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.     

Determination of formaldehyde by staircase voltammetry based on its electrocatalytic oxidation at a nickel electrode

In this paper, a novel method for detection of formaldehyde (HCHO), based on its electrocatalytic oxidation of HCHO at a nickel electrode, is reported. The mechanism of electrocatalytic oxidation and quantification of HCHO have been investigated by cyclic and staircase voltammetry, respectively. The electrocatalytic oxidation peak potential of HCHO is at about 475 mV vs. Ag/AgCl electrode; the peak current responds proportionally to concentrations of HCHO in alkaline solution. The linear range of detection is from 46.8 to 1640 μg/L (1.56 × 10⁻⁶ to 5.46 × 10⁻⁵ M) with a correlation coefficient of 0.996 and a detection limit of 23.4 μg/L (7.80 × 10⁻⁷ M). The relative standard deviation (RSD) is less than 6% (n = 5), and the recovery is in the range 98–106% for real samples. The result is consistent with that from the spectrophotometry. The text was submitted by the authors in English.     

Voltammetric and Spectrophotometric Determination of Nizatidi ne in Pharmaceutical Formulations

 Two methods are described for quantitative determination of nizatidine. The first is a cathodic stripping voltammetric method which is based on the accumulation of the compound at the hanging mercury drop electrode. The adsorptive stripping response was evaluated with respect of accumulation time, potential, concentration, pH and other variables. A linear calibration graph was obtained over the range 3.0×10⁻⁸–1.0×10⁻⁶ M with a detection limit 3.0×10⁻⁸ M after a 20s accumulation time at −0.2 V accumulation potential. On the other hand, it was found that the detection limit could be lowered to 1.0×10⁻⁸ M after 180s accumulation time at −0.2 V accumulation potential. The relative standard deviation was in the range 1.2−2.0% for six measurements. The tolerance amounts of the common excipients have also been reported. The second is a spectrophotometric method which is based on the formation and extraction of the ion-pair complex formed between nizatidine and either bromocresol green or bromothymol blue. The extracted colored ion-pair complexes absorb at 416 nm. The effect of different factors such as: type of organic solvent, pH, reagent concentration, number of extraction times, shaking time, temperature and the tolerance amount of the common excipients have been reported. The calibration graph was linear in the range 6.0×10⁻⁷–1.8×10⁻⁵ M with a detection limit of 6.0×10⁻⁷ M and molar absorptivity of 2.1×10⁴ lċmol⁻¹ċcm⁻¹ when using bromocresol green, while the calibration graph was linear in the range 3.0×10⁻⁷–1.1×10⁻⁵ M with a detection limit of 3.0×10⁻⁷ M and molar absorptivity of 3.2×10⁴ lċmol⁻¹ċcm⁻¹ when using bromothymol blue. The spectrophotometric methods offer alternative methods with reasonable sensitivity, selectivity and accuracy with relative standard deviation in the range 2.1−6.0% and 1.2−4.7% (for six measurements) when using bromothymol blue and bromocresol green, respectively. The proposed two methods were applied for the determination of nizatidine in commercially available dosage forms. A comparison between the voltammetric and the extraction-spectrophotometric methods was also reported. Received April 19, 1999. Revision August 30, 1999.     

A nitric oxide biosensor based on the photovoltaic effect of nano titanium dioxide on hemoglobin

A nitric oxide biosensor based on the photovoltaic effect of nano titanium dioxide on hemoglobin was fabricated with high sensitivity, selectivity, as well as stability. The linear detection concentration range was 5.0 × 10⁻⁶–4.0 × 10⁻⁴ M. The detection limit was 1.0 × 10⁻⁶ M with a sensitivity of 8 nA/μM. The possible coexisting compounds would not interfere with the nitric oxide detection. The article is published in the original.     

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.     

A simple optical sensor for cadmium ions assay in water samples using spectrophotometry

A new simple and inexpensive optical chemical sensor for cadmium(II) ions is presented. The cadmium sensing system was prepared by incorporating 2-amino-cyclopentene-1-dithiocarboxylic acid (ACDA) on a triacetylcellulose membrane. The absorption spectra of the optical sensor membrane in Cd(II) solution showed a maximum peak at 430 nm. The proportionality in intensity of the membrane color on the optode to varying amounts of Cd(II) suggests its potential applications for screening Cd(II) in aqueous samples by visual colorimetry. The sensor provided a wide concentration range of 3.0 × 10⁻⁶–3.4 × 10⁻⁴ M of Cd(II) ions with a detection limit of 1.0 × 10⁻⁶ M (0.2 μg/mL). The relative standard deviations for eight replicate measurements of 8.0 × 10⁻⁶ and 5.0 × 10⁻⁵ M Cd(II) were 2.7 and 2.3%, respectively. The response time of the optode was 6 min. The influence of interfering ions on the determination of 1.0 × 10⁻⁵ M Cd(II) was studied and the main interferences were removed by extraction method. The sensor was applied to the determination of Cd(II) in water samples.     

