Development of an acetylene black–dihexadecyl hydrogen phosphate composite-modified glassy-carbon electrode,and its application in the determination of lovastatin in dosage drug forms

An electrochemical method has been established for the determination of lovastatin (LV). It is based on the enhanced oxidation of lovastatin at a novel acetylene black–dihexadecyl hydrogen phosphate composite-modified glassy-carbon electrode (AB–DHP/GCE) in the presence of Triton X-100. This electrode was prepared by dispersion of acetylene black particles in an aqueous suspension of DHP and the formation of a stable film of the resulting AB–DHP composite on the surface of a glassy carbon electrode (GCE). As a result of modification of the AB–DHP composite, the electrochemical response of lovastatin at GCE was apparently enhanced; this was apparent as amplification of the oxidation current and the negative shift of the oxidation potential. The oxidation current can be further increased in the presence of a trace amount of Triton X-100. The enhanced oxidation of lovastatin at AB–DHP/GCE was due to enlargement of the effective electrode area, catalysis of lovastatin oxidation by AB, and accumulation of lovastatin at the hydrophobic surface of the DHP layer, which would be enhanced by the coherence with Triton X-100. The effects of some working conditions on the oxidation current of lovastatin were tested and the calibration plot was examined. The result showed that the oxidation current was a linear function of lovastatin concentration in the range 2.5×10^–8–1.0×10^–6 mol L^–1 and a low detection limit of 4.0×10^–9 mol L^–1 was obtained under optimum conditions. This electrode system was applied to the determination of lovastatin in dosage drug forms and the results were in accordance with the ultraviolet–visible spectroscopy method.     

Anodic stripping voltammetric determination of mercury using multi-walled carbon nanotubes film coated glassy carbon electrode

An electrochemical method for the determination of trace levels of mercury based on a multi-walled carbon nanotubes (MWNT) film coated glassy carbon electrode (GCE) is described. In 0.1 mol L^–1 HCl solution containing 0.02 mol L^–1 KI, Hg²⁺ was firstly preconcentrated at the MWNT film and then reduced at –0.60 V. During the anodic potential sweep, reduced mercury was oxidized, and then a sensitive and well-defined stripping peak at about –0.20 V appeared. Under identical conditions, a MWNT film coated GCE greatly enhances the stripping peak current of mercury in contrast to a bare GCE. Low concentrations of I^– remarkably improve the determining sensitivity, since this increases the accumulation efficiency of Hg²⁺ at the MWNT film coated GCE. The stripping peak current is proportional to the concentration of Hg²⁺ over the range 8×10^–10–5×10^–7 mol L^–1. The lowest detectable concentration of Hg²⁺ is 2×10^–10 mol L^–1 at 5 min accumulation. The relative standard deviation (RSD) at 1×10^–8 mol L^–1 Hg²⁺ was about 6% (n=10). By using this proposed method, Hg²⁺ in some water samples was determined, and the results were compared with those obtained by atomic absorption spectrometry (AAS). The two results are similar, suggesting that the MWNT-film coated GCE has great potential in practical analysis.     

Graphene‐Nafion Composite Film Modified Electrode for Voltammetric Sensor for Determination of Dihydromyricetin

A simple but highly snesitive electrochemical sensor for the determination of dihydromyricetin (DMY) based on graphene‐Nafion nanocomposite film modified Glassy carbon electrode (GCE) was reported. The characteristic of the sensor was examined by scanning electron microscopic (SEM) and electrochemical impedance spectroscopy (EIS). Compares with bare GCE, pre‐anodized glassy carbon electrode (GCE(ox)) and Nafion modified electrode, the sensor exhibited the more superior ability of detecting DMY, due to the synergetic graphene and Nafion. Other, the dependence of the current on pH, instrumental parameters, accumulation time and potential were investigated to optimize the experimental conditions in the determination of DMY. Under the selected conditions, the response peak currents were linear relationship with the DMY concentrations in the range of 8.0 × 10^?8 ～ 2.0 × 10^?5 mol L^?1 with a detection limit of 2.0 × 10^?8 mol L^?1. And, the method was also applied successfully to detect DMY in Ampelopsis grossedentata samples.     

