Electroanalytical determination of TBHQ, a synthetic antioxidant, in soybean biodiesel samples

This paper reports an electroanalytical method developed for tert-butylhydroquinone (TBHQ) determination in biodiesel in the presence of surfactant Triton X-100 (T-100). T-100 was shown to improve the electroanalytical signal and its use was decisive for direct analysis of TBHQ in biodiesel, only requiring previous dilution of biodiesel samples in methanol. Several parameters were studied and optimized for the development of this methodology. Under optimal conditions, oxidation peak current was proportional to TBHQ concentration in the range of 1.05-10.10 × 10⁻⁶ mol L⁻¹, with limits of detection and quantification of 3.43 × 10⁻⁸ mol L⁻¹ and 1.14 × 10⁻⁷ mol L⁻¹, respectively, by square wave voltammetry (SWV). The results achieved with the proposed method were satisfactory, relative to those obtained using high-performance liquid chromatography (HPLC).     

Selective and sensitive detection of dopamine in the presence of ascorbic acid by molecular sieve/ionic liquids composite electrode

A simple, sensitive, and reliable method based on a molecular sieve/ionic liquids composite electrode has been successfully developed for selective determination of dopamine (DA). The electrochemical behavior of dopamine (DA) at the modified electrode was investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV). The influence of experimental parameters including pH of solution, amount of modifier, accumulation potential and time on the response of DA was investigated. At the optimum conditions, the peak current of DA was linear with the concentration of DA in the wide range of 5.0 × 10⁻⁸ mol L⁻¹ to 8 × 10⁻⁴ mol L⁻¹, with the correlation coefficient of 0.9982. The detection limit was 1.0 × 10⁻⁸ mol L⁻¹ (S/N = 3) in the presence of 0.2 mM ascorbic acid (AA). The interference studies showed that the modified electrode had excellent selectivity. What's more, the modified electrode also exhibited good reproducibility and stability for determination of DA, and could be applied to determine human serum samples.     

Development of a voltammetric sensor based on a molecularly imprinted polymer (MIP) for caffeine measurement

A new voltammetric sensor for caffeine measurement is introduced. A caffeine-selective molecularly imprinted polymer (MIP) and a non-imprinted polymer (NIP) were synthesized and then used for carbon paste (CP) electrode preparation. The MIP, embedded in the carbon paste electrode, functioned as a selective recognition element and a pre-concentrator agent for caffeine determination. The prepared electrode was used for caffeine measurement via a three-step procedure including analyte extraction in the electrode, electrode washing and electrochemical measurement of caffeine. The MIP-CP electrode showed very high recognition ability in comparison to NIP-CP. It was shown that electrode washing after caffeine extraction led to enhanced selectivity. Differential pulse voltammetry for caffeine determination was more effective than square wave voltammetry. Some parameters affecting sensor response were optimized, and a calibration curve was then plotted. A linear range of 6 × 10⁻⁸ to 2.5 × 10⁻⁵ mol L⁻¹ was obtained. The detection limit of the sensor was calculated to be equal to 1.5 × 10⁻⁸ mol L⁻¹. This sensor was used successfully for caffeine determination in spiked beverage and tea samples.     

Electrochemical mechanism and kinetics studies of haloperidol and its assay in commercial formulations

The kinetics and mechanism for electrochemical reduction of haloperidol, a psychotherapeutic drug used in the treatment of schizophrenia, were studied using square wave and cyclic voltammetries allied to a hanging mercury drop electrode. The experimental and voltammetric parameters were optimized at 0.04 mol L⁻¹ Brinton–Robinson buffer (pH 10), with a pulse potential frequency of 100 s⁻¹, a pulse amplitude of 30 mV and scan increment of 2 mV. Two well-defined peaks were observed, which exhibited properties of fast electron transfer with a strong adsorption process of reactants and products on the electrode surface. The first peak was related to a fast and reversible anion-radical formation originating from the reduction of the carbonyl group, and the second was related to the irreversible reduction of the anion-radical previously formed. Analytical parameters such as: linearity range, equation of the analytical curves, correlation coefficients, detection and quantification limits, recovery efficiency, and relative standard deviation for intraday and interday were compared to similar results obtained by use of the UV–vis spectrophotometry technique, and the analytical results obtained in commercial formulations show that the voltammetric procedure using a hanging mercury drop electrode is suitable for analyzing haloperidol in complex commercial formulation samples.     

