Sensitive voltammetric detection of clomipramine at 16-mercapto-hexadecanoic acid self-assembled monolayer modified gold electrode

Clomipramine, an effective and important antipsychotic drug with low redox activity and poor hydrophilicity, was found to effectively accumulate on hydrophobic 16-mercaptohexadecanoic acid (i.e. MHA) self-assembled monolayer (SAM) modified gold electrode (i.e. MHA/Au) and generating a sensitive anodic peak at about 0.86 V (vs. SCE) in 0.05 M Tris–HCl (pH = 8.1) buffer solution. Thus, quantitative measurement of clomipramine was established with high sensitivity under optimum conditions. The anodic peak current was linear to clomipramine concentration in the range from 1 × 10⁻⁶ to 5 × 10⁻⁵ M, with a detection limit of 6 × 10⁻⁹ M. This method was successfully applied to the detection of clomipramine in drug tablets and proved to be reliable compared to UV. The spectral features, electrochemical characteristics and wettability of MHA-SAM were also studied. Correspondence: Jilie Kong, Department of Chemistry, Fudan University, Shanghai 200433, P.R. China     

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.     

Sensitive determination of adenine on poly(amidosulfonic acid)-modified glassy carbon electrode

A novel and reliable direct electrochemical method was established for the detection of adenine, based on the differential pulse anodic stripping response at a poly(amidosulfonic acid) (poly-ASA)-modified glassy carbon electrode (GCE) fabricated by electropolymerization. The characterization of electrochemically synthesized poly-ASA film was investigated by atomic force microscopy, electrochemical impedance spectroscopy, and voltammetric methods. This poly-ASA-modified GCE could greatly enhance the detection sensitivity of adenine. At optimum conditions, the anodic peak exhibits a good linear concentration dependence in the range from 3.0 × 10⁻⁸ to 1.0 × 10⁻⁶ M (r = 0.9994). The detection limit is 8.0 × 10⁻⁹ M (S/N = 3). The proposed method could be used to determinate the adenine in tablets of vitamin B₄ with satisfactory results.     

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.     

Determination of rutin using a CeO2 nanoparticle-modified electrode

CeO₂ nanoparticles approximately 12 nm in size were synthesized and subsequently characterized by XRD, TEM and UV-vis spectroscopy. Then, a gold electrode modified with CeO₂ nanoparticles was constructed and characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The modified electrode demonstrated strong catalytic effects with high stability towards electrochemical oxidation of rutin. The anodic peak currents (measured by differential pulse voltammetry) increased linearly with the concentration of rutin in the range of 5.0 × 10⁻⁷–5.0 × 10⁻⁴ mol · L⁻¹. The detection limit (S/N = 3) was 2.0 × 10⁻⁷ mol · L⁻¹. The relative standard deviation (RSD) of 8 successive scans was 3.7% for 5.0 × 10⁻⁶ mol · L⁻¹ rutin. The method showed excellent sensitivity and stability, and the determination of rutin in tablets was satisfactory.     

Immobilization of Hemoglobin on the Gold Colloid Modified Pretreated Glassy Carbon Electrode for Preparing a Novel Hydrogen Peroxide Biosensor

A novel hydrogen peroxide (H₂O₂) biosensor was developed by immobilizing hemoglobin on the gold colloid modified electrochemical pretreated glassy carbon electrode (PGCE) via the bridging of an ethylenediamine monolayer. This biosensor was characterized by UV-vis reflection spectroscopy (UV-vis), electrochemical impendence spectroscopy (EIS) and cyclic voltammetry (CV). The immobilized Hb exhibited excellent electrocatalytic activity for hydrogen peroxide. The Michaelis–Menten constant (K _m) was 3.6 mM. The currents were proportional to the H₂O₂ concentration from 2.6 × 10⁻⁷ to 7.0 × 10⁻³ M, and the detection limit was as low as 1.0 × 10⁻⁷ M (S/N = 3).     

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.     