Voltammetric Sensor for the Determination of Parathion Using an Electropolymerized Poly(Carmine) Film Electrode

A voltammetric sensor for the determination of parathion has been developed based on the use of a poly(carmine) film electrode. The reduction of parathion at the poly(carmine) modified glassy carbon electrode (GCE) is studied by cyclic voltammetry (CV) and linear scan voltammetry (LSV). Parathion yields a well-defined reduction peak at a potential of −0.595 V on the poly(carmine) modified GCE in pH 6.0 phosphate buffer solution (PBS). Compared with that on a bare GCE, the reduction peak current of parathion is significantly enhanced. All the experimental parameters are optimized for the determination of parathion. The reduction peak current is linear with the parathion concentration in the range of 5.0 × 10⁻⁸ to 1.0 × 10⁻⁵ mol L⁻¹, and the detection limit is 1.0 × 10⁻⁸ mol L⁻¹.     

Electrocatalytic Oxidation and Direct Determination of L-Tyrosine by Square Wave Voltammetry at Multi-wall Carbon Nanotubes Modified Glassy Carbon Electrodes

The electrochemical behavior of L-tyrosine was investigated at a multi-wall carbon nanotubes modified glassy carbon electrode. L-tyrosine itself showed a poor electrochemical response at the bare glassy carbon electrode; however, a multi-wall carbon nanotubes film fabricated on the glassy carbon electrode can directly enhance the electrochemical signal of L-tyrosine when applying cyclic voltammetry and square wave stripping voltammetry without any mediator. Cyclic voltammetry was carried out to study the electrochemical oxidation mechanism of L-tyrosine, which shows a totally irreversible process and an oxidation potential of 671 mV at the modified electrode and 728 mV at the bare electrode, ΔE_p = 57 mV. The anodic peak current linearly increases with the square root of scan rate in the low range, suggesting that the oxidation of L-tyrosine on the multi-wall carbon nanotubes modified electrode is a diffusion-controlled process. The square wave stripping voltammetry currents of L-tyrosine at the multi-wall carbon nanotubes modified electrodes increased linearly with the concentration in the range of 2.0 × 10⁻⁶–5.0 × 10⁻⁴ mol L⁻¹. The detection limit was 4.0 × 10⁻⁷ mol L⁻¹. The method is simple, quick, sensitive and accurate.     

Electrochemical Behavior of 8‐Azaguanine at DNA Langmuir–Blodgett Modified Glassy Carbon Electrode and Its Analytical Application

A highly sensitive electrochemical biosensor for the detection of trace amounts of 8‐azaguanine has been designed. Double stranded (ds)DNA molecules are immobilized onto a glassy carbon electrode surface with Langmuir–Blodgett technique. The adsorptive voltammetric behaviors of 8‐azaguanine at DNA‐modified electrode were explored by means of cyclic voltammetry and square wave voltammetry. Compared with bare glassy carbon electrode (GCE), the Langmuir–Blodgett film modified electrode can greatly improve the measuring sensitivity of 8‐azaguanine. Under the optimum experimental conditions, the Langmuir–Blodgett film modified electrode in pH 3.0 Britton–Robinson buffer solutions shows a linear voltammetric response in the range of 5.0×10^?8 to 1.0×10^?5 mol L^?1 with detection limit 9.0×10^?9 mol L^?1. The method proposed was applied successfully for the determination of 8‐azaguanine in diluted human urine with wonderful satisfactory.     

Electrochemical deposition of silicate–cetyltrimethylammonium bromide nanocomposite film on glassy carbon electrode for sensing of methyl parathion

A novel electrochemical sensor for methyl parathion based on silicate– cetyltrimethylammonium bromide nanocomposite film has been fabricated by electro-assisted deposition onto glassy carbon electrode in one-step via an electrochemical modulation of pH at the electrode/solution interface to promote controlled gelification of tetraethylorthosilicate sol, and was characterized with scanning electron microscopy, X-ray diffraction, and electrochemical impedance spectroscopy. The electrochemical sensing of methyl parathion on the film-modified electrode was investigated applying cyclic voltammetry and square wave voltammetry. Compared to the unmodified electrode, the shapes of the redox peaks were improved and the peak currents significantly increased. Experimental parameters such as deposition time, pH value, and accumulation conditions have been optimized. A linear relationship between the peak current and methyl parathion concentration was obtained in the range from 1.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 1.04 × 10 ⁻⁸ mol L⁻¹ (S/N = 3) after accumulation at 0 V for 120 s. The film electrode shows great promise for determination of methyl parathion in real samples.      

