Diffusion coefficient measurements in microfluidic devices

A glassy carbon electrode (GCE) modified with Pd/IrO(2) provides excellent electrocatalytic oxidation of hydrogen peroxide. Glucose oxidase (GOD) and xanthine oxidase (XOD) were co-immobilized on the modified electrode with a thin film Nafion coated on the enzyme layer to form a glucose (Glu)/hypoxanthine (Hx) sensor, without interference from electroactive species such as ascorbic acid (AA) and uric acid (UA). Its response was evaluated with respect to the enzyme amount on the electrode, pH and temperature of the electrolyte. The prepared bienzymic biosensor, used as the detector of HPLC gave a detection limit of 1.0x10(-6) mol l(-1) Glu and 2.0x10(-7) mol l(-1) Hx (Hx) with a linear concentration range of 5.0x10(-6)-2.5x10(-3) mol l(-1) and 1.0x10(-6)-5.0x10(-4) mol l(-1), respectively. Coupled with microdialysis, it was used to monitor the concentrations of Glu and Hx in rat brain.     

A chitosan-multiwall carbon nanotube modified electrode for simultaneous detection of dopamine and ascorbic acid.

A chemically modified electrode based on a chitosan-multiwall carbon nanotube (MWNT) coated glassy carbon electrode (GCE) is described, which exhibits an attractive ability to determine dopamine (DA) and ascorbic acid (AA) simultaneously. The modified electrode exhibited a high differential pulse voltammetry (DPV) current response to DA at 0.144 V and AA at -0.029 V (vs. SCE) in a 0.1 mol l(-1) phosphate buffer solution (pH = 7.2). The properties and behaviors of the chitosan-multiwall carbon nanotube modified electrode (MC/GCE) were characterized using cyclic voltammetry (CV) and DPV methods. The mechanism for the discrimination of dopamine from ascorbic acid at MC/GCE is discussed. The linear calibration range for DA and AA were 5 x 10(-7) mol l(-1) to 1 x 10(-4) mol l(-1) (r = 0.997), and 5 x 10(-6) mol l(-1) to 1 x 10(-3) mol l(-1) (r = 0.996), respectively. The MC/GCE showed good sensitivity, selectivity and stability.     

Covalent modification of glassy carbon electrode with glutamic acid for simultaneous determination of uric acid and ascorbic acid

A novel covalently modified glassy carbon electrode with glutamic acid has been fabricated via an electrochemical oxidation procedure and was applied to the catalytic oxidation of uric acid (UA) and ascorbic acid (AA), reducing the overpotentials by about 0.2 V and 0.3 V, respectively. Based on its strong catalytic function toward the oxidation of UA and AA, the modified electrode resolved the overlapping voltammetric response of UA and AA into two well-defined voltammetric peaks with both cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly dependent on the UA and AA concentration in the range 2 x 10(-6)-4 x 10(-4) mol L-1 and 1.0 x 10(-6)-4 x 10(-4) mol L-1 with correlation coefficients of 0.996 and 0.997, respectively. The detection limits (3 delta) for UA and AA were 1.1 x 10(-6) mol L-1 and 9.2 x 10(-7) mol L-1, respectively. The modified electrode shows good sensitivity, selectivity and stability, and has been applied to the determination of UA and AA simultaneously in human urine samples with satisfactory results.     

Electrochemical behavior of the bis(2,2'-bipyridyl)copper(II) complex immobilized on a self-assembled monolayer modified electrode for L-ascorbic acid detection

Modification of a gold electrode has been achieved by immobilizing a bis(2,2'-bipyridyl)copper(II) complex in a self-assembled monolayer (SAM) of 3-mercaptopropionic acid. The electrostatic interaction of the negatively charged SAM with a di-positive copper complex allowed the attachment. The modified electrode exhibited excellent redox behavior. The dependence of the modified electrode response was investigated in terms of pH, supporting electrolyte and ionic strength. Moreover, it showed good electrocatalytic activity for ascorbic acid oxidation, allowing convenient quantification at levels down to 8.1 x 10(-8) mol l(-1). The [Cu(bipy)2]/SAM modified electrode under optimized operational conditions (PIPES buffer 0.01 mol l(-1) at pH 6.8 and 200 mV vs. SCE) presented a linear response range between 1.0 micromol l(-1) and 100.0 micromol l(-1) for ascorbic acid. This modified electrode also presented an excellent repeatability, showing a relative standard deviation of 2.1% for a series of 12 successive measurements of a 5.0 micromol l(-1) ascorbic acid solution. Furthermore, the electroactivity was maintained over a long period (e.g., 92% after 100 determinations).     