Electrocatalytic oxidation of quinine sulfate at a multiwall carbon nanotubes-ionic liquid modified glassy carbon electrode and its electrochemical determination

The electrocatalytic oxidation of quinine sulfate (QS) was investigated at a glassy carbon electrode, modified by a gel containing multiwall carbon nanotubes (MWCNTs) and room-temperature ionic liquid of 1-Butyl-3-methylimidazolium hexafluorophate (BMIMPF₆) in 0.10 M of phosphate buffer solution (PBS, pH 6.8). It was found that an irreversible anodic oxidation peak of QS with E _pa as 0.99 V appeared at MWCNTs-RTIL/glassy carbon electrode (GCE). The electrode reaction process was a diffusion-controlled one and the electrochemical oxidation involved two electrons transferring and two protons participation. Furthermore, the charge-transfer coefficient (α), diffusion coefficient (D), and electrode reaction rate constant (k _f) of QS were found to be 0.87, 7.89 × 10⁻³ cm²⋅s⁻¹ and 3.43 × 10⁻² s⁻¹, respectively. Under optimized conditions, linear calibration curves were obtained over the QS concentration range 3.0 × 10⁻⁶ to 1.0 × 10⁻⁴ M by square wave voltammetry, and the detection limit was found to be 0.44 μM based on the signal-to-noise ratio of 3. In addition, the novel MWCNTs-RTIL/GCE was characterized by the electrochemical impedance spectroscopy and the proposed method has been successfully applied in the electrochemical quantitative determination of quinine content in commercial injection samples and the determination results could meet the requirement.     

Simultaneous Determination of Dopamine and Ascorbic Acid at a Triazole Self-Assembled Monolayer-Modified Gold Electrode

A 3-amino-5-mercapto-1,2,4-triazole (TA) self-assembled monolayer-modified gold electrode (TA SAM/Au) is characterized by X-ray photoelectron spectroscopy, A.C. impedance, cyclic voltammetry, chronoamperometry and chronocoulometry. The TA SAM/Au exhibited good promotion of the electrochemical oxidation of dopamine. Some electrochemical parameters of dopamine such as electron transfer number, exchange current density, standard heterogeneous rate constant, diffusion coefficient, etc., were measured by different electrochemical methods. The peak currents of dopamine were linearly dependent on its concentration in the range of 1.5 × 10⁻⁶–1.0 × 10⁻⁴ mol L⁻¹, with a detection limit of 5.0 × 10⁻⁷ mol L⁻¹. The oxidative peak potentials of dopamine and ascorbic acid were well separated at about 190 ± 10 mV in pH 2.0 BR buffers at TA SAM/Au, the oxidation peak current increases approximately linearly with increasing concentration of both dopamine and ascorbic acid in the concentration range of 9.98 × 10⁻⁶–4.54 × 10⁻⁴ mol L⁻¹. It can be used for simultaneous determination of dopamine and ascorbic acid.     

Application of cadmium sulfide nanoparticles as oligonucleotide labels for the electrochemical detection of NOS terminator gene sequences

A mercaptoacetic acid (MAA)-modified cadmium sulfide (CdS) nanoparticle was synthesized in aqueous solution and used as an oligonucleotide label for the electrochemical detection of nopaline synthase (NOS) terminator gene sequence. The carboxyl groups on the surface of the CdS nanoparticle can be easily covalently linked with NH₂-modified NOS oligonucleotide probe sequences. The target ssDNA sequence was fixed onto the electrode surface by covalently linking to a mercaptoethanol self-assembled gold electrode, and the DNA hybridization of target ssDNA with probe ssDNA was accomplished on the electrode surface. The CdS nanoparticles anchored on the hybrids were dissolved in the solution by the oxidation with HNO₃ and further detected by a sensitive differential pulse anodic stripping voltammetric method. The detection results can be used for monitoring the hybridization, and the NOS target sequence was satisfactorily detected in the approximate range from 8.0 × 10⁻¹² to 4.0 × 10⁻⁹ mol L⁻¹ with a detection limit of 2.75 × 10⁻¹² mol L⁻¹ (3σ). The established method extended the nanoparticle-labeled electrochemical DNA analysis to genetically modified organisms (GMOs) specific sequence samples with higher sensitivity and selectivity.     

Electrochemical behaviors of metol on ionic-liquid-modified carbon paste electrode and its analytical application

The electrochemical behaviors of metol on an ionic liquid N-butylpyridinium hexafluorophosphate modified carbon paste electrode (IL-CPE) were studied in this paper. The results indicated that a pair of well-defined quasi-reversible redox peaks of metol appeared with the decrease of overpotential and the increase of redox peak current, which was the characteristics of electrocatalytic oxidation. The electrocatalytic mechanism was discussed and the electrochemical parameters were calculated with results of the charge-transfer coefficient (α) as 0.45, the electrode reaction rate constant (k _s) as 4.02 × 10⁻³ s⁻¹, and the diffusion coefficient (D) as 6.35 × 10⁻⁵ cm²/s. Under the optimal conditions, the anodic peak current was linear with the metol concentration in the range of 5.0 × 10⁻⁶ ∼ 1.0 × 10⁻³ mol/L (n = 11, γ = 0.994) and the detection limit was estimated as 2.33 × 10⁻⁶ mol/L (3σ). The proposed method was successfully applied to determination of metol content in synthetic samples and photographic solutions.     