An enhanced electrocatalytic oxidation and determination of 2,4-dichlorophenol on multilayer deposited functionalized multi-walled carbon nanotube/Nafion composite film electrode

The voltammetric (CV and DPV) behavior of multi-walled carbon nanotube/Nafion composite coupled with a glassy carbon electrode was investigated for the determination of 2,4-dichlorophenol. The structural and morphological evaluation by XRD and FESEM revealed that the acid treated MWCNT retained their morphology without any structural change. The existence of the possible functional groups was investigated by FTIR and Raman spectroscopy. Compared to bare GCE, a significantly reduced interfacial charge transfer resistance was noticed for MWCNT/Nafion/GCE by electrochemical impedance spectroscopy (EIS). The use of Nafion not only contributed to the non-covalent functionalization of MWCNT, but also protected the electrode surface against the polymerization of phenoxy radicals forming a passivating film. For MWCNT/Nafion/GCE, the combination of anti-passivating ability and excellent catalytic properties resulted in the rapid and direct electrochemical determination of 2,4-DCP. Under optimal experimental conditions, the DPV responses for MWCNT/Nafion/GCE is linear over the 1–150 μmol/L range with a detection limit (S/N = 3) of 0.01 μmol/L. The presence of many interfering species had no influence on the signals of 2,4-DCP. The proposed sensor was successfully tested for the determination of 2,4-DCP in tap water samples and the recovery was in the range of 99.0–102.5%.     

Electroanalytical Determination of Estrone in Seawater Samples Using Functionalized Multiwalled Carbon Nanotubes

In this work, a glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes functionalized with carboxylic groups (MWCNT−COOH) was used to determine the hormone estrone in seawater samples. Modification of the electrode was optimized using three successive 10-μL aliquots of the MWCNT−COOH dispersion in ethanol (1 : 5 mL). The cyclic voltammetry results showed an oxidation peak at 0.59 V with characteristics of an irreversible process, pH dependent and controlled by adsorption of species. The results of square-wave voltammetry showed that the intensities of peak currents for the MWCNT−COOH/GCE were about 2.5 times higher than for GCE. The calibration curve showed a linearity of 0.9981 and a sensitivity of 0.1521 μA/mol L⁻¹. The limits of detection and quantification were 0.117 and 0.392 μmol L⁻¹, respectively. The recovery obtained using seawater samples was 91%, indicating the applicability of the method in marine environments.     

Fabrication of a novel Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MoO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> film modified electrode and its application as an electrochemical sensor of iodate

A novel organic gel film modified electrode was simply and conveniently fabricated by casting Li_xMoO_y and polypropylene carbonate (PPC) onto the surface of a gold electrode. The cyclic voltammetry and amperometry studies demonstrated that the Li_xMoO_y film modified electrode has a high stability and a good electrocatalytic activity for the reduction of iodate. In amperometry, a good linear relationship between the steady current and the concentration of iodate was obtained in the range from 3×10^–7 to 1×10^–4 mol L^–1 with a correlation coefficient of 0.9997 and a detection limit of 1×10^–7 mol L^–1.     

Electrochemical behaviors of ofloxacin and its voltammetric determination at carbon nanotubes film modified electrode

A multi-wall carbon nanotubes (MWNTs)-Nafion film-coated glassy carbon electrode (GCE) was fabricated and the electrochemical behavior of ofloxacin on the MWNTs-Nafion film-coated GCE were investigated by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The oxidation peak current of ofloxacin increased significantly on the MWNTs-Nafion film modified GCE compared with that using a bare GCE. This nano-structured film electrode exhibited excellent enhancement effects on the electrochemical oxidation of ofloxacin. A well-defined oxidation peak attributed to ofloxacin was observed at 0.97 V and was applied to the determination of ofloxacin. The oxidation peak current was proportional to ofloxacin concentration in the ranges 1.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol/L and 1.0 × 10⁻⁶ to 2.0 × 10⁻⁵ mol/L. A detection limit of 8.0 × 10⁻⁹ mol/L was obtained for 400 s accumulation at open circuit (S/N = 3). This method for the detection of ofloxacin in human urine was satisfactory. __________ Translated from Chinese Journal of Applied Chemistry, 2007, 24(5): 540–545 [译自: 应用化学]     

Studies on electrochemical behaviors of acyclovir and its voltammetric determination with nano-structured film electrode

