Trace determination of vardenafil hydrochloride in commercial formulation and human serum by adsorptive anodic stripping voltammetry at a carbon paste electrode

The electrochemical behavior of vardenafil HCl (VRL) at a carbon paste electrode (CPE) was investigated by cyclic voltammetry, and the mechanism of its oxidation was suggested and discussed. A simple Nujol-based CPE in combination with a sensitive square-wave adsorption anodic stripping voltammetry method was described for trace determination of VRL. The described method showed excellent performance for trace determination of VRL in its formulation “Levitra® tablets” without interference from excipients. The results were statistically compared with those obtained with an established HPLC method; nonsignificant differences were found between the described voltammetric and HPLC methods. The described stripping voltammetric method is highly sensitive (limit of detection?=?3?×?10^?10?mol?L^?1 and limit of quantitation?=?1?×?10^?9?mol?L^?1). It was successfully applied for the determination of VRL in spiked human serum without the necessity for pretreatment and/or time-consuming extraction steps prior to the analysis.     

Subnanomolar Determination of Indium by Adsorptive Stripping Differential Pulse Voltammetry Using Factorial Design for Optimization

Abstract

A highly sensitive method to determine of indium is proposed by adsorption stripping differential pulse cathodic voltammetry (AdSDPCV) method. The complex of indium ions with xylenol orange is analyzed based on the adsorption collection onto a hanging mercury drop electrode (HMDE). After accumulation of the complex at ?0.20 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from ?0.40 to ?0.75 V with the differential pulse method. Then, the reduction peak current of In(III)–XO complex is measured. The influence of chemical and instrumental variables was studied by factorial design analysis. Under optimum conditions and accumulation time of 60 s, linear dynamic range was 0.1–10 ng/ml (8.7 × 10^?10 to 8.7 × 10^?8 M) with a limit of detection of 0.03 ng/ml (2.6 × 10^?10 M); at accumulation time of 5 min, linear dynamic range was 0.04–10 ng/ml (3.4 × 10^?10 to 8.7 × 10^?8 M) with a limit of detection of 0.013 ng/ml (1.1 × 10^?10 M). The applicability of the method to analysis of real samples was assessed by the determination of indium in water, alloy, and jarosite (zinc ore) samples.     

Sensitive voltammetric assay of etoposide using modified glassy carbon electrode with a dispersion of multi-walled carbon nanotube

A sensitive electroanalytical method for the determination of anticancer drug etoposide (ETP) using adsorptive stripping differential pulse voltammetry (AdSDPV) at a multi-walled carbon nanotube-modified glassy carbon electrode (MWCNT-modified GCE) is presented. The surface morphology of modified electrode was characterized by scanning electron microscopy. The effects of accumulation time and potential, pH, scan rate, and amount of MWCNT suspension were investigated. The calibration curve was linear in the concentration range of 2.0?×?10^?8–2.0?×?10^?6 M with the detection limit of 5.4?×?10^?9 M. The reproducibility of the peak current was found at 1.55 % (n?=?5) RSD value in pH 6.0 Britton–Robinson buffer for the MWCNT-modified GCE. The method was then successfully utilized for the determination of ETP in pharmaceutical dosage form, and a recovery of 99.55 % was obtained. The possible oxidation mechanism of ETP was also discussed. The proposed electroanalytical method using MWCNT-modified GCE is the most sensitive method for the determination of ETP with lowest limit of detection in the previously published electrochemical methods.     

Voltammetric determination of mercury(II) using a modified pencil graphite electrode with 4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl

A sensitive and selective method for determination of mercury(II) with “4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl (TKO)-modified pencil graphite electrode” was developed. All factors affecting determination process were optimized. Differential pulse voltammetry with 4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl-modified electrode showed a linear response between 1.0 × 10^?5 and 1.0 × 10^?3 M (R ² = 0.9994). The detection limit of this electrode was found as 5.85 × 10^?7 M (S/N = 3). The effects of different cations on the determination of mercury(II) were investigated and found that modified electrode is highly selective. The developed method was applied for mercury determination in different water samples.     

