Fabrication of gold nanoparticles/polypyrrole composite-modified electrode for sensitive hydroxylamine sensor design

A highly sensitive hydroxylamine (HA) electrochemical sensor is developed based on electrodeposition of gold nanoparticles with diameter of 8 nm on the pre-synthesized polypyrrole matrix and formed gold nanoparticles/polypyrrole (GNPs/PPy) composite on glassy carbon electrode. The electrochemical behavior and electrocatalytic activity of the composite-modified electrode are investigated. The GNPs/PPy composite exhibits a distinctly higher electrocatalytic activity for the oxidation of HA than GNPs with twofold enhancement of peak current. The enhanced electrocatalytic activity is attributed to the synergic effect of the highly dispersed gold metal particles and PPy matrix. The overall numbers of electrons involved in HA oxidation, the electron transfer coefficient, catalytic rate constant, and diffusion coefficient are investigated by chronoamperometry. The sensor presents two wide linear ranges of 4.5 × 10⁻⁷–1.2 × 10⁻³ M and 1.2 × 10⁻³–19 × 10⁻³ M with the detection limit of 4.5 × 10⁻⁸ M (s/n = 3). In addition, the proposed electrode shows excellent sensitivity, selectivity, reproducibility, and stability properties.     

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%.     

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).     

Multi-walled carbon nanotube paste electrode for selective voltammetric detection of isoniazid

A multi-walled carbon nanotube paste electrode (MWCPE) is prepared as an electrochemical sensor with high sensitivity and selectivity in responding to isoniazid. The electrochemical oxidation of isoniazid is investigated in buffered solution by cyclic and differential pulse voltammetry. The electrode is shown to be very effective for the detection of isoniazid in the presence of other biological reductant compounds. The electrochemical oxidation of cysteine, due to the high overvoltage, is completely stopped at the surface of MWCPE. The electrode exhibits a very good resolution between the voltammetric peak of isoniazid and the peaks of ascorbic acid (AA) and dopamine (DA). A resolution of more than 450 mV between the anodic peak potentials makes the MWCPE suitable for simultaneous detection of isoniazid in the presence of AA or DA in clinical and pharmaceutical preparations. Differential pulse voltammetry (DPV) is applied as a sensitive method for the determination of isoniazid. The linear range in these determinations is 1 × 10⁻⁶–1 × 10⁻³ M for isoniazid and the detection limit is 5 × 10⁻⁷ M. The electrode was applied to the simultaneous determinations in isoniazid and AA mixtures and also, isoniazid and DA mixture over a wide concentration range. The slope variation for the calibration curves of isoniazid (RSD) was less than 4.5% (based on ten measurements over a period of three months).     

Simultaneous and sensitive determination of procaine and its metabolite for pharmaceutical quality control and pharmacokinetic research by using a graphite paste electrode

A simple, rapid, sensitive, and accurate method for simultaneous electrochemical determination of procaine and its metabolite (p-aminobenzoic acid, PABA) for pharmaceutical quality control and pharmacokinetic research was developed using a graphite paste electrode. The differential pulse voltammetric results revealed that procaine and p-aminobenzoic acid, respectively, showed well-defined anodic oxidation peaks on a carbon paste electrode with a current peak separation of 155 mV at a scan rate of 100 mV s⁻¹. This well separation of the current peaks for these two compounds in voltammetry enables us to simultaneously determine them. Good linearity (r > 0.998) between oxidation peak current and concentration was obtained in the range of 5.0 × 10⁻⁷–5.0 × 10⁻⁵ M for procaine and 5.0 × 10⁻⁷–2.0 × 10⁻⁵ M for PABA in pH 4.50 acetate buffer solution. The detection limit for both analytes is 5 × 10⁻⁸ M (S/N = 3:1). The present voltammetric method has been successfully used to determine trace p-aminobenzoic acid in procaine hydrochloride injection and procaine in plasma with a linear relationship of current to its concentration ranging from 1.0 × 10⁻⁶ to 5.0 × 10⁻⁵ M (correlation coefficient of 0.9981) with a low detection limit of 5.0 × 10⁻⁷ M (S/N = 3:1). This validated method is promising to the study of pharmacokinetics in Sprague–Dawley rat and rabbit plasma after an intravenous administration of procaine hydrochloride injection.     