Flow injection determination of bromide ion in a developer using bromide ion-selective electrode detector

A potentiometric flow injection determination method for bromide ion in a developer was proposed, by utilizing a flow-through type bromide ion-selective electrode detector. The sensing membrane of the electrode was Ag(2)S-AgBr membrane. The response of the electrode detector as a peak-shape signal was obtained for injected bromide ion in a developer. A linear relationship was found to exist between peak height and the concentration of the bromide ion in a developer in a concentration range from 1.0x10(-3) to 1.0x10(-2) mol l(-1). The relative standard deviation for 10 injections of a 6x10(-3) mol l(-1) bromide ion in a developer was 1.3% and the sampling rate was ca 17-20 samples h(-1). The present method was free from the interference of an organic reducing reagent, an organic substance in a developer sample solution for the determination of bromide ion in a developer.     

Evaluation of luminol-H(2)O(2)-KIO(4) chemiluminescence system and its application to hydrogen peroxide, glucose and ascorbic acid assays

A novel chemiluminescence (CL) system was evaluated for the determination of hydrogen peroxide, glucose and ascorbic acid based on hydrogen peroxide, which has a catalytic-cooxidative effect on the oxidation of luminol by KIO(4). Hydrogen peroxide can be directly determined by luminol-KIO(4)-H(2)O(2) CL system. The detection limit was 3.0x10(-8) mol l(-1) and the calibration graph was linear over the range of 2.0x10(-7)-6.0x10(-4) mol l(-1). The relative standard deviation of H(2)O(2) was 1.1% for 2.0x10(-6) mol l(-1) (N=11). Glucose was indirectly determined through measuring the H(2)O(2) generated by the oxidation of glucose in the presence of glucose oxidase at pH 7.6. The present method provides a source for H(2)O(2), which, in turn, coupled with the luminol-KIO(4)-H(2)O(2) CL reaction system. The CL was linearly correlated with glucose concentration of 0.6-110 mug ml(-1). The relative standard deviation was 2.1% for 10 mug ml(-1) (N=11). Detection limit of glucose was 0.08 mug ml(-1). Ascorbic acid was also indirectly determined by the suppression of luminol-KIO(4)-H(2)O(2) CL system. The calibration curve was linear over the range of 1.0x10(-7)-1.0x10(-5) mol l(-1) of ascorbic acid. The relative standard deviation was 1.0% for 8.0x10(-7) mol l(-1) (N=11). Detection limit of ascorbic acid was 6.0x10(-8) mol l(-1). These proposed methods have been applied to determine glucose, ascorbic acid in tablets and injection.     

Electrochemical determination of dopamine using a poly(2-picolinic acid) modified glassy carbon electrode

A poly(2-picolinic acid) chemically modified electrode (CME) for the determination of dopamine (DA) by cyclic voltammetry is described. Compared with a bare glassy carbon electrode, the CME exhibits a 200 mV shift of the oxidation potential of DA in the cathodic direction and a marked enhancement of the current response. In pH 7.0 buffer solution, a linear calibration graph is obtained over the range from 2.5 x 10(-7) to 1.0 x 10(-5) mol dm-3 with a correlation coefficient of 0.998. The detection limit is 3.0 x 10(-8) mol dm-3. The modified electrode eliminated efficiently the interference from ascorbic acid (AA) when present in a 150-fold concentration ratio. It also showed excellent stability and reproducibility.     

Covalent modification of glassy carbon electrodes with beta-alanine for voltammetric separation of dopamine and ascorbic acid.

beta-Alanine was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) proved the immobilization of beta-alanine monolayer on GCE. The electrode shows strong electrocatalytic functions to dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by 0.20 V and 0.23 V, respectively. Due to its different catalytic effects toward DA and AA, the modified electrode resolved the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by CV or differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentrations in the ranges of 4.0 x 10(-6)-5.0 x 10(-4) mol/L and 2.0 x 10(-5)-6.0 x 10(-3) mol/L with correlation coefficients of 0.997 and 0.995, respectively. The detection limits (3 sigma) for DA and AA were 2.4 x 10(-6) mol/L and 1.2 x 10(-5) mol/L, respectively. The electrode shows good sensitivity, selectivity and stability, and has been applied to the determination of DA and AA simultaneously in samples with satisfactory results.     

