PVC Membrane Sensor for Potentiometric Determination of Fluoxetine in Some Pharmaceutical Formulations

Abstract

The construction and general performance of a novel potentiometric membrane sensor for determination of fluoxetine has been developed. It is based on the formation of the ion association complex of fluoxetine with picrolonic acid as electroactive material, dispersed in a PVC matrix and o‐nitrophenyl octyl ether as a plasticizer. The sensor shows a fast, stable, and near Nernstian response for 1×10^?2 M to 8×10^?6 M fluoxetine at 25°C over the pH range of 1–5 with a cationic slope of 51±0.5 mV/decade. The lower detection limit is 6×10^?6 M and the response time 20–35 sec. Selectivity coefficients for fluoxetine, related to number of interfering substances, were investigated. There are negligible interferences from the studied cations, anions, and pharmaceutical excipients. The determination of fluoxetine in aqueous solution shows an average recovery of 98.6% and a mean relative standard deviation (RSD) of 1.5% at 100 µg/mL. The direct determination of fluoxetine in some formulations gave results that compare favorably with those obtained by a spectrophotometric method. The developed membrane electrode has been used as an end point indicator electrode, e.g., potentiometric titration of fluoxetine with sodium tetraphenylborate as a titrant has been monitored.     

Low-cost potentiometric sensor based on a molecularly imprinted polymer for the rapid determination of matrine in herbal medicines

Abstract

A low-cost potentiometric sensor based on a molecularly imprinted polymer was developed for the determination of matrine in herbal medicine samples. The imprinted material was synthesized by the use of matrine as template, methacrylic acid (MAA) as the monomer, ethylene glycol dimethyl acrylate (EGDMA) as the cross linker, 2,2′-azo-bisisobutyronitrile (AIBN) as the initiator, and toluene and dodecanol as the porogenic agent. The electrode sensing membrane was fabricated by incorporating the ground imprinted particles into the polyvinyl chloride substrate that was subsequently incorporated into a laboratory constructed ion-selective electrode. The prepared imprinted sensor exhibited a rapid Nernst response across the concentration range from 1?×?10^?5 to 1?×?10^?1 M with a detection limit equal to 9.3?×?10^?6 M. The analytical capabilities support the direct determination of matrine in herbal medicine. The analytical results were verified by a standard ultraviolet absorption spectrophotometry protocol. The proposed sensor manifested a series of advantages, including high selectivity and sensitivity, enhanced stability and low cost, that provides a wide number of potential applications for herbal analysis.     

Construction of an Optical Sensor for Cobalt Determination Based on Methyltrioctylammonium Chloride Immobilized on a Polymer Membrane

Abstract

An optical sensor has been designed for the determination of cobalt by spectrophotometry. The sensing membrane is made by immobilizing methyltrioctylammonium chloride on a triacetylcellulose membrane. In the presence of Co(II) and thiocyanate ions, the colorless membrane changes to blue. The response time of the optode was about 7 min. The sensor can readily be regenerated with 0.02 mol L^?1 sodium oxalate solution. This optode is stable and can be stored under water for more than a month without reagent leaching. The calibration curve was linear in the range of 8.5×10^?6–1.3×10^?4 mol L^?1 of Co(II) ion with a limit of detection 5.9×10^?6 mol L^?1. The relative standard deviations for seven replicate measurements of 3.4×10^?5 and 1×10^?4 mol L^?1 of Co(II) were 1.58 and 1.10%, respectively. The sensor was successfully applied to the determination of cobalt in food samples and vitamin B₁₂ ampoule.     

Determination of R‐Deprenyl using a Maltodextrin‐Based Enantioselective,Potentiometric Membrane Electrode

Abstract

The enantioselective, potentiometric membrane electrode (EPME) based on maltodextrin with dextrose equivalence (DE) 16.5–19.5 is proposed for the assay of R‐deprenyl. The linear concentration range for the proposed electrode is 10^?10?10^?3 mol L^?1. The slope of the electrode is 53.1 mV per decade of concentration. The detection limit is 3.6×10^?11 mol L^?1. The proposed electrode could be reliably employed for the assay of R‐deprenyl raw material and its pharmaceutical formulation, Lentogesic tablets.     