Simultaneous electrochemical detection of uric acid and ascorbic acid at a silver doped poly(glutamic acid) modified glassy carbon electrode

In this paper, the silver doped poly (L-glutamic acid) modified glassy carbon electrode (PLG-Ag/GCE) was fabricated through an electrochemical immobilization. The modified electrode was used for simultaneous determination of uric acid (UA) and ascorbic acid (AA) in 0.1 M phosphate buffer solutions (PBS). The cyclic voltammetric signals of UA and AA were well separated with a potential difference of 396 mV in pH 3.0 phosphate buffer solution. The linear calibration curves were obtained in the concentration range 5.00 × 10⁻⁷–1.00 × 10⁻⁴ M for UA and 8.00 × 10^-6–5.00 × 10⁻³ M for AA with the detection limits of 3 × 10⁻⁷ M and 4 × 10⁻⁶ M, respectively. The relative standard deviations were 1.3 and 1.0% for the determinations of UA and AA for 20 continuous measurements. The signal was highly stable and reproducible. This method was successfully applied to the determination of UA in human urine samples.     

A kinetic method for the determination of organosulfur compounds by inhibition: determination of cysteine, 2,3-dimercaptopropanol and thioglycolic acid

A kinetic method for the determination of organosulfur compounds by UV spectrophotometry is described. Organosulfur compounds have been shown to inhibit the Hg(II)-catalyzed substitution of cyanide in hexacyanoferrate(II) by 2-methylpyrazine (2-Mepz). The inhibitory effect is proportional to the concentration of inhibitor and can be used as the basis for the determination of trace amounts of organosulfur compounds such as cysteine, 2,3-dimercaptopropanol (DMP) and thioglycolic acid (TGA). Both the influence of the reaction variables and interference of a variety of ions have been studied. A mechanism for the inhibition process is proposed. The determination range depends on the amount of Hg(II) added and stability of the Hg(II)–ligand complex. Kinetic parameters were determined from Lineweaver–Burk plots, obtained in the absence and presence of the inhibitor. Excellent linearity is observed for all analytes over their respective concentration ranges with correlation coefficient >0.9. The condition calibration curves were linear in the range of 5 × 10⁻⁶–15 × 10⁻⁶ M for cysteine, 1 × 10⁻⁷–7 × 10⁻⁷ M for DMP and 1 × 10⁻⁶–10 × 10⁻⁶ M for TGA. The detection limits were 1.18 × 10⁻⁷ M for cysteine, 4.16 × 10⁻⁸ M for DMP and 1.30 × 10⁻⁷ M for TGA. The effects of amino acids that can interfere in the determination of cysteine were studied.     

Electrochemical detection of copper(II) at a gold electrode modified with a self-assembled monolayer of penicillamine

A penicillamine (PCA) self-assembled monolayer (SAM) was prepared on a gold electrode. It has been found that the modified electrode exhibited a selective response to copper ions. As demonstrated by cyclic voltammetric experiments, the SAM-based electrode showed an attractive ability to preconcentrate efficiently traces of copper(II) from solutions. Under optimum conditions, the anodic peak current was proportional to the concentration of Cu(II) in the range from 8.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M with a detection limit of 4.0 × 10⁻⁷ M. Moreover, this modified gold electrode is also characterized by excellent repeatability, showing a relative standard deviation of 3.2% for nine successive measurements of 1.0 × 10⁻⁵ M Cu(II). The PCA/Au SAM gold electrode was used for the determination of Cu(II) in a tap water sample and the results showed a good agreement with the data obtained by atomic emission spectrometry. The text was submitted by the authors in English.     

