Preconcentration with chromatomembrane cell and adsorptive polarographic determination of fluorine in air

The present paper describes a procedure in which fluorine in the air was preconcentrated in a chromatomembrane cell and its content was determined by adsorptive polarography. In a pH 4.90 buffer solution the fluorine ion can form a ternary complex with La(III) and ALC. The complex can be adsorbed at the mercury electrode and yields a sensitive oscillopolarographic wave at -0.67 V, which can be sensitized by Triton X-100. Over the range 3.0x10(-8)-1.60x10(-6) M, the peak currents are linearly proportional to the concentration of the fluoride. The detection limit is 1.0x10(-8) M. First the fluorine in the air samples was preconcentrated in the chromatomembrane cells using 0.10 M NaOH solution, then its content was determined by complex-adsorptive polarography.     

Preconcentration with membrane cell and adsorptive polarographic determination of formaldehyde in air

The present paper describes a procedure that formaldehyde in air was preconcentrated in a membrane cell and its content was determined by adsorptive polarography. First the formaldehyde in air samples was preconcentrated in a membrane cell using water, then the formaldehyde reacted with 2,4-dinitrophenyl hydrazine to form 2,4-dinitrophenyl hydrazone, which can be adsorbed at the mercury electrode and yields a sensitive adsorptive polarographic wave. Over the range 6.0x10(-10)-5.0x10(-6) M, the peak currents are linearly proportional to the concentration of formaldehyde, the detection limit is 2.0x10(-10) M.     

An optode sensor for Cu2+ with high selectivity based on porphyrin derivative appended with bipyridine.

A porphyrin derivative (fluorophore) appended with bipyridine (ionophore) has been applied for preparation of a Cu2+-sensitive optical chemical sensor, which is based on fluorescence quenching of porphyrin derivative entrapped in a poly(vinyl chloride) membrane by the energy transfer process. The sensor exhibits a linear response toward Cu2+ in the concentration range 2.0 x 10(-8) - 1.0 x 10(-5) M, with a working pH range from 6.0 to 8.0 and a high selectivity. The detection limit is 5 x 10(-9) M. The response time for Cu2+ is less than 5 min with concentrations lower than 5 x 10(-6) M. The optode can be regenerated using 0.3 M EDTA (pH 9) and acetate buffer solution. The effect of the composition of the sensor membrane was studied, and the experimental conditions were optimized. The sensor has been used for direct determination of Cu2+ in water samples with satisfied results.     

Amperometric determination of urea using an NADH-dependent coupled enzyme

Enzyme electrodes for the amperometric measurement of urea were prepared by co-immobilizing l-glutamate dehydrogenase and urease onto an Immobilon-AV affinity membrane with attachment to a glassy carbon electrode. Reduced nicotinamide adenine dinucleotide (NADH) was used as the electroactive species. The electrochemical oxidation of NADH was monitored at +1.0 V vs. Ag/AgCl. The enzyme immobilized electrode was linear over the range of 2.0 x 10(-5) to 2 x 10(-4)M. The response time of the electrode was 3 min and the optimum pH of enzyme immobilized membrane was pH 7.4-7.6 (Dulbecco's buffer solution). It was stable for at least two weeks and 50 assays. There were no interferences from other physiological material, except for high levels of ascorbic acid.     

Capillary electrochromatography with zwitterionic stationary phase on the lysine-bonded poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolithic capillary column

A polymer-based neutral monolithic capillary column was prepared by radical polymerization of glycidyl methacrylate and ethylene dimethacrylate in a 100 mum id fused-silica capillary, and the prepared monolithic column was subsequently modified based on a ring opening reaction of epoxide groups with 1 M lysine in solution (pH 8.0) at 75 degrees C for 10 h to produce a lysine chemically bonded stationary phases in capillary column. The ring opening reaction conditions were optimized so that the column could generate substantial EOF. Due to the zwitterionic functional groups of the lysine covalently bonded on the polymer monolithic rod, the prepared column can generate cathodic and anodic EOF by varying the pH values of running buffer during CEC separation. EOF reached the maximum of -2.0 x 10(-8) m2v(-1)s(-1) and 2.6 x 10(-8) m2v(-1)s(-1) with pH of the running buffer of 2.25 and 10, respectively. As a consequence, neutral compounds, ionic solutes such as phenols, aromatic acids, anilines, and basic pharmaceuticals were all successfully separated on the column by CEC. Hydrophobic interaction is responsible for separation of neutral analytes. In addition, the electrostatic and hydrophobic interaction and the electrophoretic migration play a significant role in separation of the ionic or ionizable analytes.     

