Flow injection amperometric determination of procaine in pharmaceutical formulation using a screen-printed carbon electrode

A rapid and simple method for procaine determination was developed by flow injection analysis (FIA) using a screen-printed carbon electrode (SPCE) as amperometric detector. The present method is based on the amine/hydroxylamine oxidation from procaine monitored at 0.80 V on SPCE in sodium acetate solution pH 6.0. Using the best experimental conditions assigned as: pH 6.0, flow rate of 3.8 mL min(-1), sample volume of 100 mu L and analytical path of 30 cm it is possible to construct a linear calibration curve from 9.0 x 10(-6) to 1.0 x 10(-4) mol L-1. The relative standard deviation for 5.0 x 10(-5) mol L-1 procaine (15 repetitions using the same electrode) is 3.2% and detection limit calculated is 6.0 x 10(-6) mol L-1. Recoveries obtained for procaine gave a mean values from 94.8 to 102.3% and an analytical frequency of 36 injections per hour was achieved. The method was successfully applied for the determination of procaine in pharmaceutical formulation without any pre-treatment, which are in good accordance with the declared values of manufacturer and an official method based on spectrophotometric analysis. (c) 2006 Elsevier B.V. All rights reserved.

Study of structural surface modified tin oxide membrane prepared by sol-gel route sintered at 400 degrees C

This work describes the chemical modification by Tiron(R) molecules of the surface of SnO2 nanoparticles used to prepare nanoporous membranes. Samples prepared with Tiron(R) content between 1 and 20 wt% and fired at 400 C were characterised by X-Ray Powder Diffraction (XRPD), Extended X-ray Absorption Fine Structure (EXAFS), N-2 adsorption isotherms analysis and permeation experiments. XRPD and EXAFS results show a continuous reduction of crystallite size by increasing the Tiron(R) contents until 7.5 wt%. The control exercised by Tiron(R) modifying agent in crystallite growth allows the fine tuning of the average pore size that can be screened from 0.4 to 4 nm as the amount of grafted molecules decreases from 10 to 0 wt%. In consequence, the membrane cut-off can be screened from 1500 to 3500 g.mol(-1).

Study of synthesis variables in the nanocrystal growth behavior of tin oxide processed by controlled hydrolysis

Tin dioxide nanoparticle suspensions were synthesized at room temperature by the hydrolysis reaction of tin chloride (II) dissolved in ethanol. The effect of the initial tin (II) ion concentration, in the ethanolic solution, on the mean particle size of the nanoparticles was studied. The Sn2+ concentration was varied from 0.0025 to 0.1 M, and all other synthesis parameters were kept fixed. Moreover, an investigation of the effect of agglomeration on the nanoparticle characteristics (i.e., size and morphology) was also done by modifying the pH of the SnO2 suspensions. The different samples were characterized by transmission electron microscopy, optical absorption spectroscopy in the ultraviolet range, and photoluminescence measurements. The results show that higher initial ion concentrations and agglomeration lead to larger nanoparticles. The concentration effect is explained by enhanced growth due to a higher supersaturation of the liquid medium. However, it was observed that the agglomeration of the nanoparticles in suspension induce coarsening by the oriented-attachment mechanism.

Indium tin oxide films prepared via wet chemical route

In this work, indium tin oxide (ITO) films were prepared using a wet chemical route, the Pechini method. This consists of a polyesterification reaction between an alpha-hydroxicarboxylate complex (indium citrate and tin citrate) with a polyalcohol (ethylene glycol) followed by a post annealing at 500 degrees C. A 10 at.% of doping of Sn4+ ions into an In2O3 matrix was successfully achieved through this method. In order to characterize the structure, the morphology as well as the optical and electrical properties of the produced ITO films, they were analyzed using different experimental techniques. The obtained films are highly transparent, exhibiting transmittance of about 85% at 550 nm. They are crystalline with a preferred orientation of [222]. Microscopy discloses that the films are composed of grains of 30 nm average size and 0.63 nm RMS roughness. The films' measured resistivity, mobility and charge carrier concentration were 5.8 x 10(-3) Omega cm, 2.9 cm(2)/V s and -3.5 x 10(20)/cm(3), respectively. While the low mobility value can be related to the small grain size, the charge carrier concentration value can be explained in terms of the high oxygen concentration level resulting from the thermal treatment process performed in air. The experimental conditions are being refined to improve the electrical characteristics of the films while good optical, chemical, structural and morphological qualities already achieved are maintained. (C) 2007 Elsevier B.V. All rights reserved.