Differential kinetic thermal lens determination of aniline and 4-nitroaniline

Thermal lens spectrometry was used for the differential kinetic determination of aniline (over the concentration range of 8 × 10⁻⁴–3.2 × 10⁻³ M) and 4-nitroaniline (2 × 10⁻⁴–1.6 × 10⁻³ M) present in combination in a single sample based on the oxidation reaction with periodate ions in an acidic medium (this determination is not possible with the spectrophotometric monitoring of the rate of reaction). The thermal lens procedure (λ_e = 488.0 nm; 80 mW) was characterized by good performance characteristics in the determination of aniline (c _min = 3 × 10⁻⁴ M; c _d = 8 × 10⁻⁴ M) and 4-nitroaniline (c _min = 7 × 10⁻⁵ M; c _d = 2 × 10⁻⁴ M), simplicity, and rapidity.     

Preconcentration and Voltammetric Study of Nicergoline at a Carbon Paste Electrode

 The electrochemical oxidation of nicergoline is investigated using cyclic and differential pulse voltammetry at a carbon paste electrode. For the determination of nicergoline an adsorptive stripping procedure is proposed. The response is characterized with respect to pH, ionic strength, preconcentration time, accumulation potential, nicergoline concentration, reproducibility and other variables. By differential pulse voltammetry at a carbon paste electrode and pH 8.0, a linear calibration in the range 5×10⁻⁸ M to 1×10⁻⁷ M and a detection limit of 1×10⁻⁸ M are obtained. The preconcentration medium-exchange approach was used for a selective determination of nicergoline in urine. For dilute urine samples a detection limit of 5×10⁻⁸ M is obtained after 3 min of accumulation and medium-exchange. The procedure also is applied for the determination of nicergoline in dosage form. Received August 24, 1998. Revision April 8, 1999.     

Determination of vitamin B<Subscript>1</Subscript> in seawater and microalgal fermentation media by high-performance liquid chromatography with fluorescence detection

A highly sensitive high-performance liquid chromatographic method with fluorescence detection has been developed for determination of vitamin B₁. Vitamin B₁ was converted into a fluorescent compound by treatment with hydrogen peroxide–horseradish peroxidase and the derivative was subsequently analyzed by HPLC on a Waters Spherisorb ODS2 column (250 mm×4.6 mm ID, 5 μm) with 40:60 methanol–pH 8.5 acetate buffer solution as mobile phase and fluorescence detection at 440 nm (with excitation at 375 nm). The calibration graph was linear from 5.00×10⁻¹⁰ mol L⁻¹ to 5.00×10⁻⁷ mol L⁻¹ for vitamin B₁ with a correlation coefficient of 0.9991 (n=9). The detection limit was 1.0×10⁻¹⁰ mol L⁻¹. The method was successfully used for determination of vitamin B₁ at pg mL⁻¹ levels in microalgal fermentation media and seawater after solid-phase extraction. Recovery was from 89 to 110% and the relative standard deviation was in the range 1.1 to 4.3%.     

Electroanalysis of kaempferol using pyrolytic graphite and a hemoglobin/polysorbate-20 modified electrodes

The electrochemical behavior of kaempferol, one of the most common flavonoids, was studied using a pyrolytic graphite electrode and a hemoglobin/polysorbate-20 modified electrode. The modified electrode was found to be applicable for kaempferol determination. The linear calibration was in the range from 4 × 10⁻⁷ to 4 × 10⁻⁵ M, with a limit of detection (LOD) of 1 × 10⁻⁷ M. The relative standard deviation (RSD) was 3.3% for ten successive determinations. The proposed method is sensitive, has a high reproducibility, and a wide detection range. The text was submitted by the authors in English.     

Reagentless biosensor for phenolic compounds based on tyrosinase entrapped within gelatine film

A simple and new reagentless phenolic compound biosensor was constructed with tyrosinase immobilized in the gelatine matrix cross-linked with formaldehyde. The morphologies of gelatine and gelatine/tryosinase were characterized by SEM. The tyrosinase retains its bioactivity when being immobilized by the gelatine film. Phenolic compounds were determined by the direct reduction of biocatalytically liberated quinone at -0.1 V vs SCE. The process parameters for the fabrication of the enzyme electrode were studied. Optimization of the experimental parameters has been performed with regard to pH, operating potential, temperature and storage stability. This biosensor exhibits a fast amperometric response to phenolic compounds. The linear range for catechol, phenol, and p-Cresol determination was from 5×10⁻⁸ to 1.4×10⁻⁴ M, 5×10⁻⁸ to 7.1×10⁻⁵ M, and 1×10⁻⁷ to 3.6×10⁻⁵ M, with a detection limit of 2.1×10⁻⁸ M, 1.5×10⁻⁸ M, and 7.1×10⁻⁸ M, respectively. The enzyme electrode retained ca.77% of its activity after 7 days of storage at 4°C in a dry state. The proposed sensor presented good repeatability, evaluated in terms of relative standard deviation (R.S.D.=8.6%) for eight different biosensors and was applied for determination in water sample. The recovery for the sample was from 99.0% to 99.8%.     