Facile separation and determination of Aconitine alkaloids in traditional Chinese medicines by CE with tris(2,2'-bipyridyl) ruthenium(II)-based electrochemiluminescence detection

A facile CE method coupled with tris(2,2'-bipyridyl) ruthenium(II)-based electrochemiluminescence [Ru(bpy)(3) (2+)] detection was developed for simultaneous determination of Aconitum alkaloids, i.e., hypaconitine (HA), aconitine (AC), and mesaconitine (MA) in baseline separation. The optimal separation of these Aconitum alkaloids was achieved in a fused-silica capillary column (50 cm x 25 microm id) with 30 mM phosphate solution (pH 8.40) as running buffer at 12 kV applied voltage. The three alkaloids can be determined within 10 min by a single run. The calibration curves showed a linear range from 2.0 x 10(-7) to 2.0 x 10(-5) M for HA, 3.4 x 10(-7) to 1.7 x 10(-5) M for AC, and 3.8 x 10(-7) to 1.9 x 10(-5) M for MA. The RSDs for all analytes were below 3.01%. Good linear relationships were found with correlation coefficients for all analytes exceeding 0.993. The detection limits were 2.0 x 10(-8) M for HA, 1.7 x 10(-7) M for AC, and 1.9 x 10(-7) M for MA under optimal conditions. This method was successfully applied to determine the three alkaloids in Aconitum plants.     

Electrochemical study of the antineoplastic agent etoposide at carbon paste electrode and its determination in spiked human serum by differential pulse voltammetry

The electrochemical oxidation of the antineoplastic agent etoposide was studied at carbon paste electrode in Britton-Robinson buffer solutions over the pH range 2.0-10.0 using cyclic, linear sweep and differential pulse voltammetry. Oxidation of the drug was effected in a single reversible, diffusion-controlled step within the pH range 2.0-4.0, a second oxidation process was produced above pH 4.0. Using differential pulse voltammetry (DPV), the drug yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 3.0 at 0.500 V (vs. Ag/AgCl) on carbon paste electrode. This process could be used to determine etoposide concentrations in the range 2.5 x 10(-7) to 2.5 x 10(-5) M with a detection limit of 1.0 x 10(-7) M. The method was successfully applied to the determination of the drug in spiked human serum.     

Bis-dimethylaminobenzaldehyde Schiff-base cobalt(II) complex as a neutral carrier for a highly selective iodide electrode.

A new solvent polymeric membrane electrode based on N,N'-bis-(dimethylaminobenzaldehyde)-glycine cobalt(II) [Co(II)-BDMABG] as a neutral carrier is described, which displays a preferential potentiometric response to iodide ion and an anti-Hofmeister selectivity sequence in the following order: I- > ClO4- > Sal- > SCN- > NO2- > Br- > NO3- > Cl- > SO3(2-) > SO4(2-). The electrode exhibits a near-Nernstian potential linear range of 9.0 x 10(-7)-1.0 x 10(-1) M with a detection limit of 6.8 x 10(-7) M and a slope of -53.0 mV/decade in pH 2.0 of a phosphate buffer solution at 20 degrees C. The response mechanism is discussed in view of the A.C. impedance technique and the UV spectroscopy technique. The electrode was successfully applied to the determination of iodide in Jialing River and Spring in Jinyun Mountains with satisfactory results.     

Fabrication of herbicide biosensors based on the inhibition of enzyme activity that catalyzes the scavenging of hydrogen peroxide in a thylakoid membrane.

A novel herbicide biosensor with a thylakoid modified membrane electrode is presented. Thylakoid, isolated from spinach leaves, was entrapped in a membrane of poly (vinylalcohol) with the styrylpyridinium group (PVA-SbQ). The thylakoid membrane was fixed on the surface of a platinum electrode. It was found that the enzymes in thylakoid kept their activity for several months in the membrane. The oxidative current of hydrogen peroxide in a Tris-HCl buffer solution (pH 7.4) was detected at the modified electrode by a differential pulse voltammetric method. In the presence of herbicides, the oxidation current from the hydrogen peroxide decreased due to an inhibitor effect on the enzymes in thylakoid compared with that in the absence of the herbicides. The changes in the oxidation current at the electrode were proportional to the herbicide concentrations. The sensor could be used to detect herbicides in concentration ranges of 3 x 10(-9) - 1.5 x 10(-7) M for paraquat, 1 x 10(-8) - 3 x 10(-7) M for diuron, 4 x 10(-8) - 3 x 10(-6) M for prometryn, 5 x 10(-8) - 5 x 10(-6) M for atrazine and 1 x 10(-7) - 5 x 10(-6) M for ametryn, respectively. The enzyme activity on scavenging hydrogen peroxide in the modified PVA-SbQ membrane was examined.     