Voltammetric sensing of triclosan in the presence of cetyltrimethylammonium bromide using a cathodically pretreated boron-doped diamond electrode

ABSTRACT

In the present study, a simple, cheap and sensitive electrochemical method based on a cathodically pretreated boron-doped diamond (CPT-BDD) electrode is described for the detection of triclosan with the cationic surfactant (cetyltrimethylammonium bromide, CTAB) media. The oxidation of triclosan was irreversible and exhibited an adsorption controlled process. The sensitivity of the adsorptive stripping voltammetric measurements was significantly improved with addition of CTAB. Using square-wave stripping mode, a linear response was obtained for triclosan determination in Britton-Robinson buffer solution at pH 9.0 containing 2.5 × 10^?4 M CTAB at around + 0.67 V (vs. Ag/AgCl) (after 30 s accumulation at open-circuit condition). The method could be used in the range of 0.01–1.0 μg mL^?1 (3.5 × 10^?8–3.5 × 10^?6 M), with a detection limit of 0.0023 μg mL^?1 (7.9 × 10^?9 M). The feasibility of the proposed method for the determination of triclosan in water samples was checked in spiked tap water.     

A New Flow‐Injection Chemiluminescence Method for the Determination of Acyclovir and Gancyclovir

Abstract

A rapid and sensitive flow‐injection chemiluminescence (FI‐CL) method, which is based on the CL intensity that generated from the redox reaction of Ce(IV)‐rhodamine B in H₂SO₄ medium, for the determination of acyclovir and gancyclovir is described. For acyclovir, the determination range is 3×10^?8 g mL^?1–7×10^?5 g mL^?1, with 1.56×10^?8 g mL^?1 as its determination limit. During 11 repeated measurements for 1×10^?6 g mL^?1 acyclovir, the relative standard deviation was 2.08%. For gancyclovir, the determination range was 5×10^?8 g mL^?1–7×10^?5 g mL^?1, with 2.35×10^?8 g mL^?1 as its determination limit. The relative standard deviation is 2.83% with 11 repeated measurements of 1×10^?6 g mL^?1 gancyclovir. This method can be successfully used to determine the content of acyclovir and gancyclovir in injections, acyclovir in eye drops, and, maybe, also for other ciclovirs.     

A Novel Sensitive Biosensor for Ca2+ Ion Based on Gold Nanoparticles Modified Electrode by Pulsed Electrodeposition

The work demonstrates a simple method for sensitive detection of Ca²⁺ ion by electrochemical response of alizarin red S (ARS) and Ca-ARS at a gold nanoparticle modified glassy carbon electrode (GCE). In the 0.1 M KOH, a sensitive reduction peak was observed at ?0.795 V at the gold nanoparticles modified electrode. The peak currents were proportional to the concentrations of Ca²⁺ ion in the range of 2.0 × 10^?7 M–1.2 × 10^?4 M. For the different pulse voltammetry (DPV) methods, the detection limit was 2.57 × 10^?8 M. The reaction mechanism was primarily determined by cyclic voltammetry, and the experimental results showed that the electrode processes were quasireversible responses of ARS and irreversible responses of ARS-Ca. In addition, the method was simple, fast, precise, and was used in the determination of calcium in blood serum with satisfactory results.     

Determination of Tyrosine in the Presence of Sodium Dodecyl Sulfate Using a Gold Nanoparticle Modified Carbon Paste Electrode

A carbon paste electrode modified with gold nanoparticles (AuMCPE) was used as a highly sensitive sensor for determination of Tyrosine (Tyr), in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS), in aqueous solution. The measurements were carried out by using of differential pulse voltammetry (DPV), cyclic voltammetry (CV), amd chronocoulometry and chronoamperometry methods. The prepared electrode shows voltammetric responses with high sensitivity and selectivity for Tyr in the presence of SDS. The relationship between the oxidation peak current of Tyr and its concentration was obtained linearly and it was 1.0 × 10^?7 to 1.0 × 10^?5 M with a detection limit of 5.5 × 10^?8 M in the absence of SDS. On the other hand the oxidation peak current of Tyr increased significantly at AuMCPE in the presence of SDS and its detection limit was reduced to 2.7 × 10^?9 M. The proposed voltammetric approach was also applied to the determination of Tyr concentration in human serum.     