Effect of Bi(III) concentration on the stripping voltammetric response of in situ bismuth-coated carbon paste and gold electrodes

The effect of Bi(III) concentration (over the wide concentration range of 10⁻⁷ to 10⁻⁴ M) on the determination of Pb and Cd metal ions (in the 10⁻⁸ to 10⁻⁵ M range), by means of anodic stripping voltammetry (ASV) at in situ bismuth-coated carbon paste (CPE) and gold electrodes, has been studied. It is shown that in square wave anodic stripping voltammetry (SWASV) experiments the sensitivity of the technique generally depends on the Bi(III)-to-metal ion concentration ratio. It was found that, unlike the usually recommended at least 10-fold Hg(II) excess in anodic stripping experiments at in situ prepared mercury film electrodes, Bi(III)-to-metal ion ratios less than 10 are either optimal or equally effective at CPE and Au electrode substrates. Detection limits down to 0.1 μg L⁻¹ for Pb(II) and 0.15 μg L⁻¹ for Cd(II) were estimated at CPEs under conditions of small or moderate Bi(III) excess. Depending on Bi(III) concentration and deposition time, multiple stripping peaks attributed to Bi were recorded (especially in the case of Au substrates), indicating various forms of Bi deposits.     

A novel multi-walled carbon nanotube modified sensor for the selective determination of epinephrine in smokers

Epinephrine (EP), an important neurotransmitter, energizes and speeds up the various body systems and plays an important role during the time of stress and low blood sugar level. There is a close relation between the release of epinephrine and smoking. Edge plane pyrolytic graphite electrode modified with multi-walled carbon nanotubes (MWNTs/EPPGE) has been used as a sensor for the efficient quantitative determination of epinephrine in body fluids of smokers and nonsmokers in resting stage at physiological pH 7.2 by using cyclic voltammetry (CV) and square wave voltammetry (SWV). The oxidation of epinephrine occurred in a well-defined peak having peak potential (E_p) ∼150 mV at pH 7.2. The limit of detection (3σ/slope) and limit of quantification were found to be 0.15 × 10⁻⁹ and 0.48 × 10⁻⁹ M using proposed sensor, respectively. The modified electrode was also utilized for the analysis of commercial sample of epinephrine in order to examine the accuracy of the proposed method. The analytical performance of the modified electrode has been evaluated for quantification of EP in real samples even in the presence of common coexisting biomolecules such as uric acid, ascorbic acid, dopamine and norepinephrine. The voltammetric response of the developed nanosensor towards epinephrine determination in body fluids is fast, sensitive and selective having desirable reproducibility and stability. A comparison of results with high performance liquid chromatography (HPLC) shows a good agreement.     

Enhancement of electrochemiluminesence of lucigenin by ascorbic acid at single-wall carbon nanotube film-modified glassy carbon electrode

The electrochemiluminescent behavior of lucigenin on a single-wall carbon nanotube/DMF film-modified glassy carbon electrode was studied in this paper. Comparing with the bare glassy carbon electrode, the electrochemiluminescent of lucigenin at modified electrode is more stable and without tedious procedure for clean-up the surface of modified electrode. It has been found that ascorbic acid could enhance the electrochemiluminescent intensity of lucigenin greatly at this modified electrode. Based on which, a new sensitive and simple electrochemiluminescent method for determination of ascorbic acid could be developed. The condition for the determination of ascorbic acid was optimized. Under the optimized condition, the enhanced electrochemiluminescent intensity versus ascorbic acid concentration was linear in the range of 1.0 × 10⁻⁸ to 4.0 × 10⁻⁶ mol/L with a detection limit of 2.0 × 10⁻¹⁰ mol/L, and the relative standard derivation for 1.0 × 10⁻⁷ mol/L ascorbic acid was 3.8% (n = 8). The possible mechanism was also discussed.     

