Covalent modification of a glassy carbon electrode with penicillamine for simultaneous determination of hydroquinone and catechol

A simple and highly selective electrochemical method has been developed for the simultaneous determination of hydroquinone (HQ) and catechol (CC) at a glassy carbon electrode covalently modified with penicillamine (Pen). The electrode is used for the simultaneous electrochemical determination of HQ and CC and shows an excellent electrocatalytical effect on the oxidation of HQ and CC upon cyclic voltammetry in acetate buffer solution of pH 5.0. In differential pulse voltammetric measurements, the modified electrode was able to separate the oxidation peak potentials of HQ and CC present in binary mixtures by about 103 mV although the bare electrode gave a single broad response. The determination limit of HQ in the presence of 0.1 mmol L⁻¹ CC was 1.0 × 10⁻⁶ mol L⁻¹, and the determination limit of CC in the presence of 0.1 mmol L⁻¹ HQ was 6.0 × 10⁻⁷ mol L⁻¹. The method was applied to the simultaneous determination of HQ and CC in a water sample. It is simple and highly selective.     

Covalent modification of glassy carbon electrode with cysteine for the determination of dopamine in the presence of ascorbic acid

A covalently modified glassy carbon electrode with cysteine has been fabricated via an electrochemical oxidation procedure and was applied to induce the electrochemical differentiation between dopamine (DA) and ascorbic acid (AA). Based on the electrostatic interactions between the negatively charged groups on the electrode surface and DA and AA, the modified electrode enhanced the oxidation of DA, reducing the overpotential by 180 mV, and hindered the oxidation of AA, shifting the oxidation potential positively by 170 mV. The peak current for DA at the modified electrode was greatly enhanced and that for AA was significantly decreased, which allows the determination of DA in the presence of AA. The differential pulse peak current was linearly dependent on DA concentration over the range of 5 × 10⁻⁶–2 × 10⁻⁴ mol L⁻¹. The detection limit was 1.8 × 10⁻⁶ mol L⁻¹. The selectivity and sensitivity for dopamine is due to charge discrimination and analyte accumulation. The modified electrode has been applied to the determination of DA in the presence of AA. Correspondence: L. Zhang, Department of Chemistry, College of Life and Environmental Science, Shanghai Normal University, Guilin Rd 100, Shanghai 200234, P.R. China     

Electrochemical behavior of lead(II) at poly(phenol red) modified glassy carbon electrode, and its trace determination by differential pulse anodic stripping voltammetry

Poly(phenol red) (denoted as PPR) films were electrochemically synthesized on the surface of a glassy carbon electrode (GCE) by cyclic voltammetry to obtain a chemically modified electrode (denoted as PPR-GCE). The growth mechanism of PPR films was studied by attenuated total reflection spectroscopy. This PPR-GCE was used to develop a novel and reliable method for the determination of trace Pb²⁺ by anodic stripping differential pulse voltammetry. At optimum conditions, the anodic peak exhibits a good linear concentration dependence in the range from 5.0 × 10⁻⁹ to 5.0 × 10⁻⁷ mol L⁻¹ (r = 0.9989). The detection limit is 2.0 × 10⁻⁹ mol L⁻¹ (S/N = 3). The method was employed to determine trace levels of Pb²⁺ in industrial waste water samples. Correspondence: Gongjun Yang, Ming Shen, College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P.R. China     

Electrochemical Behavior of Uric Acid and Epinephrine at a Meso-2,3-Dimercaptosuccinic Acid Self-Assembled Gold Electrode

A self-assembled electrode with a meso-2,3-dimercaptosuccinic acid (DMSA) monolayer has been characterized by electrochemical quartz crystal microbalance and complex impedance analysis, surface enhanced Raman spectroscopy and cyclic voltammetry. The self-assembled electrode was used for the simultaneous electrochemical detection of epinephrine (EP) and uric acid (UA) in phosphate buffer of pH 7.7. The simultaneous oxidation of EP and UA was performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), and the signals for each method were well separated with a potential difference of over 330 mV and without interference by each other. The detection limit of EP is 5.4 × 10⁻⁸ mol L⁻¹ by CV and 5.3 × 10⁻⁸ mol L⁻¹ by DPV and that of UA is 8.4 × 10⁻⁸ mol L⁻¹ by CV and 4.2 × 10⁻⁸ mol L⁻¹ by DPV. The DMSA self-assembled electrode can be applied to the simultaneous determination of EP and UA.     