Highly Sensitive Membrane Electrode Based on a Copper(II)-bis(N-4-Methylphenyl-Salicyldenaminato) Complex for the Determination of Chromate

A highly sensitive polyvinyl chloride (PVC) membrane electrode, based on copper(II)-bis(N-4-methylphenyl-salicyldenaminato) complex, (CuL₂), as a carrier was reported for the determination of chromate ion. The influence of membrane composition, pH, and possible interfering anions on the response of the ion selective electrode was investigated. The sensor exhibited a Nernstian slope of 29.7 mV per decade when the chromate concentration was varied between 2.0 × 10^?7–1.50 × 10^?2 M in a wide pH range (6.0 to 9.0). The detection limit of the ion selective electrode was 9.2 × 10^?8 M. The proposed sensor was used for at least 4 months without any considerable divergence in potential. It was applied as indicator electrode in potentiometric titration of chromate ion with Pb²⁺ and Tl⁺.     

Electrochemical sensor for ultrasensitive determination of ceftazidime using hollow platinum nanoparticles/reduced graphene oxide/pencil graphite electrode

In this paper, an electrochemical sensor was prepared based on the modification of pencil graphite electrode (PGE) by hollow platinum nanoparticles/reduced graphene oxide (HPtNPs/rGO/PGE) for determination of ceftazidime (CFZ). Initially, rGO was electrodeposited on the electrode surface, and then, hollow platinum nanoparticles were placed on the electrode surface via galvanic displacement reaction of Pt(IV) ions with cobalt nanoparticles (CoNPs) that had electrodeposited on the electrode surface. Several significant parameters controlling the performance of the HPtNPs/rGO/PGE were examined and optimized using central composite design as one optimization methodology. The surface morphology and elemental characterization of the bare PGE, rGO/PGE, CoNPs/rGO/PGE, and HPtNPs/rGO/PGE-modified electrodes was analyzed by field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electrochemical impedance spectroscopy. The electrochemical activity of CFZ on resulting modified electrode was investigated by cyclic voltammetry (CV) and adsorptive differential pulse voltammetry (AdDPV). Adsorptive differential pulse voltammetry indicates that peak current increases linearly with respect to increment in CFZ concentration. CFZ was determined in the linear dynamic range of 5.0 × 10^?13 to 1.0 × 10^?9 M, and the detection limit was determined as 2.2 × 10^?13 M using AdDPV under optimized conditions. The results showed that modified electrode has high selectivity and very high sensitivity. The method was used to determine of CFZ in drug injection and plasma samples.     

Sensitive Determination of Clomipramine at Poly‐ABSA/Pt Nano‐Clusters Modified Glassy Carbon Electrode

Abstract

Clomipramine, an important tricylic antidepressant drug with low redox activity, was effectively electrocatalyzed on poly‐aminobenzene sulfonic acid/Pt nano‐clusters modified glassy carbon electrode (i.e., poly‐ABSA/Pt/GCE) and generated a sensitive anodic peak at about 0.80 V in pH 8.1 PBS. ABSA was electropolymerized on the surface of GCE modified with Pt nano‐clusters. Pt nanoparticles provide a 3 D and conductive structure for the polymer immobilization. The resulting sensor exhibited a considerable enhancement in voltammetric response characteristics: extending the linear range and lowering the detection limit. The anodic peak current of clomipramine was linear with its concentration over two concentration intervals, viz., 1.0×10^?7～4.0×10^?6 M and 4.0×10^?6～4.0×10^?5 M, with the detection limit of 1.0×10^?9 M (S/N=3). This method was successfully applied to the determination of clomipramine in drug tablets and proved to be reliable compared with UV.     

Electrochemical Oxidation of Pentoxifylline and its Analysis in Pure and Pharmaceutical Formulations at a Glassy Carbon Electrode

Abstract

The oxidative behavior of pentoxifylline was studied at a glassy carbon electrode in phosphate buffer solutions using cyclic and differential-pulse voltammetry. The oxidation process was shown to be irreversible over the pH range (3.0–9.0) and was diffusion controlled. The possible mechanism of the oxidation of pentoxifylline was investigated by means of cyclic voltammetry and UV-Vis spectroscopy. An analytical method was developed for the determination of pentoxifylline in phosphate buffer solution at pH 3.0 as a supporting electrolyte. The anodic peak current varied linearly with pentoxifylline concentration in the range 2.0 × 10^?8 M to 6.0 × 10^?7 M of pentoxifylline with a limit of detection (LOD) of 4.42 × 10^?10 M. The proposed method was applied to the determination of pentoxifylline in pure and pharmaceutical formulations.     