Determination of sulfur compounds in gasoline using mercury film electrode by square wave voltammetry

A sensitive method based on square wave voltammetry is described for the quantitative determination of elemental sulfur, disulfide and mercaptan in gasoline using a mercury film electrode. These sulfur compounds can be quantified by direct dissolution of gasoline in a supporting electrolyte followed by subsequent voltammetric measurement. The supporting electrolyte is 1.4 mol L⁻¹ sodium acetate and 2% acetic acid in methanol. Chemical and optimum operational conditions for the formation of the mercury film were analyzed in this study. The values obtained were a 4.3 μm thickness for the mercury film, a 1000 rpm rotation frequency, −0.9 V applied potential and 600 s depositing time. Voltammetric measurements were obtained using square wave voltammetry with detection limits of the 3.0 × 10⁻⁹, 1.6 × 10⁻⁷ and 4.9 × 10⁻⁷ mol L⁻¹ for elemental sulfur, disulfide and mercaptan, respectively.     

Development of screen-printed carbon electrodes modified with functionalized mesoporous silica nanoparticles: Application to voltammetric stripping determination of Pb(II) in non-pretreated natural waters

A screen-printed carbon electrode modified with functionalized mesoporous silica nanoparticles (MTTZ-MSU-2) was developed and evaluated for reliable quantification of trace Pb(II) ions by anodic stripping square wave voltammetry in non-pretreated natural waters. The optimal operating conditions were 5 min preconcentration time and 120 s electrolysis time in HCl 0.2 M. The electrode displayed excellent linear behavior in the concentration range examined (1-30 μg L⁻¹) with a limit of detection of 0.1 μg L⁻¹. The screen-printed carbon modified electrode has long service time and good single and inter-electrode reproducibility. Applicability to spiked drinking water, river water and groundwater was demonstrated without any sample pre-treatment (recoveries between 97% and 106%, RSD 4-7%). On the basis of the present data, mercury-free screen-printed electrodes modified with functionalized mesoporous silicas have the potential to become the next-generation analyzers for decentralized heavy metal monitoring in environmental samples.     

Amperometric flow injection analysis as a new approach for studying disperse systems

Fast and simple quantitative determination in dispersed systems (layered double hydroxides - LDHs - suspensions in aqueous solutions) was performed by a procedure that couples flow injection and amperometric detection (FI-AM). LDH dispersions are injected in a continuous flow (1 mL min⁻¹) of 0.05 mol L⁻¹ KNO₃ solution and [Cu(H₂O)₆]²⁺, used as a probe, is detected at a glassy carbon electrode housed in a flat electrochemical cell. The current intensity, recorded at the selected working potential (−0.25 V vs Ag/AgCl/NaCl (3 mol L⁻¹)), presents a linear relationship with [Cu(H₂O)₆]²⁺ concentration and the procedure offers high sensitivity (slope = 0.036 μA/(μmol L⁻¹)), a low detection limit (=0.7 μmol L⁻¹) and a wide quantification range (4-200 μmol L⁻¹).The method was applied to [Cu(H₂O)₆]²⁺ determination in two particular LDH-aqueous solution dispersed systems: (1) [Cu(H₂O)₆]²⁺ scavenging by etilendiammintetraacetic acid (EDTA) modified Zn-Al-LDHs, and (2) [Cu(H₂O)₆]²⁺ release from a copper doped Mg-Al-LDHs. The results obtained are comparable to those reported in previous works using different quantification techniques. FI-AM determination is applied without sample pretreatment (solid-supernatant separation) providing a high sampling rate (above 120 samples h⁻¹) that allows a better comprehension of the processes, particularly at the initial stages.     