SENSITIVE L-CYSTEINE AMPEROMETRIC SENSOR BASED ON A GLASSY CARBON ELECTRODE MODIFIED BY MnO2 NANOPARTICLES

A sensitive amperometric sensor for the determination of L-cysteine was fabricated by electrodeposition of modified MnO₂ nanoparticles on a glassy carbon electrode. The morphology of the nanoparticles was characterized by scanning electron microscopy. Cyclic voltammetry was applied to investigate the mechanism of film formation and the electrochemical properties of the MnO₂ nanoparticle-modified electrode. The results of electrochemical experiments showed that the modified electrode had a favorable catalytic ability for the electrochemical oxidation of L-cysteine. Under optimized conditions, the MnO₂ nanoparticle-modified electrode exhibited a linear dependence on the concentration of L-cysteine from 1.0 × 10^?6 to 6.4 × 10^?4 M, and a detection limit of 8.0 × 10^?7 M (signal/noise = 3). The modified electrode was highly resistant towards typical inorganic salts and some biomolecules. In addition, the sensor was applied for the determination of L-cysteine in human serum with high accuracy, demonstrating its potential for practical applications.     

PVC MATRIX MEMBRANE SENSORS FOR POTENTIOMETRIC DETERMINATION OF ARECOLINE

The construction and electrochemical response characteristics of Poly (vinyl chloride) (PVC) membrane sensors for arecoline HBr (AR) are described. The sensing membranes incorporate ion association complexes of (AR) cation and sodium tetraphenyl borate (NaTPB) (sensor 1) or phosphomolybdic acid (PMA) (sensor 2) or phosphotungstic acid (PTA) (sensor 3) as electroactive materials. The sensors display a fast, stable and near-Nernstian response over a relative wide AR concentration range (1 × 10^?2 – 4 × 10^?5 M) and (1 × 10^?2 to 5 × 10^?6 M), with cationic slopes of 52.5, 50.5 and 51.5 mV per concentration decade for sensor 1, 2, and 3, respectively over a pH range of 3.0–6.0. The sensors show good discrimination of AR from several inorganic and organic compounds. The direct determination of 1.5–2360.0 μg/ml of AR show an average recovery of 99.0, 98.5 and 99.5% and a mean relative standard deviation of 1.7, 1.6 and 1.5% at 200.0 μg/ml for sensor 1, 2 and 3 respectively. The proposed sensors have been applied for direct determination of AR in human saliva. The results obtained for determination of AR in saliva using the proposed method comparable favorably with those obtained using HPLC method.     

DESIGN OF A SENSITIVE MEMBRANE OPTODE FOR IRON DETERMINATION

An optical chemical sensor has been developed for the sensitive determination of Fe (III) ions by spectrophotometry. The optical membrane was constructed by immobilization of methyltrioctylammonium chloride on triacetylcellulose polymer. The exchange of thiocyanate as counter ion in the membrane sensitized this film to Fe (III). The sensing membrane is capable of determining Fe(III) reversibly over a dynamic range of 7.11 × 10^?7?8.88 × 10^?5 mol L^?1 with a limit of detection of 6.02 × 10^?7 mol L^?1 and a response time of 5 min. This optode can easily be regenerated by 0.1 mol L^?1 of sodium fluoride solution. The relative standard deviation for eight replicate measurements of 7.11 × 10^?6 and 5.33 × 10^?5 mol L^?1 of Fe (III) was 4.2 and 3.7%, respectively. The sensor was successfully applied for the determination of iron in tablet and water samples.     

Electrochemical Behavior of Uric Acid at a Meso‐2,3‐Dimercaptosuccinic Acid Self‐Assembled Gold Electrode

Abstract

The fabrication and electrochemical characteristics of a meso‐2,3‐dimercaptosuccinic acid (DMSA) self‐assembled monolayer modified gold electrode were investigated. The DMSA self‐assembled electrode can enhance the electrochemical stability of uric acid (UA) and the electrochemical reaction of UA on the DMSA electrode has been studied by cyclic voltammetry and electrochemical quartz crystal microbalance. Some electrochemical parameters, such as diffusion coefficient, standard rate constant, electron transfer coefficient, and protons transfer number have been determined for the electrochemical behavior on the DMSA 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 DMSA/Au electrode. In phosphate buffer (pH 5.0), the peak current is proportional to the concentration of UA in the range of 8.0×10^?5?1.0×10^?2 mol L^?1 and 8.0×10^?5?8.0×10^?3 mol L^?1 for the cyclic voltammetry and differential pulse voltammetry methods with the detection limits of 1×10^?6 and 8×10^?7 mol L^?1, respectively. This method can be applied to the determination of the UA concentration.     