A multi-wall carbon nanotubes (MWNTs)-dihexadecyl hydrogen phosphate (DHP) film-coated glassy carbon electrode (GCE) was fabricated, and the electrochemical behaviors of acyclovir on the MWNTs-DHP film-coated GCE were investigated by using cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and chronocoulometry (CC). The oxidation peak current of acyclovir increased significantly and the peak potential shifted negatively at the MWNTs-DHP film-modified GCE, compared with that at a bare GCE. The results showed that this nano-structured film electrode exhibited excellent enhancement effects on the electrochemical oxidation of acyclovir. Consequently, a simple and sensitive electroanalytical method was developed for the determination of acyclovir. The oxidation peak current was proportional to the concentration of acyclovir from 8.0 × 10⁻⁸ to 1.0 × 10⁻⁵ mol/L. The detection limit was about 3.0 × 10⁻⁸ mol/L for 60 s accumulation at 0.00 V. The proposed method was demonstrated by using acyclovir tablets and the result was satisfying.     

Electrochemical Determination of Tannins Using Multiwall Carbon Nanotubes Modified Glassy Carbon Electrode

A novel chemically modified electrode is prepared on the basis of the attachment of multiwall carbon nanotubes (MWNTs) to the surface of a glassy carbon electrode (GCE) in the presence of a hydrophobic surfactant. The electrochemical behavior of tannins at the MWNTs-modified GCE is investigated. Tannins yield a well-defined oxidation at about 0.30 V (SCE) at the MWNTs-modified GCE. MWNT-film shows remarkable enhancement effect on the oxidation peak current of tannins. The experimental parameters are optimized, and a direct electrochemical method to detect tannins is proposed. The oxidation peak current is proportional to the concentration of tannins over the range from 4 × 10^–7 to 2 × 10^–4 M, and the detection limit is 1 × 10^–7 mol/l after 5 min of accumulation. The relative standard deviation of 6% for determination of 2 × 10^–6 mol/l tannins indicates excellent reproducibility. The analysis method is demonstrated by using tea and Chinese gall samples.     

Electrochemical behavior of a covalently modified glassy carbon electrode with aspartic acid and its use for voltammetric differentiation of dopamine and ascorbic acid

Aspartic acid was covalently grafted on to a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation of the amino-containing compound. X-ray photoelectron spectroscopic (XPS) measurement and cyclic voltammetric experiments proved the aspartic acid was immobilized as a monolayer on the GCE. Electron transfer to Fe(CN)₆^4– in solution of different pH was studied by cyclic voltammetry. Changes in solution pH resulted in the variation of the charge state of the terminal group; surface pK_a values were estimated on the basis of these results. Because of electrostatic interactions between the negatively charged groups on the electrode surface and dopamine (DA) and ascorbic acid (AA), the modified electrode was used for electrochemical differentiation between DA and AA. The peak current for DA at the modified electrode was greatly enhanced and that for AA was significantly reduced, which enabled determination of DA in the presence of AA. The differential pulse voltammetric (DPV) peak current was linearly dependent on DA concentration over the range 1.8×10^–6–4.6×10^–4 mol L^–1 with slope (nA mol^–1 L) and intercept (nA) of 47.6 and 49.2, respectively. The detection limit (3) was 1.2×10^–6 mol L^–1. The high selectivity and sensitivity for dopamine was attributed to charge discrimination and analyte accumulation. The modified electrode has been used for determination of DA in samples, in the presence of AA, with satisfactory results.     

Electrochemical Sensor Based on Multi‐walled Carbon Nanotube/Gold Nanoparticle Modified Glassy Carbon Electrode for Detection of Estradiol in Environmental Samples

We report a rapid and simple method for sensing estradiol by electro‐oxidation on a multi‐walled carbon nanotube (MWCNT) and gold nanoparticle (AuNP) modified glassy carbon electrode (GCE). Compared with a bare GCE, AuNP/GCE and MWCNT/GCE, the composite modified GCE shows an enhanced response to estradiol in 0.1 M phosphate buffer solution. Experimental parameters, including pH and accumulation time for estradiol determination were optimised at AuNP/MWCNT/GCE. A pH of 7.0 was found to be optimum pH with an accumulation time of 5 minutes. Estradiol was determined by linear sweep voltammetry over a dynamic range up to 20 %mol L^?1 and the limit of detection was estimated to be 7.0×10^?8 mol L^?1. The sensor was successfully applied to estradiol determination in tap water and waste water.     