An electroanalytical study of the drug proflavine

A square wave adsorptive stripping voltammetric (SWAdSV) method was developed for the determination of proflavine. The electrochemical behaviour of proflavine was investigated by cyclic (CV) and square wave voltammetry (SWV) at the hanging mercury drop electrode (HMDE) and carbon paste electrode (CPE). Different parameters were tested to optimize the conditions of the determination. Better results were obtained by square wave voltammetry using CPE where two oxidation and a reduction peak, appeared, at 0.19, 0.94 and 0.20 V, respectively. The peak at 0.19 V is quasi-reversible and deposition dependent. Linearity was observed in the range of (0.2–23.4) × 10⁻⁸ M (r = 0.998) during the anodic scan and in the range of (1.17–117) × 10⁻⁸ M (r = 0.999) during the cathodic scan. The second peak at 0.94 V is irreversible and deposition independent. The linearity of this peak was observed in the range of (1.29–11.7) × 10⁻⁸ M (r = 0.998). The method was applied to the analysis of bovine serum and gave satisfactory results. Correspondence: S. Th. Girousi, Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, Thessaloniki 54124, Greece     

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.     

Electrochemical oxidation of salicylic acid at well-aligned multiwalled carbon nanotube electrode and its detection

In this paper, an electrochemical sensor for sensitive and convenient determination of salicylic acid (SA) was constructed using well-aligned multiwalled carbon nanotubes as electrode material. Compared to the glassy carbon electrode, the electro-oxidation of SA significantly enhanced at the multiwalled carbon nanotube (MWCNT) electrode. The MWCNT electrode shows a sensitivity of 59.25 μA mM⁻¹, a low detection limit of 0.8 × 10⁻⁶ M and a good response linear range with SA concentration from 2.0 × 10⁻⁶ to 3.0 × 10⁻³ M. In addition, acetylsalicylic acid was determined indirectly after hydrolysis to SA and acetic acid, which simplified the detection process. The mechanism of electrochemical oxidation of SA at the MWCNT electrode is also discussed.     

Electrochemistry and voltammetric determination of tannic acid on a single-wall carbon nanotube-coated glassy carbon electrode

The voltammetric behavior of tannic acid (TA) on a single-wall carbon nanotubes (SWNTs) modified glassy carbon electrode has been investigated by cyclic voltammetry. TA can generate a well-defined anodic peak on the modified electrode at around 0.42 V (vs. SCE) in 0.10 M phosphate buffer solutions (pH = 4.0). The electrochemical reaction involves 1e transfer, accompanied by one proton. The electrode process is controlled by adsorption. The parameters affecting the response of TA, such as solution pH, accumulation time and accumulation potential are optimized for the determination of TA. Under the optimum conditions, the peak current changes linearly with the TA concentration in the range of 5.0 × 10⁻⁸–1.0 × 10⁻⁶ M. The lowest detectable concentration of TA is 8.0 × 10⁻⁹ M after 180 s accumulation. This method has been successfully applied to the determination of TA in tea and beer samples. In addition, the influence of potential interferents is examined. In the presence of bovine serum albumin, the peak current of TA decreases linearly due to the formation of a super-molecular complex.     