A Chitosan-Graphene Electrochemical Sensor for the Determination of Copper(II)

Graphite oxide was prepared by oxidizing graphite powder, reduced to graphene using hydrazine hydrate, and the grapheme was mixed with chitosan to form a composite that was used to modify a glassy carbon electrode for the determination of copper(II). The electrochemical behavior of the modified electrode was studied by cyclic and square wave voltammetries. The morphology and structure of the composite were characterized by infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. In addition, the proportion of composite material, pH, and adsorption time was optimized. Under the optimized experimental conditions, the sensor showed a linear dynamic range from 1.0 × 10^?9 to 1.5 × 10^?8 mol · L^?1 for copper(II) with a limit of detection of 4.3 × 10^?10 mol · L^?1 at a signal-to-noise ratio of three. The sensor displayed excellent electrochemical response and high sensitivity.     

Electrochemical Behavior of Epinephrine at Two‐Component Self‐Assembled Monolayer of meso‐2,3‐Dimercaptosuccinic Acid and Penicillamine on Gold Electrode

Abstract

A mixed, self‐assembled monolayer (SAM) of meso‐2,3‐dimercaptosuccinic acid (DMSA) and penicillamine (PCA) was prepared on a gold electrode. The mixed SAM of DMSA and PCA, for which the volume ratio of DMSA:PCA was 2:1, showed an obvious electrochemical activity for the oxidation of epinephrine (EP). In the phosphate buffer (pH 7.7), a sensitive oxidation peak was observed at 0.213 V on the DMSA and PCA modified Au electrode. The peak current was proportional to the concentration of EP in the range between 5.0×10^?6 and 8.0×10^?4 mol L^?1. For the cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods, the detection limits were 3.9×10^?7 and 2.5×10^?7 mol L^?1, respectively. The reaction mechanism has been primarily discussed. The electrode reaction of EP was an irreversible process with two electrons and two protons transfer at the SAM gold electrode. The SAM gold electrode was applied to the determination of EP in epinephrine hydrochloride injection samples with satisfactory results.     

Development of Sulfide‐Selective Optode Membranes Based on Immobilization of Methylene Blue on Optically Transparent Triacetylcellulose Film

Abstract

The development of reversible sulfide‐selective optode membranes, based on immobilization of methylene blue (MB) on optically transparent triacetylcellulose film, is described. The sensing scheme of the sulfide‐selective optode membranes is based on the decreasing absorbance of the membrane at 654 nm in the presence of sulfide, which can be related to the sulfide concentration in solution. The dynamic working range, detection limit, sensitivity, selectivity, and effect of pH are discussed in detail.

Under optimum experimental conditions, the membrane system shows a calibration response range from 3.1×10^?5 to 6.1×10^?4 M in a phosphate buffer of pH 7.5. Typical response times in the samples are 15–20 min. The lifetime of the system was about 30 days, with a relative standard deviation of <2%. The sensing membrane showed a good selectivity to sulfide over other anions. The optode membrane was applied to the determination of sulfide in real samples.     

Potentiometric Detection of Anions Separated by Liquid Chromatography Using a Metallic Silver Wire Electrode

Abstract

A silver metallic wire electrode, coated with AgCl, used for potentiometric detection of inorganic anions in liquid chromatography, is described. The electrode response to the anions was evaluated by both static and flow injection measurements, and results have shown that the electrode exhibits sensitive response to CI^? and SCN^? with a detection limit of 10^?6 M. The electrode was used as a potentiometric detector for the determination of anions following separation by ion chromatography using the eluent containing 5 mM phthalate at pH 4.2. Calibration plots were not linear, but give a useful working range of 5 x10^?5 to 3 x10^?2 M. It also demonstrated to be a useful detector for the detection of anions separated, where the separation of anions was preformed with a C₁₈ column using a 0.1 mM octylammonium salicylate as an ion-paring reagent, by ion-pair chromatography. The determination of chloride in waste water samples were demonstrated by proposed method.