Hybrid electrochemical biosensor for organophosphorus pesticides quantification

An electrochemical biosensor for organophosphorus (OP) pesticides trace level concentrations determination was developed and characterized. It integrates a hybrid biorecognition element consisting of immobilized Arthrobacter globiformis and free acetylcholinesterase (ACh) with a Clark type oxygen probe transducer. The bacteria convert the ACh-generated choline to betaine with oxygen consumption measured as a Clark probe current change. This change representing the sensor response correlates to the concentration of the OP pesticides inhibiting the Ach-catalyzed acetylcholine hydrolysis to choline. The conditions for maximal sensor response to choline were optimized according to the methodology of design of experiments. The analytical performances of the enzyme substrate determination in a wide concentration range (0.1-20 μmol dm⁻³ of acetylcholine) and different ACh activities were established. It was demonstrated that the biosensor ensures reproducible, accurate and reliable chlorophos quantification reaching a limit of detection (LOD) of 1 nmol dm⁻³ and a sensitivity of 0.0252 μA/p(mol dm⁻³) under optimal experimental conditions. The biosensor response time is 200 s and the storage stability is t_L50 = 49 days for the bacterial membrane at ambient temperature. The device is reusable, the bacterial membrane being not affected by OP. The biosensor was applied to chlorophos determination in contaminated milk.     

Anodic voltammetry of abacavir and its determination in pharmaceuticals and biological fluids

Abacavir has an antiretroviral activity against HIV and is oxidizable at the glassy carbon electrode. Cyclic voltammetry studies showed one well-defined oxidation wave or splitted two waves depending on pH. The oxidation was irreversible and exhibited diffusion controlled process depending on pH. The mechanism of the oxidation process was discussed. According to the linear relation between the peak current and the concentration, differential pulse voltammetric (DPV) and square wave voltammetric (SWV) methods for its quantitative determination in pharmaceutical dosage forms and biological fluids were developed. These two voltammetric techniques for the determination of abacavir in Britton-Robinson buffer at pH 2.0, which allows quantitation over the 8×10⁻⁷ to 2×10⁻⁴ M range in supporting electrolyte for both methods were proposed. The linear response was obtained in Britton-Robinson buffer in the ranges of 1×10⁻⁵ to 1×10⁻⁴ M for spiked urine sample at pH 2.0 and 2×10⁻⁵ to 2×10⁻⁴ M for spiked serum samples at pH 3.0 for both techniques. The repeatability and reproducibility of the methods for all media (such as supporting electrolyte, serum and urine samples) were determined. Precision and accuracy were also checked in all media. The standard addition method was used in biological media. No electroactive interferences from the endogenous substances were found in the biological fluids.     

Chitosan–Fe3O4 nanocomposite based electrochemical sensors for the determination of bisphenol A

This paper reports the application of chitosan–Fe₃O₄ (CS–Fe₃O₄) nanocomposite modified glassy carbon electrodes for the amperometric determination of bisphenol A (BPA). We observed that the CS–Fe₃O₄ nanocomposite could remarkably enhance the current response and decrease its oxidation overpotential in the electrochemical detection. Experimental parameters, such as the amount of the CS–Fe₃O₄, the accumulation potential and time, the pH value of buffer solution etc. were optimized. Under the optimized conditions, the oxidation peak current was proportional to BPA concentration in the range between 5.0 × 10⁻⁸ and 3.0 × 10⁻⁵ mol dm⁻³ with the correlation coefficient of 0.9992 and the limit of detection of 8.0 × 10⁻⁹ mol dm⁻³ (S/N = 3). The proposed sensors were successfully employed to determine BPA in real plastic products and the recoveries were between 92.0% and 06.2%. This strategy might open more opportunities for the electrochemical determination of BPA in practical applications. Additionally, the leaching studies of BPA on incubation time using the as-prepared modified electrode were successfully carried out.     

Fabrication of carbon nanotube and dysprosium nanowire modified electrodes as a sensor for determination of curcumin

Two sensitive sensors for determination of curcumin (CM) were described. CM can be detected using multiwall carbon nanotube (MWCNT)-modified electrodes and dysprosium nanowire carbon paste electrode using the technique of adsorptive stripping voltammetry (AdSV) in stationary solution and the fast Fourier transform voltammetry at the flowing solution. Both electrodes did show less passivation effect that occurs on the unmodified electrodes and displayed better stability and reproducibility. This electrode enabled selective determination of CM in the presence of interfering species. Under optimized conditions, CM could be detected over a linear range with a detection limit of 5.0 × 10⁻⁹ mol L⁻¹ and 5.0 × 10⁻¹⁰ mol L⁻¹ for the traditional square wave and fast Fourier transform square wave voltammetry (FFTSWV) with RSD between 0.2 and 0.5%. Comparison with other reported methods showed these studies are about 100 times more sensitive than previous ones. Good selectivity and high sensitivity obtained by Square wave voltammetry can open new possibilities of direct CM determination.     