The complex (2,3;6,7;10,11;14,15-tetraphenyl-4,9,13,16-tetraoxo-1,5,8,12-tetraazacyclohexadecane) copper(II) as a carrier for a salicylate-sensitive poly(vinylchloride) membrane electrode

A new salicylate-selective electrode based on the complex (2,3;6,7;10,11;14,15-tetraphenyl-4,9,13,16-tetraoxo-1,5,8,12-tetraazacyclohexadecane) copper(II) [CuL] as the membrane carrier was developed. The electrode exhibits a good Nernstian slope of −60.9 ± 1.0 mV/decade and a linear range from 1.0 × 10⁻⁶ to 1.0 × 10⁻¹ M for salicylate. The detection limit is 5.0 × 10⁻⁷ M. The electrode has a fast response time (5–15 s) and can be used for more than three months. The selective coefficients were determined by the fixed interference method (FIM) and separate solution method (SSM). The salicylate-selective electrode could be used in the pH range 3.5–10.5. It was employed as an indicator electrode for direct determination of salicylate in pharmaceutical samples. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 9, pp. 1147–1154. The text was submitted by the authors in English.     

Selective lanthanum ions optical sensor based on covalent immobilization of 4-hydroxysalophen on a hydrolyzed triacetylcellulose membrane

An optical sensor membrane is described for the determination of lanthanum(III) ions based on the immobilization of 4-hydroxysalophen on a hydrolyzed triacetylcellulose membrane. 4-Hydroxysalophen is covalently bonded to a transparent hydrolyzed triacetylcellulose film. The sensing membrane in contact with lanthanum ions at pH 4.0 changes color from white-yellow to orange (323 to 433 nm). Under the optimum conditions, the proposed membrane displayed a linear range from 1.0 × 10⁻⁶ to 1.0 × 10⁻² M La(III) with a limit of detection of 1 × 10⁻⁷ M. The response time of the membrane was within 5–6 min depending on the concentration of La(III) ions. The selectivity of the probe towards lanthanum ions was found to be excellent. The sensor was successfully applied to the determination of La(III) in water, industrial waste water, and in NIST-615 (glass matrix) and NIST-3127a (lanthanum solution) samples with satisfactory results.     

Voltammetric determination of thiocytosine based on its electrocatalytic oxidation on the surface of carbon-paste electrode modified with cobalt Schiff base complexes

The electrochemical oxidation of thiocytosine on the surface of carbon-paste electrode modified with Schiff base (salophen derivatives) complexes of cobalt is studied. The effect of the substituents in the structure of salophen on the catalytic property of the modified electrode is investigated by using cyclic and differential pulse voltammetry. Cobalt (II)-5-nitrosalophen, because of its electrophilic functional groups, leads to a considerable enhancement in the catalytic activity, sensitivity (peak current), and a marked increase in the anodic potential of the modified electrode. The differential pulse voltammetry is applied as a very sensitive method for the detection of thiocytosine. The linear dynamic range was between 1 × 10⁻³ to 4 × 10⁻⁶ M with a slope of 0.0168 μA/μM, and the detection limit was 1 × 10⁻⁶ M. The modified electrode is successfully applied for the voltammetric detection of thiocytosine in human synthetic serum sample and also pharmaceutical preparations. A linear range from 1 × 10⁻³ to 1 × 10⁻⁵ M with a slope of 0.0175 μA/μM is resulted for the standard addition of thiocytosine spiked to the buffered human serum, which is differing from the curve in buffer solution about 4%. The electrode has a very good reproducibility (relative standard deviation for the slope of the calibration curve is less than 3.5% based on six determinations in a month), high stability in its voltammetric response and low detection limit for thiocytosine, and high electrochemical sensitivity with respect to other biological thiols such as cysteine.     