Direct electrochemistry and electrocatalysis of nitrite based on nano-alumina-modified electrode

Simple and sensitive electrochemical method for the determination of nitrite, based on a nano-alumina-modified glassy carbon electrode (GCE), is described. Nitrite yields a well-defined oxidation peak whose potential is 0.74 V at the nano-alumina-coated GCE in 0.1 mol L⁻¹ phosphate buffer (pH 5.0). Compared with bare GCE, the nano-alumina-modified GCE has evident catalytic effect towards the oxidation of nitrite, and its peak current can be significantly enhanced. Some of the experimental parameters were optimized for the determination of nitrite. The oxidation peak current was proportional to nitrite concentration in the range of 5.0 × 10⁻⁸–1.1 × 10⁻³ mol L⁻¹, and a detection limit of 1.0 × 10⁻⁸ mol L⁻¹ was obtained. This method has been successfully used to the determination of nitrite in sausage sample. Furthermore, results obtained by the method have been compared with spectrophotometric method.     

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.     

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     

Voltammetric sensor for glutathione determination based on ferrocene-modified carbon paste electrode

The electrocatalytic oxidation of glutathione (GSH) has been studied at the surface of ferrocene-modified carbon paste electrode (FMCPE). Cyclic voltammetry (CV), double potential step chronoamperometry, and differential pulse voltammetry (DPV) techniques were used to investigate the suitability of incorporation of ferrocene into FMCPE as a mediator for the electrocatalytic oxidation of GSH in buffered aqueous solution. Results showed that pH 7.00 is the most suitable for this purpose. In the optimum condition (pH 7.00), the electrocatalytic ability of about 480 mV can be found and the heterogeneous rate constant of catalytic reaction was calculated as . Also, the diffusion coefficient of glutathione, D, was found to be 3.61 × 10^–5 cm² s⁻¹. The electrocatalytic oxidation peak current of glutathione at the surface of this modified electrode was linearly dependent on the GSH concentration and the linear analytical curves were obtained in the ranges of 3.2 × 10^–5 M–1.6 × 10^–3 M and 2.2 × 10^–6 M–3.5 × 10^–3 M with cyclic voltammetry and differential pulse voltammetry methods, respectively. The detection limits (3σ) were determined as 1.8 × 10^–5 M and 2.1 × 10^–6 M using CV and DPV, respectively. Finally, the electrocatalytic oxidation of GSH at the surface of this modified electrode can be employed as a new method for the voltammetric determination of glutathione in real samples such as human plasma.     

Application of a Single-Wall Carbon Nano-Tube Film Electrode to the Determination of Trace Amounts of Folic Acid

Single-wall carbon nano-tubes were used to modify the surface of a glassy carbon electrode (GC) and applied in the determination of folic acid with voltammetry. The experiments demonstrated that the presence of a carbon nano-tube film on the electrode greatly increased the reduction peak current of folic acid. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used in a comparative investigation of the electrochemical reduction of folic acid with the film electrode. Effects of pH on the peak current and the peak potential were studied in the pH range of 4.0–8.0 with Britton-Robinson buffer solution. The reduction peak current was found to be linearly related to folic acid concentration over the range of 1 × 10⁻⁸ to 1 × 10⁻⁴ mol L⁻¹ with a detection limit of 1 × 10⁻⁹ mol L⁻¹ after 5 min accumulation. The film electrode provides an efficient way for eliminating interferences from some inorganic and organic species in the solution. The high sensitivity, selectivity and stability of the film electrode demonstrate its practical application from a simple and rapid determination of folic acid in tablets.     

Adsorptive Voltammetric Studies on the Cerium(III)–Alizarin Complexon Complex at a Carbon Paste Electrode

A novel procedure was developed for the determination of trace cerium on the basis of anodic adsorption voltammetry of the Ce(III)–alizarin complexon (ALC) complex at a carbon paste electrode (CPE). The procedure is convenient to determine cerium individually in the presence of other rare earths because there is a 100 mV difference between the peak potentials of Ce(III)–ALC and other rare earth(III)–ALC complexes in a supporting electrolyte of 0.08 M HAc–NaAc and 0.012 M potassium biphthalate (pH 4.7) when performing linear-scanning from −0.2 to 0.8 V (vs. SCE) at 100 mV/s. The second-order derivative peak currents are directly proportional to the Ce(III) concentration over a range of 6.0 × 10⁻⁹–3.0 × 10⁻⁷ M. The detection limit is as low as 2.0 × 10⁻⁹ M (S/N = 3) for a 120 s preconcentration. An RSD of 3.5% was obtained for 15 determinations of Ce(III) at a concentration of 4.0 × 10⁻⁸ M on the same CPE surface. The method was applied successfully to the determination of cerium in samples of rare earth nodular graphite cast iron.     