Electrochemical behavior and determination of epinephrine at a mercaptoacetic acid self-assembled gold electrode

The electrochemical behavior of epinephrine (EP) at a mercaptoacetic acid (MAA) self-assembled monolayer modified gold electrode was studied. The MAA/Au electrode is demonstrated to promote the electrochemical response of epinephrine by cyclic voltammetry. The possible reaction mechanism is also discussed. The diffusion coefficient D of EP is 6.85 × 10⁻⁶ cm² s⁻¹. In 0.1 mol L⁻¹ phosphate buffer (pH 7.20), a sensitive oxidation peak was observed at 0.177 V, and the peak current is proportional to the concentration of EP in the range of 1.0 × 10⁻⁵–2.0 × 10⁻⁴ mol L⁻¹ and 1.0 × 10⁻⁷–1.0 × 10⁻⁶ mol L⁻¹. The detection limit is 5 × 10⁻⁸ mol L⁻¹. The modified electrode is highly stable and can be applied to the determination of EP in practical injection samples. The method is simple, quick, sensitive and accurate.     

Sensitive voltammetric sensor of dihydromyricetin based on Nafion/SWNT-modified glassy carbon electrode

A novel voltammetric sensor, based on single-walled carbon nanotubes (SWNT) dispersed in Nafion and modified glassy carbon electrode (GCE), was fabricated and used to determine the trace amounts of dihydromyricetin (DMY). The electrochemical behavior of DMY at this sensor was investigated in 0.1 mol L⁻¹ sulfuric acid solutions + 0.1 mol L⁻¹ NaCl by cyclic voltammetry and squarewave voltammetry. Compared with bare GCE, the electrode presented an excellent response of DMY through an adsorption-controlled quasi-reversible process. Under the optimum conditions, the response peak currents were linear relationship with the DMY concentrations in the range of 1.0 × 10⁻⁷–1.0 × 10⁻⁵ mol L⁻¹ with a detection limit of 9 × 10⁻⁸ mol L⁻¹. Based on this voltammetric sensor, a simple and sensitive electroanalytical method for DMY was proposed and applied to quantitative determination of DMY in Ampelopsis grossedentata samples. In addition, the oxidation mechanism was proposed and discussed, which could be a reference for the pharmacological action of DMY in clinical study.     

Electrocatalytic oxidation of nitrite at a terpyridine manganese(II) complex modified carbon past electrode

A carbon past electrode modified with [Mn(H₂O)(N₃)(NO₃)(pyterpy)], ( \textpyterpy = 4￠- ( 4 - \textpyridyl ) - 2,2￠:\text6￠,\text2￠￠- \textterpyridine ) \left( {{\text{pyterpy}} = 4\prime - \left( {4 - {\text{pyridyl}}} \right) - 2,2\prime:{\text{6}}\prime,{\text{2}}\prime\prime - {\text{terpyridine}}} \right) complex have been applied to the electrocatalytic oxidation of nitrite which reduced the overpotential by about 120 mV with obviously increasing the current response. Relative standard deviations for nitrite determination was less than 2.0%, and nitrite can be determined in the ranges of 5.00 × 10⁻⁶ to 1.55 × 10⁻² mol L⁻¹, with a detection limit of 8 × 10⁻⁷ mol L⁻¹. The treatment of the voltammetric data showed that it is a pure diffusion-controlled reaction, which involves one electron in the rate-determining step. The rate constant k′, transfer coefficient α for the catalytic reaction, and diffusion coefficient of nitrite in the solution, D, were found to be 1.4 × 10⁻², 0.56× 10⁻⁶, and 7.99 × 10⁻⁶ cm² s⁻¹, respectively. The mechanism for the interaction of nitrite with the Mn(II) complex modified carbon past electrode is proposed. This work provides a simple and easy approach to detection of nitrite ion. The modified electrode indicated reproducible behavior, anti-fouling properties, and stability during electrochemical experiments, making it particularly suitable for the analytical purposes.     