Voltammetric study of glibenclamide at carbon paste and Sephadex-modified carbon paste electrodes

The oxidative behaviour of the antidiabetic agent glibenclamide on a bare carbon paste electrode (CPE) and a Sephadex-modified carbon paste electrode (SMCPE) was explored by cyclic and differential pulse voltammetry (DPV). The analysis procedure consisted of an open circuit accumulation step in stirred sample solution of Britton-Robinson buffer (0.04 mol L^–1, pH 2.0). This was followed by medium exchange to a clean solution of Britton-Robinson buffer (0.04 mol L^–1, pH 5.0), and subsequently an anodic potential scan was effected to obtain the voltammetric peak. The glibenclamide oxidation peak current obtained by DPV was proportional to the concentration of the glibenclamide in the range of 1.0×10^–9 mol L^–1 to 5.0×10^–8 mol L^–1 for 180 s accumulation time, with a detection limit of 4.0×10^–10 mol L^–1. A method was developed for the determination of glibenclamide in formulation and spiked human serum. Moreover, the proposed procedure was used to estimate the serum concentrations after oral administration of a 5 mg tablet of glibenclamide to three diabetic subjects.     

Voltammetric Determination of Phenoxybenzyl‐Type Insecticides at Chemically Modified Conducting Polymer‐Carbon Nanotubes Coated Electrodes

The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M₁) and polypyrrole (herein called as modifier M₂) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L^?1 and 0.05–100 mg L^?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M₁)‐GCE respectively. The MWCNT(M₂)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L^?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L^?1, 0.9 μg L^?1 and 0.1 μg L^?1 for CYP, DEL and FEN respectively on MWCNT(M₂)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.     

Electrocatalytic Properties and Voltammetric Determination of Melatonin at a Nanostructured Film Electrode

A multi-wall carbon nanotube (MWNT) film coated glassy carbon electrode (GCE) was fabricated, and the electrochemical behavior of melatonin on the MWNT film coated GCE was investigated. The oxidation peak current of melatonin increases significantly and the oxidation peak position shifts positively at the MWNT film modified GCE compared to that at a bare GCE. This indicates that MWNTs feature highly effective catalysis to the electrochemical oxidation of melatonin. A simple and sensitive electroanalytical method was developed for the determination of melatonin. The oxidation peak current is proportional to the concentration of melatonin from 8×10^–8 to 1×10^–5molL^–1. The detection limit is about 2×10^–8molL^–1 for 3min accumulation. The proposed method was demonstrated to work satisfactorily with commercial capsules.     

Electrochemistry of sinapine and its detection in medicinal plants

Sinapine (O-sinapoyl choline) is a crucial component, with much medicinal value, of many dietary and medicinal plants. It has been found that sinapine gives an electrochemical response at a pyrolytic graphite electrode. The electrochemical properties of sinapine have been investigated. The peak current in the cyclic voltammogram is linear in the concentration range 1.9×10^–6–2.5×10^–4 mol L^–1 and the limit of detection is 9.9×10^–7 mol L^–1. These properties can be applied to the determination of sinapine in extracts from three kinds of medicinal plant. The electrochemical method reported here is highly selective, sensitive, and stable.     

Voltammetric determination of trace doxorubicin at a nano-titania/nafion composite film modified electrode in the presence of cetyltrimethylammonium bromide

A sensitive electrochemical method was developed for the determination of doxorubicin at a glassy carbon electrode (GCE) modified with a nano-titania (nano-TiO₂)/nafion composite film. Nano-TiO₂ was dispersed into nafion to give a homogeneous suspension. After solvent evaporation, a uniform film of nano-TiO₂/nafion composite was obtained on the GCE surface. The nano-TiO₂/nafion composite film modified GCE exhibited excellent electrochemical behavior toward the reduction of doxorubicin. Compared to the reduction of doxorubicin at the bare GCE, the reduction current of doxorubicin at the nano-TiO₂/nafion composite film modified GCE was greatly enhanced. Based on this, a novel voltammetric method was applied to the determination of doxorubicin. The experimental parameters that influence the reduction current of doxorubicin, were optimized. Under optimal conditions, a linear response of doxorubicin was obtained in the range from 5.0?×?10^?9 to 2.0?×?10^?6 mol L^?1 (R?=?0.998) and with a limit of detection (LOD) of 1.0?×?10^?9 mol L^?1(S/N?=?3). The RSD of the measurement is 4.7%, and the RSD of the inter-electrode is of 5.1% which indicate the reproducibility of this method. The current response decreased only by around 3.8% of its initial response after 2 weeks exposing the electrode in air. The procedure was applied to assay doxorubicin in human plasma samples with the recoveries of 94.9–104.4%.