Electrochemical study of zolpidem at glassy carbon electrode and its determination in a tablet dosage form by differential pulse voltammetry

The oxidative behaviour of, a hypnotic drug, zolpidem was studied at glassy carbon electrode in Britton-Robinson buffer over the pH range 2.0-11.0 using cyclic, linear sweep and differential pulse voltammetry. Oxidation of the drug was effected in a single irreversible, diffusion-controlled step. Using differential pulse voltammetry (DPV), the drug yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 8.0 at +0.889 V (vs. Ag/AgCl) on glassy carbon electrode. This process could be used to determine zolpidem concentrations in the range 5.0 x 10(-7) M to 1.0 x 10(-5) M with a detection limit of 2.0 x 10(-7) M. The method was applied, without any interference from the excipients, to the determination of the drug in a tablet dosage form.     

Study on the determination of metronidazole in human serum by adsorptive stripping voltammetry

In Britton-Robinson buffer, metronidazole is preconcentrated on a HMDE at 0.0 V (vs. AgAgCl). An adsorptive stripping peak is observed at -0.62 V. The response is linear from 1 x 10(-8) to 1 x 10(-6)M with 1.5 min accumulation. The method has been successfully applied to the determination of metronidazole in human serum and formulations.     

A facile and sensitive chemiluminescence detection of amino acids in biological samples after capillary electrophoretic separation

It was found that native amino acids enhanced the chemiluminescence (CL) reaction between luminol and BrO(-) in an alkaline aqueous solution. This has led to the development of a facile and highly sensitive CL detection scheme for the determination of amino acids in biological samples after capillary electrophoretic (CE) separation. The CE-CL conditions were optimized. An electrophoretic buffer of 2.5 x 10(-2) M sodium borate (pH 9.4) containing 1 x 10(-4) M luminol was used. The oxidizer solution of 8 x 10(-4) M NaBrO in 0.1 M sodium carbonate buffer solution (pH 12.5) was introduced post-column. Under the optimal conditions, the detection limits were 1.0 x 10(-7) M for glutamic acid (Glu) and 1.3 x 10(-7) M (S/N = 3) for aspartic acid (Asp). The relative standard deviations (RSDs) of peak area and migration time were in the ranges of 3.8-4.3% and 1.4-1.6%, respectively. The present method was applied to the determination of excitatory amino acids (i.e., Asp and Glu) in rat brain tissue and monkey plasma. The levels of these major excitatory amino acids in monkey plasma were quantified for the first time and found to be 1.17 +/- 0.17 x 10(-5) M (mean +/- SD, n = 6) for Glu and 1.64 +/- 0.19 x 10(-6) M for Asp, which were comparable with the levels in human plasma.     

Determination of bisphenol A and 10 alkylphenols in serum using SDS micelle capillary electrophoresis with gamma-cyclodextrin.

A new micelle capillary electrophoresis based on cyclodextrin micellar electrokinetic chromatography (MEKC) for the determination of bisphenol A and 10 alkylphenols in rat serum is reported. Several surfactants and dextrins were studied. Bisphenol A and alkylphenols were separated using a 50 microm x 50 cm capillary with 20 mM borate phosphate buffer (pH 8.0) containing 20 mM sodium dodecylsulfate and 5 mM gamma-cyclodextrin as carrier. The method could determine 0.6-2000 microg/mL of phenols in 100 microL serum by photometric detection at 214 nm. Using 2.0 mL serum, 1.0 ng/mL of phenols could be determined. The relative standards deviations were 6.3-7.7% at 10 microg/mL in serum. The recoveries were 91.8-93.0% with 10 microg/mL serum samples.     

Ion-selective electrodes for potentiometric determination of ranitidine hydrochloride, applying batch and flow injection analysis techniques.

