the advantages of low resistance, short conditioning time and fast response.     

Sulfate-selective electrode based on a complex of copper.

A new sulfate-selective electrode based on the complex N,N'-bis(2-amino-1-oxo-phenelenyl)phenylenediamine copper(II) (CuL) as the membrane carrier was developed. The electrode exhibited a good Nernstian slope of -29.5 +/- 0.5 mV/decade and a linear range of 1.0 x 10(-7) - 1.0 x 10(-1) M for sulfate. The limit of detection was 1.0 x 10(-8) M. It has a fast response time of 10 s and can be used for more than three months. The selective coefficients were determined by the fixed interference method (FIM). The electrode could be used in the pH range 3.5 - 8.0. It was employed as an indicator electrode for direct determination of sulfate in pharmacy and cement samples.     

An electrochemical biosensor for nitric oxide based on silver nanoparticles and hemoglobin.

A nitric oxide (NO) biosensor based on silver nanoparticles was fabricated with high sensitivity and selectivity as well as stability. Silver nanoparticles could preserve the microstructures of hemoglobin, but the electrochemical reactivity of the protein and its detection sensitivity toward NO could be greatly enhanced. Accordingly, a NO biosensor was developed. The linear concentration range was from 1.0 x 10(-6) to 5.0 x 10(-5) M. Its detection limit was 3.0 x 10(-7) M with a sensitivity of 0.0424 microA microM(-1) NO. The possible co-existing compounds would not interfere with the detection.     

Simultaneous electrochemical determination of uric acid and ascorbic acid on a glassy carbon electrode modified with cobalt(II) tetrakisphenylporphyrin.

A cobalt(II) tetrakisphenylporphyrin (Co(II)TPP) film modified glassy carbon electrode (Co(II)TPP-GCE) was prepared by just coating Co(II)TPP solution on the surface of the electrode. It can be used for the simultaneous determination of ascorbic acid and uric acid. The anodic peaks of AA and UA can be separated well. Owing to the strongly hydrophobic property of porphyrin, the modified electrode has good stability and long life. The linear range for UA and AA were 2.0 x 10(-6)-1.0 x 10(-4) M and 9.0 x 10(-6)-2.0 x 10(-3) M with detection limits of 5.0 x 10(-7) and 5.0 x 10(-6) M, respectively. Furthermore, metalloporphyrins of other kinds were also used to construct modified electrodes. Their performances were inferior compared with that of the Co(II)TPP modified electrode.     

Electrocatalytic determination of L-ascorbic acid by modified glassy carbon with Ni(Me2(CH3CO)2[14]tetraenoN4) complex.

A novel modified glassy carbon electrode containing Ni(Me2(CH3CO)2[14]tetraenoN4) complex was used as an electrocatalytic sensor for the determination of L-ascorbic acid in pH = 6.6. The peak potential shifted to negative by 205 mV compared with that for a bare electrode in cyclic voltammograms. The calibration curve was linear up to 6.2 x 10(-3) M with a detection limit 3.1 x 10(-7) M and an RSD% better than 2.47%. This newly modified electrode was applied to commercial pharmaceutical tablets, injections and foods. The obtained results were identical to those obtained by the classical 2,6-dichlorophenolindophenol method.     

Facile and controllable preparation of glucose biosensor based on Prussian blue nanoparticles hybrid composites

A glucose biosensor based on polyvinylpyrrolidone (PVP) protected Prussian blue nanoparticles (PBNPs)-polyaniline/multi-walled carbon nanotubes hybrid composites was fabricated by electrochemical method. A novel route for PBNPs preparation was applied in the fabrication with the help of PVP, and from scanning electron microscope images, Prussian blue particles on the electrode were found nanoscaled. The biosensor exhibits fast current response (<6 s) and a linearity in the range from 6.7x10(-6) to 1.9x10(-3) M with a high sensitivity of 6.28 microA mM(-1) and a detection limit of 6x10(-7) M (S/N=3) for the detection of glucose. The apparent activation energy of enzyme-catalyzed reaction and the apparent Michaelis-Menten constant are 23.9 kJ mol(-1) and 1.9 mM respectively, which suggests a high affinity of the enzyme-substrate. This easy and controllable construction method of glucose biosensor combines the characteristics of the components of the hybrid composites, which favors the fast and sensitive detection of glucose with improved analytical capabilities. In addition, the biosensor was examined in human serum samples for glucose determination with a recovery between 95.0 and 104.5%.     

Electrocatalytic oxidation of hydroxylamine on glassy carbon electrodes modified by hybrid copper-cobalt hexacyanoferrate films.

An electrochemical sensor for amperometric detection of hydroxylamine was developed by electrodeposition of hybrid copper-cobalt hexacyanoferrate films on a glassy carbon electrode. The modified electrode could reduce the overpotential of the hydroxylamine oxidation by about 400 mV. This sensor exhibited a linear relationship between the response current and the hydroxylamine concentration in the range of 1.8 x 10(3) M to 4.6 x 10(-6) M with a detection limit of 2.1 x 10(-7) M. Good agreement was obtained between results from the present method and conventional UV-visible spectrophotometry results. The sensor had good recovery, stability and anti-interference ability.     