Electrochemical behavior of adriamycin at an electrode modified with silver nanoparticles and multi-walled carbon nanotubes, and its application

An electrochemical sensor has been constructed for the determination of adriamycin (ADM) that is based on a glassy carbon electrode modified with silver nanoparticles and multi-walled carbon nanotubes with carboxy groups. The modified electrode was characterized by scanning electron microscopy and exhibits a large enhancement of the differential pulse voltammetric response to ADM. Signals are linear with the concentrations of ADM in the range from 8.2?×?10^?9 M to 19.0?×?10^?9 M, with a detection limit of 1.7?×?10^?9 M. The sensor is highly reproducible and exhibits excellent stability. It was to detect calf thymus DNA.     

Modified Glassy Carbon Electrode with Multiwall Carbon Nanotubes as a Voltammetric Sensor for Determination of Leucine in Biological and Pharmaceutical Samples

Abstract

A simple and highly sensitive method is described for voltammetric determination of leucine in blood and urine samples; namely, a glassy carbon electrode with an effective method is modified with multiwall carbon nanotubes (MWNTs). The cyclic voltammetric results indicated that MWNTs remarkably enhanced electrocatalytic activity toward the oxidation of leucine. Under the optimum condition the calibration curve was linear in the concentration range 9.0 × 10^?6 ? 1.5 × 10^?3 mol L^?1, with the detection limit of 3.0 × 10^?6 mol L^?1 and a relative standard deviation (RSD%) lower than 3.0% (n = 5). Also, some kinetic parameters were determined and a multistep mechanism for oxidation of leucine was proposed.     

A simple method for determination of urapidil at a glassy carbon electrode modified with poly(sodium4-styrenesulfonate) functionalized graphene

ABSTRACT

A simple, highly sensitive voltammetric method for the determination of urapidil at poly(sodium4-styrenesulfonate) functionalized graphene-modified electrode (PSS-Gr/GCE) was described. Based on the PSS-Gr composites-modified glassy carbon electrode as a simple voltammetric sensor, it exhibited good conductivity and high sensitivity to urapidil. Under the optimize condition, a good linear relationship was obtained between peak currents and urapidil concentrations in the wider range of 2.0 × 10^?9–8.0 × 10^?8 mol L^?1 and 2.0 × 10^?7–2.0 × 10^?5 mol L^?1 with detection limit of 8 × 10^?10 mol L^?1 (S/N = 3). Based on the high sensitivity and good selectivity of the proposed electrode, the proposed method could apply to the detect of urapidil in urapidil sustained release tablets with satisfactory results.     

Highly sensitive spectrofluorimetric assay of glutathione in vegetables

A highly sensitive and simple spectrofluorimetric method for the determination of reduced glutathione based on the fluorescence quenching effect of glutathione on the hemoglobin-catalyzed reaction of H₂O₂ with L-tyrosine was developed. The concentration of glutathione is linear with the fluorescence quenching (??F) of system under the optimal experimental conditions. The calibration graph is linear in the range 6.25 × 10^?9 to 3.75 × 10^?6 M with the detection limit of 2.23 × 10^?9 M. This method can be used for the determination of glutathione in vegetables with satisfactory results.     

Electrochemical Sensor Based on Molecularly Imprinted Polymer Film Prepared with Functional Abietic‐Type Acids as Cross‐Linker for the Determination of Quinine

A novel cross‐linker (functional abietic‐type acids) for preparing highly sensitive, molecularly imprinted sensors was proposed for quinine determination. A MIP film was created on a glassy carbon electrode for determination of quinine using free radical polymerization method. The modification procedure was characterized via electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The interaction between functional monomer and target molecule was observed by UV spectrometric methods. Under the optimal experimental conditions, the peak currents were proportional to the concentrations of quinine in the range from 8.0×10^?7 to 2.6×10^?4 M with a detection limit of 2.0×10^?8 M. Meanwhile the prepared sensor showed sensitive and selective binding sites for quinine. Determination of quinine in tonic water showed good recovery.     