New ranitidine hydrochloride (RaCl)-selective electrodes of the conventional polymer membrane type are described. They are based on incorporation of ranitidine-tetraphenylborate (Ra-TPB) ion-pair or ranitidine-phosphotungstate (RaPT) ion-associate in a poly(vinyl chloride) (PVC) membrane plasticized with dioctylphthalate (DOP) or dibutylphthalate (DBP). The electrodes are fully characterized in terms of the membrane composition, solution temperature, and pH. The sensors showed fast and stable responses. Nernstian response was found over the concentration range of 2.0 x 10(-5) M to 1.0 x 10(-2) M and 1.0 x 10(-5) M to 1.0 x 10(-2) M in the case of Ra-TPB electrode and over the range of 1.03 x 10(-5) M to 1.00 x 10(-2) M and 1.0 x 10(-5) M to 1.0 x 10(-2) M in the case of Ra-PT electrode for batch and FIA systems, respectively. The electrodes exhibit good selectivity for RaCl with respect to a large number of common ions, sugars, amino acids, and components other than ranitidine hydrochloride of the investigated mixed drugs. The electrodes have been applied to the potentiometric determination of RaCl in pure solutions and in pharmaceutical preparations under batch and flow injection conditions with a lower detection limit of 1.26 x 10(-5) M and 5.62 x 10(-6) M at 25 +/- 1 degrees C. An average recovery of 100.91% and 100.42% with a relative standard deviation of 0.72% and 0.53% has been achieved.     

Determination of trace levels of diosmin in a pharmaceutical preparation by adsorptive stripping voltammetry at a glassy carbon electrode.

A systematic study on the electrochemical behavior of diosmin in Britton-Robinson buffer (pH 2.0-10.0) at a glassy carbon electrode (GCE) was made. The oxidation process of the drug was found to be quasi-reversible with an adsorption-controlled step. The adsorption stripping response was evaluated with respect to various experimental conditions, such as the pH of the supporting electrolyte, the accumulation potential and the accumulation time. The observed anodic peak current at +0.73 V vs. Ag/AgCl reference electrode increased linearly over two orders of magnitude from 5.0x10(-8) M to 9.0x10(-6) M. A limit of detection down to 3.5x10(-8) M of diosmin at the GCE was achieved with a mean recovery of 97+/-2.1%. Based on the electrochemical data, an open-circuit accumulation step in a stirred sample solution of BR at pH 3.0 was developed. The proposed method was successfully applied to the determination of the drug in pharmaceutical formulations. The results compared favorably with the data obtained via spectrophotometric and HPLC methods.     

Ferrocene branched chitosan for the construction of a reagentless amperometric hydrogen peroxide biosensor

Chitosan was chemically branched with ferrocene moieties and further used as a support for the immobilization of horseradish peroxidase on a glassy carbon electrode. The reagentless biosensor device showed a linear amperometric response toward hydrogen peroxide concentrations between 35 x 10(-6) M and 2.0 x 10(-3) M. The biosensor reached 95% of the steady-state current in about 20 s and its sensitivity was 28.4 x 10(-3) microA x M(-1). The enzyme electrode retained 94% of its initial activity after 2 weeks of storage at 4 degrees C in 50 x 10(-3) M sodium phosphate buffer at pH 7.0.     

Permselectivity of neurotransmitters at overoxidized polypyrrole-film-coated glassy carbon electrodes

The permselectivity of neurotransmitters such as dopamine, epinephrine, and norepinephrine at overoxidized polypyrrole (OPPY)-film-coated glassy carbon electrodes has been investigated. The chemically-modified electrodes exhibit attractive permselectivity and antifouling properties of rejecting anionic species, e.g. ascorbate, etc. Compared with the response of neurotransmitters at modified electrodes overoxidized in phosphate buffer solution (pH 7.4), higher sensitivity and reversibility response can be obtained at modified electrodes overoxidized in sodium hydroxide solution. The effect of film thickness on the permselective response was tested. Rotating disk electrode experiments were used to determine the apparent diffusion coefficients of several electroactive solutes in the OPPY films. The influence of the hydrophobicity of the organic ions on the permeability within the polymer films was discussed. Dopamine and epinephrine were determined at the 1 x 10(-6)-1 x 10(-4) M level by means of voltammetry after an exposure period of 2 min in 0.1 M phosphate buffer (pH 7.4) with detection limits of 8 x 10(-7) M and 6 x 10(-7) M respectively.     