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.     

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 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.     

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.     

CO<Subscript>2</Subscript> corrosion inhibition of X-70 pipeline steel by carboxyamido imidazoline

The corrosion inhibition of X-70 pipeline steel in saltwater saturated with CO₂ at 50 °C with carboxyamido imidazoline has been evaluated by using electrochemical techniques. Techniques included polarization curves, linear polarization resistance, electrochemical impedance, and electrochemical noise measurements. Inhibitor concentrations were 0, 1.6 × 10⁻⁵, 3.32 × 10⁻⁵, 8.1 × 10⁻⁵, 1.6 × 10⁻⁴, and 3.32 × 10⁻⁴ mol l⁻¹. All techniques showed that the best corrosion inhibition was obtained by adding 8.1 × 10⁻⁵ mol l⁻¹ of carboxyamido imidazoline. For inhibitor concentrations higher than 8.1 × 10⁻⁵ mol l⁻¹ a desorption process occurs, and an explanation has been given for this phenomenon.     

Electrochemical evaluation and determination of antiretroviral drug fosamprenavir using boron-doped diamond and glassy carbon electrodes

Fosamprenavir is a pro-drug of the antiretroviral protease inhibitor amprenavir and is oxidizable at solid electrodes. The anodic oxidation behavior of fosamprenavir was investigated using cyclic and linear sweep voltammetry at boron-doped diamond and glassy carbon electrodes. In cyclic voltammetry, depending on pH values, fosamprenavir showed one sharp irreversible oxidation peak or wave depending on the working electrode. The mechanism of the oxidation process was discussed. The voltammetric study of some model compounds allowed elucidation of the possible oxidation mechanism of fosamprenavir. The aim of this study was to determine fosamprenavir levels in pharmaceutical formulations and biological samples by means of electrochemical methods. Using the sharp oxidation response, two voltammetric methods were described for the determination of fosamprenavir by differential pulse and square-wave voltammetry at the boron-doped diamond and glassy carbon electrodes. These two voltammetric techniques are 0.1 M H₂SO₄ and phosphate buffer at pH 2.0 which allow quantitation over a 4 × 10⁻⁶ to 8 × 10⁻⁵ M range using boron-doped diamond and a 1 × 10⁻⁵ to 1 × 10⁻⁴ M range using glassy carbon electrodes, respectively, in supporting electrolyte. All necessary validation parameters were investigated and calculated. These methods were successfully applied for the analysis of fosamprenavir pharmaceutical dosage forms, human serum and urine samples. The standard addition method was used in biological media using boron-doped diamond electrode. No electroactive interferences from the tablet excipients or endogenous substances from biological material were found. The results were statistically compared with those obtained through an established HPLC-UV technique; no significant differences were found between the voltammetric and HPLC methods.     

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).     

Selective and sensitive molecularly imprinted sol–gel film-based electrochemical sensor combining mercaptoacetic acid-modified PbS nanoparticles with Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@Au–multi-walled carbon nanotubes–chitosan

A sensitive molecularly imprinted electrochemical sensor was developed for selective detection of streptomycin by combination of mercaptoacetic acid-modified PbS nanoparticles with Au-coated Fe₃O₄ magnetic nanoparticles dispersed multi-walled carbon nanotubes doped chitosan film. The imprinted sensor was fabricated onto the Au electrode via stepwise modification of nanocomposites and an electrodeposited thin film of molecularly imprinted polymers via sol–gel technology. The morphologies and electrochemical behaviors of the imprinted sensor were characterized by scanning electron microscope, cyclic voltammetry, and differential pulse voltammetry, respectively. The prepared sensor showed very high recognition ability and selectivity for streptomycin. Under optimal conditions, the imprinted sensor displayed good electrocatalytic activity to the redox of streptomycin. And the differential voltammetric anodic peak current was linear to the logarithm of streptomycin concentration in the range from 1.0 × 10⁻⁶ to 1.0 × 10⁻³ mol L⁻¹, and the detection limit obtained was 1.5 × 10⁻⁹ mol L⁻¹. This proposed imprinted sensor was used successfully for streptomycin determination in different injection solution samples.     

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