Simultaneous voltammetric determination of dihydroxybenzene isomers using a poly(acid chrome blue K)/carbon nanotube composite electrode

A novel modified electrode was fabricated by electropolymerization of acid chrome blue K at a multi-walled carbon nanotubes modified glassy carbon electrode. The electrode developed was used for simultaneous determination of the isomers of dihydroxybenzene in environmental samples using first order linear sweep derivative voltammetry with background subtraction. A linear relationship between peak current and concentration of hydroquinone, catechol and resorcinol was obtained in the range of 1 × 10⁻⁶–1 × 10⁻⁴ mol L⁻¹, and the detection limits were estimated to be 1 × 10⁻⁷, 1 × 10⁻⁷ and 9 × 10⁻⁸ mol L⁻¹, respectively. The constructed electrode showed excellent reproducibility and stability. Real water samples were analyzed and satisfactory results were obtained. This method provides a new way of constructing electrodes for environmental and biological analysis.     

Electrochemical determination of acetaminophen using a glassy carbon electrode coated with a single-wall carbon nanotube-dicetyl phosphate film

Single-wall carbon nanotubes (SWNT) were dispersed into water in the presence of dicetyl phosphate (DCP), and then a SWNT-DCP film-coated glassy carbon electrode (GCE) was constructed. The electrochemical behavior of acetaminophen at bare GCE and SWNT-DCP modified GCE were compared, suggesting that the SWNT-DCP-modified GCE significantly enhances the oxidation peak current of acetaminophen. A sensitive and simple electrochemical method with a good linear relationship in the range of 1.0 × 10⁻⁷–2.0 × 10⁻⁵ mol L⁻¹, was developed for the determination of acetaminophen. The detection limit is 4.0 × 10⁻⁸ mol L⁻¹ for 3-min accumulation. This method was successfully demonstrated with tablets.     

Determination of chromium(VI) and total chromium in water by in-electrode coulometric titration in a porous glassy carbon electrode

Chromium(VI) is determined through its direct electrochemical reduction in the bulk of a porous glassy carbon electrode. An electrode filled with the acidified sample and Cr(VI) is reduced by means of a constant current whereas the potential of the electrode is monitored. The limits of detection and quantification were found to be 1.9 and 6.0 μg · L⁻¹, resp. The linear range, repeatability and reproducibility were found to be 5–500 μg · L⁻¹, 1.2, and 1.8%, resp. The influence of Fe(III), Ca(II), Mg(II), sulphates, nitrates, humic acids and surfactants was investigated. Total chromium was measured after chemical oxidation of Cr(III) to chromate by permanganate. The method was applied to analyses of water samples.     

Selective determination of uric acid in the presence of ascorbic acid using a penicillamine self-assembled gold electrode

The electrochemical behaviors of uric acid (UA) at the penicillamine (Pen) self-assembled monolayers modified gold electrode (Pen/Au) have been studied. The Pen/Au electrode is demonstrated to promote the electrochemical response of UA by cyclic voltammetry (CV). The diffusion coefficient D of UA is 6.97 × 10⁻⁶ cm² s⁻¹. In differential pulse voltammetric (DPV) measurements, the Pen/Au electrode can separate the UA and ascorbic acid (AA) oxidation potentials by about 120 mV and can be used for the selective determination of UA in the presence of AA. The detection limit was 1 × 10⁻⁶ mol L⁻¹. The modified electrode shows excellent sensitivity, good selectivity and antifouling properties.     