Determination of ascorbic acid content of some fruit juices and wine by voltammetry performed at pt and carbon paste electrodes

A method was developed for assessing ascorbic acid concentration in fruit juices and wine by differential pulse voltammetry. The oxidation peak for ascorbic acid occurs at about 530 mV (versus SCE) on a Pt strip working electrode and at about 470 mV on a carbon paste working electrode. The influence of the operational parameters like the pulse amplitude and the pulse period on the analytical signal was investigated. The obtained calibration graph shows a linear dependence between the peak height and ascorbic acid concentration within the range 0.31-20 mM with a Pt working electrode, and within the range 0.07-20 mM with a carbon paste working electrode. The equation of the calibration graph was y = 21.839x + 35.726, r2 = 0.9940, when a Pt strip electrode was used (where y represents the value of the current intensity measured for the peak height, expressed as μA and x the analyte concentration, as mM). R.S.D. = 2.09%, n = 10, C(ascorbic acid) = 2.5 mM. The equation of the calibration graph was y = 3.4429x + 5.7334, r2 = 0.9971, when a carbon paste electrode was used (where y represents the value of intensity measured for the peak height, expressed as μA and x the analyte concentration, as mM). R.S.D. = 2.35%, n = 10, C(ascorbic acid) = 2.5 mM. The developed method was applied to ascorbic acid assessment in fruit juices and wine. The ascorbic acid content determined ranged between 6.83 mg/100 mL juice for soft drinks (Fanta Madness) and 54.74 mg/100 mL for citrus (lemon) juices obtained by squeezing fruit. Different ascorbic acid concentrations (from standard solutions) were added to the analysed samples, the degree of recovery being comprised between 94.74 and 104.97%. The results of ascorbic acid assessment by differential pulse voltammetry were compared with those obtained by cyclic voltammetry. The results obtained by the two methods were in good agreement.     

Voltammetric and amperometric determination of ascorbic acid at a chemically modified carbon fibre microelectrode

A carbon fibre microelectrode was modified by electrodeposition of a thin copper-heptacyanonitrosylferrate (CuHNF) film on its surface. The film showed the ability to catalyse electrochemical oxidation of ascorbic acid. The catalytic reaction was limited either by diffusion, or by the electrochemical reaction of the catalyst. A linear, cyclic voltammetric response for ascorbic acid was obtained between 5.0 x 10(-5) and 6.0 x 10(-3)M. By amperometric measurements the linear range could be extended to 8.0 x 10(-6)-2.0 x 10(-3)M. The modified electrode showed good stability and reproducibility.     

Studies on the Electrochemistry of Dopamine at a Pyrocatechol Sulfonephthalein Modified Glassy Carbon electrode

IntroductionThere has been a considerable interest in developing the methods to measure the secretionneurotransmitters. Electrochemical teChniques have proven to be significantly advantageous tothe biosciencesLlj. The application of ultramicroelectrodes to neuroscien.ce, which has been pioneered by Adams[2], to monitor the concentration of neurotransmitters in the central nervesystem has had a special impact. Several neurotransmitters, e. g., dopamine(DA) are electroactlve and therefore can …     

Flow injection turbidimetric determination of thiamine in pharmaceutical formulations using silicotungstic acid as precipitant reagent

A simple flow injection system is proposed for the determination of thiamine in pharmaceutical formulations. The determination is based on the precipitation reaction of thiamine with silicotungstic acid in acidic medium to form a thiamine silicotungstate suspension that is measured at 420 nm. Adding 0.05% (w/v) poly(ethyleneglycol) in the carrier solution (0.5 mol l(-1) hydrochloric acid), an improvement in the sensitivity, repeatability and baseline stability of the flow injection system was obtained. The calibration graph was linear in the thiamine concentration range from 5.0x10(-5) to 3.0x10(-4) mol l(-1) with a detection limit of 1.0x10(-5) mol l(-1). The relative standard deviations for ten successive measurements of 1.0x10(-4) mol l(-1) and 2.5x10(-4) mol l(-1) thiamine were less than 1% and an analytical frequency of 90 h(-1) was obtained.     