Mechanisms of NO release by N1-nitrosomelatonin: nucleophilic attack versus reducing pathways

A new type of physiologically relevant nitrosamines have been recently recognized, the N(1)-nitrosoindoles. The possible pathways by which N(1)-nitrosomelatonin (NOMel) can react in physiological environments have been studied. Our results show that NOMel slowly decomposes spontaneously in aqueous solution, generating melatonin as the main organic product (k = (3.7 +/- 1.1) x 10(-5) s(-1), Tris-HCl (0.2 M) buffer, pH 7.4 at 37 degrees C, anaerobic). This rate is accelerated by acidification (k(pH 5.8) = (4.5 +/- 0.7) x 10(-4) s(-1), k(pH 8.8) = (3.9 +/- 0.6) x 10(-6) s(-1), Tris-HCl (0.2 M) buffer at 37 degrees C), by the presence of O(2) (k(o) = (9.8 +/- 0.1) x 10(-5) s(-1), pH 7.4, 37 degrees C, [NOMel] = 0.1 mM, P(O(2)) = 1 atm), and by the presence of the spin trap TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl; k(o) = (2.0 +/- 0.1) x 10(-4) s(-1), pH 7.4, 37 degrees C, [NOMel] = 0.1 mM, [TEMPO] = 9 mM). We also found that NOMel can transnitrosate to l-cysteinate, producing S-nitrosocysteine and melatonin (k = 0.127 +/- 0.002 M(-1) s(-1), Tris-HCl (0.2 M) buffer, pH 7.4 at 37 degrees C). The reaction of NOMel with ascorbic acid as a reducing agent has also been studied. This rapid reaction produces nitric oxide and melatonin. The saturation of the observed rate constant (k = (1.08 +/- 0.04) x 10(-3) s(-1), Tris-HCl (0.2 M) buffer, pH 7.4 at 37 degrees C) at high ascorbic acid concentration (100-fold with respect to NOMel) and the pH independence of this reaction in the pH range 7-9 indicate that the reactive species are ascorbate and melatonyl radical originated from the reversible homolysis of NOMel. Taking into account kinetic and DFT calculation data, a comprehensive mechanism for the denitrosation of NOMel is proposed. On the basis of our kinetics results, we conclude that under physiological conditions NOMel mainly reacts with endogenous reducing agents (such as ascorbic acid), producing nitric oxide and melatonin.     

Electrochemical behaviour of sertraline at a hanging mercury drop electrode and its determination in pharmaceutical products

The electrochemical behaviour of sertraline at a hanging mercury drop electrode (HMDE) was described. Different voltammetric techniques, such as cyclic, linear sweep, differential pulse and square wave voltammetry, were used. Voltammograms were obtained at different pH values with a Britton-Robinson buffer solution used as supporting electrolyte. The best results were found by square wave voltammetry with electrodeposition at alkaline pH using a borate buffer with a pH = 8.2 for the samples, containing 12% (v/v) methanol. Under optimised conditions, a linear relationship between 2.33 x 10(-7) and 3.15 x 10(-6) M of sertraline with a limit of detection of 1.98 x 10(-7) M was obtained. The electrochemical method developed was applied to the determination of sertraline in pharmaceutical formulations. Recoveries were close to 100%, thus proving efficacy of the proposed method for the quantification of sertraline in commercial samples.     

Determination of copper(II) by anodic stripping voltammetry at a 2,5-dimercapto-1,3,4-thiadiazol self-assembled monolayer-based gold electrode.

2,5-Dimercapto-1,3,4-thiadiazol (DMTD) can bind on the surface of a gold electrode through the strong gold-sulfur interaction. The fabrication and electrochemical characteristics of the DMTD self-assembled monolayer (SAM)-modified gold electrode were investigated. The DMTD SAM electrode exhibited a significantly increased sensitivity. Cu(II) was accumulated in phosphate buffer (pH 4.6) at a potential of -0.6 V (vs. Ag/AgCl) for 40 s and then determined by anodic stripping voltammetry (ASV) in copper-free phosphate buffer (pH 5.0). The effects of various parameters, such as the pH values of the preconcentration solution and measurement solution, the accumulation potential, and the accumulation time, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 8.0 x 10(-6) to 8.0 x 10(-5) mol l(-1) with a correlation coefficient of 0.9978. The relative standard deviations for eight successive determinations were 4.3 and 2.9% for 1.0 x 10(-5) and 2.0 x 10(-5) mol l(-1) Cu(II), respectively. The detection limit (three times signal to noise) was 4.0 x 10(-7) mol l(-1). The proposed voltammetric method was utilized successfully to detect the concentration of Cu(II) ions in tap water samples.