A Novel Adsorptive Square Wave Voltammetric Method for Pico Molar Monitoring of Lorazepam at Gold Ultra Microelectrode in a Flow Injection System by Application of Fast Fourier Transform Analysis

Abstract

This paper describes development of a new analysis system for determination of lorazepam by a novel square wave voltammetry method to perform a very sensitive method. The method used for determination of lorazepam involves measuring the changes in admittance voltammogram of a gold ultramicroelectrode (in 0.05 M H₃PO₄ solution) caused by adsorption of the lorazepam on the electrode surface. Variation of admittance in the detection process is created by inhibition of oxidation reaction of the electrode surface, by adsorbed lorazepam. Furthermore, signal-to-noise ratio is significantly increased by application of discrete fast Fourier transform (FFT) method, background subtraction, and two-dimensional integration of the electrode response over a selected potential range and time window. Also in this work, some parameters such as SW frequency, eluent pH, and accumulation time were optimized. Calibration plots are given for solutions containing 10^?6–10^?11 M of lorazepam. The detection limit is calculated to be 6.0 × 10^?12 M (～ 2 pg/ml). The relative standard deviation at concentration 3.0 × 10^?8 M is 6.1% for 5 reported measurements.     

Anodic Voltammetric Behavior and Determination of Antihistaminic Agent: Fexofenadine HCl

Abstract

A voltammetric study of the oxidation of fexofenadine HCl (FEXO) has been carried out at the glassy carbon electrode. The electrochemical oxidation of FEXO was investigated by cyclic, linear sweep, differential pulse (DPV), and square wave (SWV) voltammetry using glassy carbon electrode. The oxidation of FEXO was irreversible and exhibited diffusion‐controlled process depending on pH. The dependence of intensities of currents and potentials on pH, concentration, scan rate, nature of the buffer was investigated. Different parameters were tested to optimize the conditions for the determination of FEXO. For analytical purposes, a very well resolved diffusion‐controlled voltammetric peak was obtained in Britton‐Robinson buffer at pH 7.0 with 20% constant amount of methanol for DPV and SWV techniques. The linear response was obtained in supporting electrolyte in the ranges of 1.0×10^?6–2.0×10^?4 M with a detection limit of 6.6×10^?9 M and 5.76×10^?8 M and in serum samples in the ranges of 2.0×10^?6–1.0×10^?4 M with a detection limit of 8.08×10^?8 M and 4.97×10^?8 M for differential pulse and square wave voltammetric techniques, respectively. Only square wave voltammetric technique can be applied to the urine samples, and the linearity was obtained in the ranges of 2.0×10^?6–1.0×10^?4 M with a detection limit of 2.00×10^?7 M. Based on this study, simple, rapid, selective and sensitive two voltammetric methods were developed for the determination of FEXO in dosage forms and biological fluids. For the precision and accuracy of the developed methods, recovery studies were used. The standard addition method was used for the recovery studies. No electroactive interferences were found in biological fluids from the endogenous substances and additives present in tablets.     

Photo-induced flow-injection determination of nitrate in water

A sensitive flow-injection method for the chemiluminescent determination of ultra-low concentration of nitrate in water is presented. Nitrate is on-line photolytically converted to peroxynitrite by absorption of UV light inside of 60 mm long quartz capillary (i.d. 530 µm, o.d. 720 µm). Peroxynitrite is subsequently determined by the chemiluminescent reaction with luminol. The detection limit of nitrate is 7 × 10^?10 M (S/N = 3). The linear range of the method is 2 × 10^?9–1 × 10^?5 M nitrate. The interference of nitrite is eliminated by its conversion to nitrogen after mixing of sample with a solution of sulfamidic acid. Other common anions do not interfere. The interference of cations is eliminated by passing the sample through a cation-exchange column. The FIA procedure allows analysing of 15 samples per hour. The method was applied to the determination of nitrate in various real water samples. The results are in good agreement with a reference ion chromatographic method.