     

Electrochemical determination of hydrogen peroxide using a novel prussian blue–polythiophene–graphene oxide membrane-modified glassy carbon electrode

A polythiophene–graphene oxide compound membrane and Prussian blue were deposited sequentially on the surface of a glassy carbon electrode by cyclic voltammetry. Due to its excellent electrocatalysis and its analogy with peroxidase enzymes, Prussian blue has been widely used in amperometric biosensors. The polythiophene–graphene oxide compound membrane exhibited good electroconductibility and a large specific surface area. The fabricated Prussian blue/polythiophene/graphene oxide/glassy carbon electrode was characterized by transmission electron microscopy, scanning electron microscopy, and cyclic voltammetry. Under the optimal experimental conditions, the detection of hydrogen peroxide was studied by its amperometric current–time curve. Due to the presence of polythiophene–graphene oxide compound membrane and Prussian blue, the hydrogen peroxide sensor shows a linear calibration range of 1.0?×?10^?6–1.0?×?10^?4?mol?L^?1, detection limits of 3.2?×?10^?7?mol?L^?1 at a signal-to-noise ratio of 3, and recoveries from 95.0 to 105.0%. The results show that the modified glassy carbon electrode has potential practical application for the determination of hydrogen peroxide based on its sensitivity and long-term stability.     

A HYDROGEN PEROXIDE SENSOR BASED ON PRUSSIAN BLUE AND DNA-MODIFIED ELECTRODE

The polyvinylpyrrolidone (PVP) protected Prussian blue (PB) nanoparticles were prepared for use as a sensor for the catalytic reduction of hydrogen peroxide. The nanoparticles were used to modify a gold electrode, which was applied to detect hydrogen peroxide. Impedance spectra and differential pulse voltammetry were applied to detect the performance of the novel electrode and its response to H₂O₂ and Ramos cell smash fluid. Under the optimized experimental conditions, hydrogen peroxide was detected in a linear range of 6.25 × 10^?7 to 1.0 × 10^?5 mol · L^?1, and the detection limit was 7.12 × 10^?8 mol · L^?1 according to 3σ rule. Under the same conditions, hydrogen peroxide was determined in Ramos cell smash fluid with a linear range from 400–80000 mol mL^?1, with a detection limit of 114 mL^?1 according to 3σ rule. The modified electrode with Prussian blue nanoparticles displayed high sensitivity, good reproducibility, and long-term stability to hydrogen peroxide.     

Batch and Flow‐Injection Determination of Catecholamines Using Ion Selective Electrodes

Abstract

New epinephrine (EP), dopamine (DA), and L‐Dopa (LD) ion selective PVC membrane electrodes based on ion‐pairs of catecholamines with tetraphenylborate (TPhB) are prepared. In the present work, plastic membrane selective electrodes have been constructed. They are based on the incorporation of EP‐TPhB, DA‐TPhB, or LD‐TPhB ion exchangers in poly(vinylchloride) (PVC) membranes plasticized with di(2‐ethylhexyl)sebacate (DES). The electrodes show a near – Nernstian response in the concentration ranges: 1.0×10^?4—1.0×10^?2 mol/L (epinephrine), 5.0×10^?5–1.0×10^?2 mol/L (dopamine), and 5.0×10^?4–1.0×10^?2 mol/L (L‐Dopa). The electrodes selective for epinephrine and L‐Dopa are used as detectors in the flow injection system. The proposed methods allow determination of catecholamines in pharmaceutical preparations.     

Determination of polydatin by gold nanoparticle-enhanced chemiluminescence of silver nitrate and luminol

A novel flow injection method for the determination of polydatin is reported based on the inhibition of silver nitrate, luminol, and gold nanoparticles chemiluminescence. Under the optimum condition, the decrease in chemiluminescence was proportional to the concentration of polydatin from 1.0 × 10^?8 to 1.0 × 10^?5 mol/L. The detection limit was 2.1 × 10^?9 mo1/L and the relative standard deviation was 2.1% for the determination of 1.0 × 10^?6 mol/L polydatin. This method was successfully employed for the determination of polydatin in Polygonum cuspidatum roots and human urine.     