Voltammetric determination of trace quantities of 6-thioguanine based on the interaction with DNA at a mercury electrode

Herein, a sensitive square wave voltammetric (SWV) method is described for the quantitative determination of an anticancer drug, 6-thioguanine (6-TG). The interaction of 6-TG with double stranded DNA (ds-DNA) in the solution phase resulted in a well amplified SWV response at the surface of hanging mercury dropping electrode (HMDE). Accumulation and stripping steps were made in the sample medium conditioned with acetate buffer (pH 4.8). Optimized conditions for the accumulation step included the deposition potential at −0.10 V, a deposition time of 30 s, a frequency of 50 Hz, a pulse amplitude of 20 mV, and a step potential of 7 mV. In the solution containing 2.0 mg L⁻¹ ds-DNA, determination was performed within a wide concentration range of 2.4 × 10⁻⁹ to 1.8 × 10⁻⁵ mol L⁻¹, and a detection limit of 2.1 nmol L⁻¹ 6-TG. An overall conclusion was that the intercalation of 6-TG into ds-DNA in a solution medium of the acetate buffer is a possible reason for the observed behavior. The method was applied for the determination of 6-TG in 6-thioguanine tablets and spiked blood serum samples. No statistically significant differences were observed between the expected and obtained concentrations. The new method is sufficiently sensitive to detect ultra trace amounts of 6-TG content.     

Development of a biomimetic chitosan film-coated gold electrode for determination of dopamine in the presence of ascorbic acid and uric acid

A gold electrode surface was modified using a dinuclear copper complex [Cu^II₂ (Ldtb)(μ-OCH₃)](BPh₄) and then coated with a chitosan film. This biomimetic polymer film-coated electrode was employed to eliminate the interference from ascorbic acid and uric acid in the sensitive and selective determination of dopamine. The optimized conditions obtained for the biomimetic electrode were 0.1 M phosphate buffer solution (pH 8.0), complex concentration of 2.0 × 10⁻⁴ M, 0.1% of chitosan and 0.25% of glyoxal. Under the optimum conditions, the calibration curve was linear in the concentration range of 4.99 × 10⁻⁷ to 1.92 × 10⁻⁵ M, and detection and quantification limits were 3.57 × 10⁻⁷ M and 1.07 × 10⁻⁶ M, respectively. The recovery study gave values of 95.2-102.6%. The lifetime of this biomimetic sensor showed apparent loss of activity after 70 determinations. The results obtained with the modified electrode for dopamine quantification in the injection solution matrix were in good agreement with those of the pharmacopoeia method.     

Promethazine determination in plasma samples by using carbon paste electrode modified with molecularly imprinted polymer (MIP): Coupling of extraction, preconcentration and electrochemical determination

A promethazine (PMZ) molecularly imprinted polymer (MIP) and a non-imprinted polymer (NIP) were synthesized by two different formulations of methacrylic acid-ethylene glycol dimethacrylate (MAA-EGDMA) and vinyl benzene-divinyl benzene (VB-DVB). Then, the MIPs were used to modify the carbon paste electrode (CP). The response difference between MIP-CP and NIP-CP electrodes, containing VB-DVB polymer, was higher than that for MIP-CP and NIP-CP modified with polymer of MAA-EGDMA, indicating the lower nonselective surface adsorption property of the VB-DVB based MIP. The MIP, incorporated in the carbon paste electrode, functioned as selectively recognition element and pre-concentrator agent for PMZ determination. The prepared electrode was used for PMZ measurement by the three steps procedure including analyte extraction in the electrode, electrode washing and electrochemical measurement of PMZ. It was shown that the electrode washing, after PMZ extraction, led to enhanced selectivity. Square wave voltammetry (SWV) for PMZ determination by proposed electrode was proved to be better than that of differential pulse voltammetry. Some parameters, effective on the electrode response, were optimized and then a calibration curve was plotted. Two dynamic linear range of 7 × 10⁻⁹ to 4 × 10⁻⁷ and 4 × 10⁻⁷ to 7 × 10⁻⁶ mol L⁻¹ were obtained. The detection limit of the method was calculated equal to 3.2 × 10⁻⁹ mol L⁻¹. This method was used successful for PMZ determination in blood serum sample.     