Subnanomolar determination of a beryllium ion by a novel Be(II) microsensor based on 4-nitrobenzo-9-crown-3-ether

In this work, for the first time, we introduce a highly selective and sensitive Be(II) microsensor. 4-nitrobenzo-9-crown-3-ether (NBCE) was used as a membrane-active component to prepare a Be(II)-selective polymeric membrane microelectrode. The electrode exhibits a Nernstian response toward Be(II) ions over a very wide concentration range (1.0 × 10⁻⁴–1.0 × 10⁻¹⁰ M), with a detection limit of 3.5 × 10⁻¹¹ M (∼350 pg/L). In fact, the electrode presents a fast response time in the whole concentration range (6 s). The proposed microelectrode can be used for at least six weeks without any considerable divergence in the potentials. The proposed membrane sensor revealed a selectivity toward Be(II) ions over a wide variety of other metal ions including common alkali, alkaline-earth, and rare-earth ions. It could be used in the pH range of 3.0–11.5. The microelectrode was successfully used as an indicator electrode for the titration of 20 mL of 1.0 × 10⁻⁶ M Be²⁺ solution with 1.0 × 10⁻⁴ M of EDTA. It was also applied to the direct determination of beryllium ions in beryl and binary mixtures. The text was submitted by the authors in English.     

Flow-injection analysis for the determination of total inorganic carbon and total organic carbon in water using the H2O2–luminol–uranine chemiluminescent reaction

In the presence of carbonate and uranine, the chemiluminescent intensity from the reaction of luminol with hydrogen peroxide was dramatically enhanced in a basic medium. Based on this fact and coupled with the technique of flow-injection analysis, a highly sensitive method was developed for the determination of carbonate with a wide linear range. The method provided the determination of carbonate with a wide linear range of 1.0 × 10⁻¹⁰–5.0 × 10⁻⁶ mol L⁻¹ and a low detection limit (S/N = 3) of carbonate of 1.2 × 10⁻¹¹ mol L⁻¹. The average relative standard deviation for 1.0 × 10⁻⁹–9.0 × 10⁻⁷ mol L⁻¹ of carbonate was 3.7% (n = 11). Combined with the wet oxidation of potassium persulfate, the method was applied to the simultaneous determination of total inorganic carbon (TIC) and total organic carbon (TOC) in water. The linear ranges for TIC and TOC were 1.2 × 10⁻⁶–6.0 × 10⁻² mg L⁻¹ and 0.08–30 mg L⁻¹ carbon, respectively. Recoveries of 97.4–106.4% for TIC and 96.0–98.5% for TOC were obtained by adding 5 or 50 mg L⁻¹ of carbon to the water samples. The relative standard deviations (RSDs) were 2.6–4.8% for TIC and 4.6–6.6% for TOC (n = 5). The mechanism of the chemiluminescent reaction was also explored and a reasonable explanation about chemical energy transfer from luminol to uranine was proposed. Figure Chemiluminescence profiles in batch system. 1, Injection of 100 μL of K₂CO₃ into 1.0 mL luminol-1.0 mL H₂O₂ solution; 2-3 and 4-5, Injection in sequence of 100 μL of K₂CO₃ and 100 μL of uranine into 1.0 ml luminol-1.0 mL H₂O₂ solution; C_luminol = 1.0 × 10⁻⁷ mol/L, C_H2O2 = 1.0 × 10⁻⁵ mol/L, C_uranine = 1.0 × 10⁻⁵ mol/L, C_K2CO3 = 1.0 × 10⁻⁷ mol/L except for 4-5 where C_K2CO3 = 1.0 × 10⁻⁴ mol/L     

Electrochemical behavior of phenol at acetylene black-dihexadecyl hydrogen phosphate composite modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide

The electrochemical response of phenol at acetylene black (AB)-dihexadecyl hydrogen phosphate (DHP) composite modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) was investigated. In this system, a sensitive oxidation peak at 0.62 V (SCE) was obtained. The electrode process and the influence of CTAB on the oxidation of phenol were explored by chronocoulometry and linear sweep voltammetry (LSV). Experimental conditions for the determination of phenol were optimized. In the range of 5.0 × 10⁻⁷ to 1.2 × 10⁻⁵ M, the phenol concentration was linear with the oxidation peak current and the detection limit was found to be 1.0 × 10⁻⁷ M for 3 min accumulation. The method was applied for the determination of phenol in lake water and the results were satisfactory. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 2, pp. 222–229. The text was submitted by the authors in English.