A stable glucose biosensor prepared by co-immobilizing glucose oxidase into poly(p-chlorophenol) at a platinum electrode

An amperometric glucose biosensor was successfully developed by electrochemical polymerization of p-chlorophenol (4-CP) at a Pt electrode in the presence of glucose oxidase. The amperometric response of this biosensor to hydrogen peroxide, formed as the product of enzymatic reaction, was measured at a potential of 0.6 V (vs. SCE) in phosphate buffer solution. The performances of sensors, prepared at different monomer concentrations and polymerization potentials, were investigated in detail. The biosensor prepared under optimal conditions had a linear response to glucose ranging from 2.5 x 10(-4) to 1.5 x 10(-2) mol L(-1) with a correlation coefficient of 0.997 and a response time of less than 2 s. Substrate selectivity of the polymer-based enzyme electrode was tested for coexisting interferents such as uric acid and ascorbic acid, and no discernible response was observed. After 90 days, the response of the biosensor remained almost unchanged, indicating very good stability.     

抗坏血酸在聚槲皮素修饰电极上的电化学行为

采用电聚合方法制备了一种新的聚槲皮素(PQu)修饰电极,并用循环伏安法研究了该电极的电化学行为。在pH=4.0的B-R缓冲溶液中有一对准可逆的氧化还原峰,实验表明聚槲皮素电极过程是2电子2质子的可逆反应。该膜对抗坏血酸有良好的电催化作用,氧化峰电流与抗坏血酸浓度在4.76×10-6~1.0×10-4mol/L范围内呈良好的线性关系,检出限达1.5×10-6mol/L。尿酸不干扰抗坏血酸的测定。     

Optimization of polymeric triiodide membrane electrode based on clozapine-triiodide ion-pair using experimental design

Central composite design (CCD) and response surface methodology (RSM) were developed as experimental strategies for modeling and optimization of the influence of some variables on the performance of a new PVC membrane triiodide ion-selective electrode. This triiodide sensor is based on triiodide-clozapine ion-pair complexation. PVC, plasticizers, ion-pair amounts and pH were investigated as four variables to build a model to achieve the best Nernstian slope (59.9 mV) as response. The electrode is prepared by incorporating the ion-exchanger in PVC matrix plasticized with 2-nitrophenyl octal ether, which is directly coated on the surface of a graphite electrode. The influence of foreign ions on the electrode performance was also investigated. The optimized membranes demonstrate Nernstian response for triiodide ions over a wide linear range from 5.0 x 10(-6) to 1.0 x 10(-2)mol L(-1) with a limit of detection 2.0 x 10(-6) mol L(-1) at 25 degrees C. The electrodes could be used over a wide pH range 4-8, and have the advantages of easy to prepare, good selectivity and fast response time, long lifetime (over 3 months) and small interferences from hydrogen ion. The proposed electrode was successfully used as indicator electrode in potentiometric titration of triiodide ions and ascorbic acid.     

PCA/GC电极同时测定尿酸(UA)和抗坏血酸(AA)

制备聚肉桂酸(PCA)修饰电极(PCA/GC),研究尿酸(UA)和抗坏血酸(AA)在该电极上的电化学行为.结果表明,在UA和AA共存体系中,UA、AA在PCA/GC电极上氧化峰电流增大且峰电位分别负移至50mV、330mV,二者相差280mV,据此可同时检测UA和AA.在pH6.0磷酸盐缓冲液中,UA、AA的氧化峰电流与其浓度分别在2.0×10-6～1.0×10-4mol·L-1、2.0×10-5～6.0×10-4mol·L-1范围内呈线性关系.该电极重现性好,适用于尿样中UA的检测.     

Charge-transfer triiodide ion-selective electrode based on 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane.

A new PVC membrane electrode for the triiodide ion based on a charge-transfer complex of iodine with 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane as a membrane carrier was prepared. The electrode exhibits a Nernstian response for triiodide ions over a wide concentration range (1.0 x 10(-1)-1.0 x 10(-5) M) with a slope of 59.3 +/- 0.9 mV decade(-1) and a detection limit of 6.3 x 10(-6) M. It has a response time of 30 s and can be used for at least 3 months without any divergence in the potential. The potentiometric response is independent of the pH, in the pH range 1.6 - 10.0. The proposed electrode has shown very high selectivity for the triiodide ion over a wide variety of other anions. This electrode was successfully applied as an indicator electrode in the potentiometric titration of ascorbic acid and hydroquinone from pharmaceutical preparations as well as ascorbic acid in orange juice and dissolved O2 in tap water.     