Anodic behavior of sertindole and its voltammetric determination in pharmaceuticals and human serum using glassy carbon and boron-doped diamond electrodes

The electrochemical oxidation of sertindole was investigated using cyclic, linear sweep voltammetry at a glassy carbon and boron-doped diamond electrodes. The aim of this study was to determine sertindole levels in serum and pharmaceutical formulations, by means of electrochemical methods. In cyclic voltammetry, depending on pH values, sertindole showed one or two irreversible oxidation responses. These two responses were found related to the different electroactive part of the molecule. Using second and sharp oxidation peak, two voltammetric methods were described for the determination of sertindole by differential pulse and square wave voltammetry at the glassy carbon and boron-doped diamond electrodes. Under optimized conditions, the current showed a linear dependence with concentration in the range between 1 × 10⁻⁶ and 1 × 10⁻⁴ M in acetate buffer at pH 3.5 and between 4 × 10⁻⁶ and 1 × 10⁻⁴ M in spiked human serum samples for both methods. The repeatability, reproducibility, selectivity, precision and accuracy of all the methods in all media were investigated and calculated. These methods were successfully applied for the analysis of sertindole pharmaceutical dosage forms and human serum samples. No electroactive interferences from the tablet excipients and endogenous substances from biological material were found.     

A simple electroanalytical method for the analysis of the dye solvent orange 7 in fuel ethanol

The purpose of this paper is to develop a simple, rapid and accurate electroanalytical method for the determination of solvent orange 7 (SO-7), commercially used as a dye marker in fuel ethanol samples. SO-7 is oxidized in a mixture of Britton-Robinson buffer with N,N-dimethylformamide (1:1, v/v) at a glassy carbon electrode and presents a well-defined peak around +0.70 V vs. Ag/AgCl, which can be monitored by linear-scan voltammetry (LSV) and square-wave voltammetry (SWV). Using optimized parameters based on the SWV technique, it is possible to get a linear relationship between the peak current and the SO-7 dye concentration from 4.0 × 10⁻⁶ to 18.0 × 10⁻⁶ mol L⁻¹ (r = 0.995). The proposed method was successfully applied to the direct quantification of the SO-7 dye in fuel ethanol samples, which gave good average recovery for commercial samples containing 5.0 mg L⁻¹ and 10.0 mg L⁻¹ of SO-7 dye, respectively.     

Study and determination of the herbicide cyclosulfamuron by square wave stripping voltammetry

The voltammeric behavior of the herbicide cyclosulfamuron has been studied by square wave stripping voltammetry (SWSV). Cyclosulfamuron was reduced on a static mercury drop electrode (SMDE) and gave a well-defined peak in the pH range of 3.0-7.0. The peak potential (E_p) shifts to a more negative potential with increasing pH. The ratio ΔE_p/ΔpH over the pH range studied was 59.5 mV/pH. A systematic study of the various experimental parameters that affect the stripping response was studied by SWV. The square wave parameters used were a frequency of 150 Hz, an amplitude of −60 mV and a staircase step of 6.0 mV. The quantifications were performed by the standard addition method, from the SW voltammetric peak obtained at −1348 mV. Calibration curves were linear in the range of 10-350 μg L⁻¹ with a detection limit of 3.5 μg L⁻¹ under the conditions used (pH 6.0 buffer solution, E_acc = −400 mV vs. Ag/AgCl, t_acc = 75 s). The validity of the developed methodology was assessed by recovery experiments at the 25-100 μg L⁻¹ level. The mean results for 3 determinations were 49.7 ± 3.3 μg L⁻¹, which is very close to the amount of cyclosulfamuron added to soil (50 μg L⁻¹), with a recovery of 99.4%. The sufficiently good recoveries and low relative standard deviation (RSD) data reflects the high accuracy and precision of the proposed SW voltammetric method. The possible influences of various inorganic species and other pesticides were also investigated.