维生素B1的电化学聚合及催化作用

用循环伏安法在石墨电极上制备了VB1聚合膜修饰电极,VB1聚合膜在pH5的PBS中有一对氧化还原峰,峰电位Epd=350mV,Epc=325mV,峰电流与扫描速率的平方根成正比,表明电子在膜中的传递为扩散控制,且聚合膜与VB1单体有不同的电化学性质。实验表明VB1聚合膜对多巴胺、肾上腺素等神经递质有显著的电催化作用。     

Redox protein-polymer films for simultaneous determination of ascorbic Acid and hydrogen peroxide

Layer by layer films of protein and redox polymer were constructed and used to simultaneously analyze ascorbic acid and hydrogen peroxide. The films were made using hemoglobin and poly[4-vinylpyridine Os(bipyridine)(2)Cl]-co-ethylamine (Pos-Ea). The film growth was monitored using cyclic voltammetry, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). Reversible pairs of oxidation-reduction peaks were observed using cyclic voltammetry corresponding to the Os(II)/Os(III) from redox polymer and HbFe(III)/HbFe(II) redox couples at 0.35 and -0.25 V vs. Ag/AgCl, respectively. The two redox centers were independent of each other. This enabled the simultaneous and independent determination of ascorbic acid and hydrogen. Peak currents were linearly related to concentration for both analytes in a mixture. The linear range of ascorbic acid was 0 - 1 mM (R(2) = 0.9996, n = 5) at scan rate of 50 mV s(-1) (sensitivity 3.5 microA/mM) while hydrogen peroxide linear range was 1.0 - 10.0 microM (R(2) = 0.991, n = 6) with sensitivity of 1.85 microA/microM.     

Simultaneous Determination of Hydroquinone and Catechol at a Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes

A simply and high selectively electrochemical method for simultaneous determination of hydroquinone and catechol has been developed at a glassy carbon electrode modified with multiwall carbon nanotubes (MWNT). It was found that the oxidation peak separation of hydroquinone and catechol and the oxidation currents of hydroquinone and catechol greatly increase at MWNT modified electrode in 0.20 M acetate buffer solution (pH 4.5). The oxidation peaks of hydroquinone and catechol merge into a large peak of 302 mV (vs. Ag/AgCl, 3 M NaCl) at bare glassy carbon electrode. The two corresponding well‐defined oxidation peaks of hydroquinone in the presence of catechol at MWNT modified electrode occur at 264 mV and 162 mV, respectively. Under the optimized condition, the oxidation peak current of hydroquinone is linear over a range from 1.0×10^?6 M to 1.0×10^?4 M hydroquinone in the presence of 1.0×10^?4 M catechol with the detection limit of 7.5×10^?7 M and the oxidation peak current of catechol is linear over a range from 6.0×10^?7 M to 1.0×10^?4 M catechol in the presence of 1.0×10^?4 M hydroquinone with the detection limit of 2.0×10^?7 M. The proposed method has been applied to simultaneous determination of hydroquinone and catechol in a water sample with simplicity and high selectivity.     

Electrocatalytical oxidation of hydroquinone with ferrocene covalently bound to L-cysteine self-assembled monolayers on a gold electrode

The preparation of a gold electrode modified by ferrocenecarboxylic acid (FcA) covalently bound to L-cysteine self-assembled monolayer (FcA-SAM) is described. The modified electrode shows an excellent electrocatalytic activity for the oxidation of hydroquinone (QH2) and accelerates the electron transfer rate. The anodic overpotential is reduced by ca. 290 mV compared to those obtained at bare gold electrodes. The charge transfer coefficient and the apparent surface electron transfer rate constant for the redox couple of Q/QH2 at the modified electrode are found to be 0.425 and 0.96 s(-1), respectively. The catalytic current response of DPV increases linearly with the QH2 concentration from 5.7 x 10(-7) to 3.2 x 10(-4) M. The estimation of QH2 in a simulative sample is satisfactory. The method is simple, quick, and sensitive.     

Direct electrochemical behavior of cytochrome c on DNA-modified glassy carbon electrode and its application to cytochrome c biosensor.

DNA was immobilized on glassy carbon electrodes to fabricate DNA-modified electrodes. The direct electron transfer of horse heart cytochrome c on DNA-modified glassy carbon electrode was achieved. A pair of well-defined redox peaks of cytochrome c appeared at Epc = -0.017 V and Epa = 0.009 V (vs. Ag/AgCl) in 10 mM phosphate buffer solution (pH 7.0) at a scan rate of 50 mV/s. The electron transfer coefficient (alpha) and the standard rate constant of the surface reaction (Ks) of cytochrome c on DNA-modified electrodes could be estimated to be 0.87 and 34.52 s(-1), respectively. The DNA-modified glassy carbon electrode could be applied to detect cytochrome c by means of differential pulse voltammetry (DPV). The cathodic peak current was proportional to the quantity of cytochrome c in the range of 4.0 x 10(-6) M to 1.2 x 10(-5) M. The correlation coefficient is 0.996, and with the detection limit was 1.0 x 10(-6) M (three times the ratio of signal to noise, S/N = 3).     

Novel sulfate ion-selective polymeric membrane electrode based on a derivative of pyrilium perchlorate

A sulfate ion-selective PVC membrane sensor based on 4-(4-bromophenyl)-2,6-diphenylpyrilium perchlorate (BDPP) as a novel sensing material is successfully developed. The electrode shows a good selectivity for sulfate ion with respect to common organic and inorganic anions. The sensor exhibits a good linear response with slope of -28.9+/-0.5 mV per decade over the concentration range of 1.0x10(-6)-1.0x10(-2) M, and a detection limit of 8.0x10(-7) M of SO(4)(2-) ions. The electrode response is independent of pH in the range of 4.0-9.0. The proposed sensor was applied as an indicator electrode in potentiometric titration of sulfate and barium ions, and to the determination of zinc in zinc sulfate tablets.