CERIUM(IV)-BASED CHEMILUMINESCENCE OF FELODIPINE SENSITIZED BY RHODAMINE 6G

A simple, rapid, and sensitive flow injection chemiluminescence (FI-CL) method was proposed for the determination of felodipine. The method was based on the CL-emitting reaction between the studied drug and cerium(IV) in a nitric acid medium and measurement of the CL intensity produced by rhodamine 6G used as a sensitizer. Under the optimum conditions, the proposed procedure had a linear range between 5.0 × 10^?9 and 7.0 × 10^?6 g mL^?1, with a detection limit of 2.0 × 10^?9 g mL^?1. The relative standard deviation was 2.3% for 1.0 × 10^?7 g mL^?1 felodipine solution (n = 11). It was applied to the determination of felodipine in pharmaceutical preparations and biological fluids with satisfactory results. The possible mechanism of the chemiluminescence reaction was also discussed briefly.     

Immersion‐Angle Dependence of the Resonant‐Frequency Shift of a Quartz Crystal Microbalance in Three Types of Newtonian Liquids

Abstract

The present work reports the new characteristics of the immersion‐angle dependence of the resonant‐frequency shift (ΔF) of the one‐face sealed quartz crystal microbalance (QCM) in three types of Newtonian liquids, i.e., sucrose, glucose, and glycerol solutions. Below some 1.80×10^?2 g cm^?2 · s^?1/2, the ΔF values are dependent on the immersion angles in all solutions. However, we have found that the transition phenomenon of ΔF occurs between 1.78×10^?2 and 4.80×10^?2 g · cm^?2 · s^?1/2 in the sucrose solution, between 1.75×10^?2 and 4.34×10^?2 g · cm^?2 · s^?1/2 in the glucose solution and between 1.83×10^?2 and 3.03×10^?2 g · cm^?2 · s^?1/2 in the glycerol solution, respectively. Moreover, above the concentrations of the end points of the transition phenomenon, the ΔF values of the sucrose solution are equal to those of 90° at all immersion angles. On the other hand, those of the glucose and the glycerol solutions are the same as those of 30°. This difference may be caused by inherent characteristics of adsorption to the surface of the QCM electrode.     

Characterization and application of lornoxicam,europium(III), and lysozyme fluorescence

A novel and sensitive spectrofluorimetric method was developed for the determination of lornoxicam. The method was based on the fluorescence enhancement of europium(III) by formation of a ternary complex with lornoxicam in the presence of lysozyme as the co-ligand. The fluorescence signal for the lornoxicam-europium (III)-lysozyme system was monitored at an excitation wavelength of 620 nm and an emission wavelength of 390 nm. The parameters affecting the fluorescence intensity were optimized systematically and under these conditions the signal was directly proportional to the concentration of lornoxicam from 9.0 × 10^?5 to 1.0 × 10^?2 µg · mL^?1. The detection limit was 2.7 × 10^?5 µg · mL^?1. The relative standard deviation for thirteen replicate measurements of 1.0 × 10^?3 µg · mL^?1 lornoxicam was 1.8%. This method was employed for the determination of lornoxicam in pharmaceutical formulations and biological fluids. The mechanism of fluorescence for the lornoxicam-europium(III)-lysozyme system was discussed.     

DETERMINATION OF LEAD(II) BY FLOW-INJECTION ANALYSIS USING LUMINOL-POTASSIUM PERIODATE POST-CHEMILUMINESCENCE REACTION

The post-chemiluminescence (PCL) phenomenon arising from the potassium periodate–luminol reaction induced by lead(II) was investigated. A strong PCL signal was observed when lead(II) was injected into the mixture of potassium periodate and luminol in a flow-cell. The influencing factors on the PCL intensity of the system were investigated. Under the optimum experimental conditions, the present method allowed the determination of lead(II) in the concentration range of 1.0 × 10^?8 to 1.0 × 10^?5 mol/L and the detection limit for lead(II) was 2.3 × 10^?10 mol/L. The relative standard deviation was 3.2% for 11 replicate analyses of 1.0 × 10^?6 mol/L lead(II). Combined with cotton cellulose xanthate for separation, the proposed method was applied to the determination of lead(II) in real water samples with satisfactory results.