Adsorptive anodic stripping voltammetry of zirconium(IV)-alizarin red S complex at a carbon paste electrode

A sensitive adsorptive anodic stripping procedure for the determination of trace zirconium at a carbon paste electrode (CPE) has been developed. The method is based on adsorptive accumulation of the Zr(IV)-alizarin red S(ARS) complex onto the surface of the CPE, followed by oxidation of adsorbed species. The optimal experimental conditions include the use of 0.10 mol · L⁻¹ ammonium acetate buffer (pH 4.3), ARS, an accumulation potential of 0.20 V (versus SCE), an accumulation time of 2 min, a scan rate of 200 mV · s⁻¹ and a second-order derivative linear scan mode. The oxidation peak for the complex appears at 0.69 V. The peak current is proportional to the concentration of Zr(IV) over the range of 1.0 × 10⁻⁹–2.0 × 10⁻⁷ mol · L⁻¹, and the detection limit is 3 × 10⁻¹⁰ mol · L⁻¹ for a 2 min adsorption time. The relative standard deviations (n = 8) for 5.0 × 10⁻⁸ and 5.0 × 10⁻⁹ mol · L⁻¹ Zr(IV) are 3.3 and 4.8%, respectively. The proposed method was applied to the determination of zirconium in ore samples with satisfactory results.     

Simultaneous voltammetric determination of ascorbic acid and uric acid using a Nafion/multi-wall carbon nanotubes composite film-modified electrode

A Nafion/multi-wall carbon nanotubes (MWNT) composite film-modified electrode was fabricated. The modified electrode showed excellent electrocatalytic activity toward ascorbic acid (AA) and uric acid (UA) in 0.1-mol L⁻¹ NaCl medium (pH 6.5). Compared to the bare electrode that only displayed a broad and overlapped oxidation peak, the Nafion/MWNT film-modified electrode not only remarkably enhanced the anodic peak currents of AA and UA but also avoided the overlapping of the anodic peaks of AA and UA with a 320-mV separation of both peaks. Under the optimized conditions, the peak currents of AA and UA were proportional to their concentration at the ranges of 8.0 × 10⁻⁵ to 6.0 × 10⁻³ mol L⁻¹ and 6.0 × 10⁻⁷ to 8.0 × 10⁻⁵ mol L⁻¹, respectively. The proposed method was used for the detection of AA and UA in real samples with satisfactory results.     

Simultaneous voltammetric measurement of ascorbic acid and dopamine on poly(caffeic acid)-modified glassy carbon electrode

A poly(caffeic acid) thin film was deposited on the surface of a glassy carbon electrode by potentiostatic technique in an aqueous solution containing caffeic acid. The poly(caffeic acid)-modified electrode was used for the determination of ascorbic acid (AA), dopamine (DA), and their mixture by cyclic voltammetry. This modified electrode exhibited a potent and persistent electron-mediating behavior followed by well-separated oxidation peaks toward AA and DA at a scan rate of 10 mV s⁻¹ with a potential difference of 135 mV, which was large enough to determine AA and DA individually and simultaneously. The catalytic peak current obtained was linearly dependent on the AA and DA concentrations in the range of 2.0 × 10⁻⁵−1.2 × 10⁻³ and 1.0 × 10⁻⁶−4.0 × 10⁻⁵ mol L⁻¹ in 0.15 mol L⁻¹ phosphate buffer (pH 6.64). The detection limits for AA and DA were 9.0 × 10⁻⁶ and 4.0 × 10⁻⁷ mol L⁻¹, respectively. The modified electrode shows good sensitivity, selectivity, and stability and has been applied to the determination of DA and AA in real samples with satisfactory results.     