Electrochemical oxidation behavior of bisphenol A at surfactant/layered double hydroxide modified glassy carbon electrode and its determination

Electrochemical behavior of bisphenol A (BPA) at glassy carbon electrode-modified with layered double hydroxide (LDH) and anionic surfactant (sodium dodecyl sulfate) is investigated by electrochemical techniques. Compared with the bare electrode and LDH-modified electrode, the oxidation peak potential of BPA shifted negatively and the peak current increased significantly due to the enhanced accumulation of BPA via electrostatic interaction with LDH at the hydrophobic electrode surface. Some determination conditions such as LDH loading, pH, scan rate, accumulation potential, and accumulation time on the oxidation of BPA were optimized. And some kinetic parameters were investigated. Under the optimized conditions, the oxidation current was proportional to BPA concentration in the range of 8 × 10⁻⁹ to 2.808 × 10⁻⁶ M with the detection limit of 2.0 × 10⁻⁹ M by amperometry. The fabricated electrode showed good reproducibility, stability, and anti-interference. The proposed method was successfully applied to determine BPA in water samples, and the results were satisfactory.     

Simultaneous determination of uric acid and ascorbic acid at a ferrocenium–thioglycollate modified electrode

Self-assembled monolayers (SAMS) of chemisorbed thioglycollate on a gold electrode surface have been used as a base interface for the electrostatic adsorption of ferrocenium ion. Electrochemical impedance spectra (EIS) and cyclic voltammetry (CV) were used to evaluate the electrochemical properties of the supramolecular film. The bare gold electrode failed to distinguish the oxidation peaks of ascorbic acid (AA) and uric acid (UA) in phosphate buffer solution (PBS, pH 7.0), while the ferricinium–thioglycollate modified electrode could separate them efficiently. In differiential pulse voltammetric measurements, the prepared gold electrode could separate AA and UA signals, allowing the simultaneous determination of AA and UA. Under optimal conditions and within the linear range of 1.0 × 10⁻⁶ to 5.0 × 10⁻⁴ M, the detection limits of AA and UA achieved were 2.0 × 10⁻⁷ and 1.0 × 10⁻⁷ M, respectively. The applicability of the prepared electrode was demonstrated by measuring AA and UA in human urine without any pretreatment. Figure Fabrication process for the modified electrode     

A New Differential Pulse Voltammetric Method for the Determination of Nitrate at a Copper Plated Glassy Carbon Electrode

 A differential pulse voltammetric method for the determination of nitrate has been described, which is applicable to the analysis of natural water samples with nitrate levels greater than 2.8 × 10⁻⁶ M. A reduction peak for the nitrate ions at a freshly copper plated glassy carbon electrode was observed at about −0.50 V vs Ag ∣AgCl∣KCl_satd electrode in a solution of 2.0 × 10⁻² M Cu²⁺, 0.5 M H₂SO₄ and 1.0 × 10⁻³ M KCl and exploited for analytical purposes. The working linear range was established by regression analysis and found to extend from 2.8 ×10⁻⁶ M to 8.0 × 10⁻⁵ M. The proposed method was applied for the determination of nitrate in natural waters. The detection limit of the method was 2.8 × 10⁻⁶ M and the sensitivity was 0.9683 A·L/mol. The possible interferences by some ions such as phosphate, nitrite and some halides were determined and found to lead to shifts of the peak position and increasing the peak heights. Received March 15, 1999. Revision July 9, 1999.     

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.     

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.