Electrocatalytic characteristics of a 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone modified carbon-paste electrode in the oxidation of ascorbic acid.

A carbon-paste electrode spiked with 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone was constructed by the incorporation of 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone in a graphite powder silicon oil matrix. It shown by cyclic voltammetry and double potential-step chronoamperometry, which this ferrocene derivative modified a carbon-paste electrode, can catalyze the ascorbic acid oxidation in an aqueous buffered solution. It has been found that under the optimum conditions (pH 7.00), the oxidation of ascorbic acid at the surface of this carbon paste modified electrode occurs at a potential of about 260 mV less positive than that of an unmodified carbon-paste electrode. The catalytic oxidation peak current was linearly dependent on the ascorbic acid concentration, and a linear calibration curve was obtained in the range of 6 x 10(-5) M-7 x 10(-3) M of ascorbic acid with a correlation coefficient of 0.9997. The detection limit (2sigma) was determined to be 6.3 x 10(-5) M. This method was also used for the determination of ascorbic acid in some pharmaceutical samples, such as effervescent tablets, ampoules and multivitamin syrup, by using a standard addition method. The reliability of the method was established by a parallel determination against the official method.     

Covalent modification of glassy carbon electrodes with glycine for voltammetric separation of dopamine and ascorbic acid

Glycine was covalently grafted on to a glassy carbon electrode (GCE) by amine cation radical formation in electrooxidation of the amino-containing compound. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry proved the immobilization of glycine on the GCE. The modified electrode reduced the overpotentials of dopamine (DA) and ascorbic acid (AA) by approximately 0.15 V and 0.23 V, respectively, and resolved the overlapping voltammetric response of DA and AA into two well-defined voltammetric peaks in cyclic voltammetry (CV) or differential pulse voltammetry (DPV), unlike the unmodified GCE; this can be used for the simultaneous determination of these species in a mixture. The differential pulse peak current was linearly dependent on DA and AA concentration in the range 5 x 10(-6)-8 x 10(-4) mol L(-1) and 6 x 10(-5)-4 x 10(-3) mol L(-1), with correlation coefficients of 0.996 and 0.994, respectively. The detection limits (3delta) for DA and AA were 1.8 x 10(-6) mol L(-1) and 2.1 x 10(-5) mol L(-1), respectively. The modified electrode is very sensitive, selective and stable, and has been applied to the determination of DA and AA simultaneously in samples with satisfactory results.     

Electroregenerable anion-exchange resin with triiodide carbon paste electrode for the voltammetric determination of adrenaline

An electroregenerable carbon paste electrode modified with triiodide ions immobilized in an anion-exchange resin (Lewatit M500) is proposed for the determination of adrenaline in pharmaceutical products by differential-pulse voltammetry (DPV). Adrenaline was chemically converted into adrenochrome by the I3- ions at the electrode surface. The electrochemical reduction back to adrenaline was obtained at a potential of -0.16 V vs. Ag/AgCl (3 mol l(-1) KCl). A 20% decrease of the initial analytical signal was observed after 350-400 determinations; the carbon paste electrode was 100% electroregenerated at a fixed potential of +0.65 V vs. Ag/AgCl (3 mol l(-1) KCl) in 0.1 mol l(-1) KI solution for 20 min. The differential-pulse voltammograms were obtained by applying a sweep potential between 0.0 and -0.34 V, following the adrenochrome reduction at -0.16 V. Under the optimum conditions established, such as pH 6.0; scan rate 20 mV s(-1) and pulse amplitude 50 mV, the calibration curve was linear from 2.0 x 10(-5) to 3.1 x 10(-4) mol l(-1) adrenaline with a detection limit of 3.9 x 10(-6) mol l(-1). The recovery of adrenaline ranged from 99.8 to 103.1% and the RSD was 2.6% for the solution containing 1.0 x 10(-4) mol l(-1) adrenaline (n = 10). The results obtained for adrenaline in pharmaceutical samples using the proposed carbon paste electrode are in agreement with those obtained using a pharmacopoeial procedure at the 95% confidence level.