Covalent Modification of Glassy Carbon Electrode with L-Cysteine for the Determination of Acetaminophen

A novel L-cysteine film modified electrode has been fabricated by means of an electrochemical oxidation procedure, and it was successfully applied to the electrochemical determination of acetaminophen. This method utilizes the electrooxidation of amines to their analogous cation radicals to form a chemically stable covalent linkage between the nitrogen atom of the amine and edge plane sites at the glassy carbon electrode surface. The electrochemical behaviour of acetaminophen at the film electrode was investigated in 0.1 mol L⁻¹ phosphate buffer (pH 6.20). It was found that the redox peak current of acetaminophen was enhanced greatly on the film electrode. Linearity between the oxidation peak current and the acetaminophen concentration was obtained in the range of 1.0 × 10⁻⁴–2.0 × 10⁻⁷ mol L⁻¹ with a detection limit of 5.0 × 10⁻⁸ mol L⁻¹. For seven parallel detections of 1.0 × 10⁻⁵ mol L⁻¹ acetaminophen, the relative standard deviation (RSD) was 1.46%, suggesting that the film electrode has excellent reproducibility. Application to the determination of acetaminophen in drug tablets and human urine demonstrated that the film electrode has good stability and high sensitivity.     

Determination of thiocyanate ions at nanolevel in real samples using coated graphite electrode based on synthesised macrocyclic Zn(II) complex

The electrode characteristics and selectivities of PVC-based thiocyanate selective polymeric membrane electrode (PME) incorporating the newly synthesized zinc complex of 6,7:14,15-Bzo₂-10,11-(4-methylbenzene)-[15]-6,8,12,14-tetraene-9,12-N₂-1,5-O₂ (I ₁ ) and zinc complex of 6,7:14,15-Bzo₂-10,11-(4-methylbenzene)-[15]-6,14-diene-9,12-dimethylacrylate-9,12-N₂-1,5-O₂ (I ₂ ) are reported here. The best response was observed with the membrane having a composition of I₂:PVC:o-NPOE:HTAB in the ratio of 6:33:59:2 (w/w; milligram). This electrode exhibited Nernstian slope for thiocyanate ions over working concentration range of 4.4 × 10⁻⁷ to 1.0 × 10⁻² mol L⁻¹ with detection limit of 2.2 × 10⁻⁷ mol L⁻¹. The performance of this electrode was compared with coated graphite electrode (CGE), which showed better response characteristics w.r.t Nernstian slope 59.0 ± 0.2 mV decade⁻¹ activity, wide concentration range of 8.9 × 10⁻⁸ to 1.0 × 10⁻² mol L⁻¹ and detection limit of 6.7 × 10⁻⁸ mol L⁻¹. The response time for CGE and PME was found to be 8 and 10 s, respectively. The proposed electrode (CGE) was successfully applied to direct determination of thiocyanate in biological and environmental samples and also as indicator electrode in potentiometric titration of SCN⁻ ion.     

Electrochemical behaviors of GMP based on solid-phase extractionon at Cu-Mg-Al hydrotalcite-like compound (HTLC) modified glass carbon electrode

Guanosine-5′-monophosphate (GMP) was investigated the electrochemical behaviors based on solid-phase extractionon (SPE) at Cu-Mg-Al hydrotalcite-like compound (HTLC) modified glass carbon electrode. Cu-Mg-Al hydrotalcite-like compound (HTLC) was proved as a new sorbent for SPE of GMP, which showed an irreversible adsorption oxidation process on the HTLC/GCE with the oxidation peak potential located at 1.15 V (vs. SCE) in a pH 5.0 acetate buffer solution. Influencing factors of the electrochemical behavior of GMP on the HLTC/GCE were optimized and kinetic parameters were calculated. Under the optimal conditions, with differential pulse voltammetry (DPV), a linear relationship was obtained between the oxidation peak current and the GMP concentration in the range from 1.0 × 10^− 6 to 8.0 × 10⁻⁴ mol L⁻¹ with the detection limit as 5.0 × 10⁻⁷ mol L⁻¹ (signal-to-noise ratio of 3). The modified electrode surface has very good reproducibility and stability.     

Simultaneous determination of uric acid and ascorbic acid at the film of chitosan incorporating cetylpyridine bromide modified glassy carbon electrode

A glassy carbon electrode (GCE) modified with the film composed of chitosan incorporating cetylpyridine bromide is constructed and used to determine uric acid (UA) and ascorbic acid (AA) by differential pulse voltammetry (DPV). This modified electrode shows efficient electrocatalytic activity and fairly selective separation for oxidation of AA and UA in mixture solution. UA is catalyzed by this modified electrode in phosphate buffer solution (pH 4.0) with a decrease of 80 mV, while AA is catalyzed with a decrease of 200 mV in overpotential compared to GCE, and the peak separation of oxidation between AA and UA is 260 mV, which is large enough to allow the determination of one in presence of the other. Under the optimum conditions, the anodic peak currents (I _pa) of DPV are proportional to the concentration of UA in the range of 2.0 × 10⁻⁶ to 6.0 × 10⁻⁴ M, with the detection limit of 5.0 × 10⁻⁷ M at a signal-to-noise ratio of 3 (S/N = 3) and to that of AA in the range of 4.0 × 10⁻⁶ to 1.0 × 10⁻³ M, with the detection limit of 8.0 × 10⁻⁷ M (S/N = 3).     

Electrochemical behavior of uric acid at a penicillamine self-assembled gold electrode

The fabrication and electrochemical characteristics of a penicillamine (PCA) self-assembled monolayer modified gold electrode were investigated. The electrode can enhance the electrochemical response of uric acid (UA), and the electrochemical reaction of UA on the PCA electrode has been studied by cyclic voltammetry and differential pulse voltammetry. Some electrochemical parameters, such as diffusion coefficient, standard rate constant, electron transfer coefficient and proton transfer number have been determined for the electrochemical behavior on the PCA self-assembled monolayer electrode. The electrode reaction of UA is an irreversible process, which is controlled by the diffusion of UA with two electrons and two protons transfer at the PCA/Au electrode. In phosphate buffer (pH 5.0), the peak current is proportional to the concentration of UA in the range of 6.0 × 10⁻⁵–7.0 × 10⁻⁴ mol L⁻¹ and 2.0 × 10⁻⁵–7.0 × 10⁻⁴ mol L⁻¹ for the cyclic voltammetry and differential pulse voltammetry methods with the detection limits of 5.0 × 10⁻⁶ and 3.0 × 10⁻⁶ mol L⁻¹, respectively. The method can be applied to determine UA concentration in real samples.     

Simple sensor for simultaneous determination of dihydroxybenzene isomers

A simple sensor based on bare carbon ionic liquid electrode was fabricated for simultaneous determination of dihydroxybenzene isomers in 0.1 mol L⁻¹ phosphate buffer solution (pH 6.0). The oxidation peak potential of hydroquinone was about 0.136 V, catechol was about 0.240 V, and resorcinol 0.632 V by differential pulse voltammetric measurements, which indicated that the dihydroxybenzene isomers could be separated absolutely. The sensor showed wide linear behaviors in the range of 5.0 × 10⁻⁷–2.0 × 10⁻⁴ mol L⁻¹ for hydroquinone and catechol, 3.5 × 10⁻⁶–1.535 × 10⁻⁴ mol L⁻¹ for resorcinol, respectively. And the detection limits of the three dihydroxybenzene isomers were 5.0 × 10⁻⁸, 2.0 × 10⁻⁷, 5.0 × 10⁻⁷ mol L⁻¹, respectively (S/N = 3). The proposed method could be applied to the determination of dihydroxybenzene isomers in artificial wastewater and the recovery was from 93.9% to 104.6%.