Aspects of cathodic stripping voltammetry at the hanging mercury drop electrode and in non-mercury disposable sensors

Cathodic stripping voltammetry (CSV) and accumulation at the hanging mercury drop electrode are reviewed briefly. Proposals in a recent IUPAC technical report are considered. Three recent developments in CSV are discussed: the adaptation of CSV methods developed for use with the hanging mercury drop electrode for use with screen-printed carbon electrodes in disposable sensors, the use of reactive accumulation, and the chemometric use of kinetic methods of determination with pulse methods in CSV.

Small angle X-ray scattering study of surface modified tin oxide nanoparticles prepared by sol-gel route

The surface properties of SnO2 nanoparticles were modified by grafting ionic (Tiron (R). (OH)(2)C6H2(SO3Na)(2)(H2O)-H-.) or non-ionic (Catechol (R). C6H4-1,2-(OH)(2)) capping Molecules during aqueous sol-gel processing to improve the redispersibility of powdered xerogel. The effect of the amount of grafted organic molecules on the redispersibility of powders in aqueous solution at several basic pH values was Studied. The nanostructural features of the colloidal suspensions were analyzed by small angle X-ray scattering (SAXS) measurements. Irrespective of the nature and amount of grafted molecules, complete redispersion was obtained in aqueous solution at pH = 13. The redispersion at pH = 11 results in a mixture of dispersed primary particles and aggregates. The proportion of well dispersed nanoparticles and aggregates (and their average size) can be tuned by the quantity of grafted ionic molecules.

Inhibiting effect of citric acid on the pitting corrosion of tin

Potentiostatic and potentiodynamic studies were carried out to establish the inhibiting effects of citric acid on the pitting corrosion of tin. The critical potential (E-crit), which leads to pitting or general corrosion, was determined in sodium perchlorate solution in the pH range 1.0 to 4.0. Pit nucleation and growth, at pH 4.0, can be described by instantaneous nucleation followed by progressive nucleation. The results show that the minimum acid concentration needed to inhibit pitting of tin is 10(-2) M. Pitting occurrence by direct interaction between metal and perchlorate anions was observed.

Sintering and crystallite growth of nanocrystalline copper doped tin oxide

The effect of Cu2+ contents and of firing temperature on sintering and crystallite growth of nanocrystalline SnO2 xerogels was analyzed by thermoanalysis (mass loss (TG), linear shrinkage, and differential thermal analysis (DTA)), X-ray powder diffraction (XRPD), and EXAFS (extended X-ray absorption fine structures) measurements. Samples were prepared by two methods: (a) coprecipitation of a colloidal suspension from aqueous solution containing both Sn(IV) and Cu(II) ions and (b) grafting copper(II) species on the surface of tin pride gel. The thermoanalysis has shown that the shrinkage associated with the mass loss decreases by increasing the amount of copper. The EXAFS measurements carried out at the Cu K edge have evidenced the presence of copper in substitutional solid solution for the dried xerogel prepared with 0.7 mol % of copper, while for higher concentration of doping, copper has been observed also at the external surface of crystallites. The solid solution is metastable and copper migrates toward the surface during firing. The XRPD and DTA results have shown a recrystallization process near 320 degrees C, which leads to crystallite growth. The presence of copper segregated near the crystallite surface controls its growth.

Preconcentration of rutin at a poly glutamic acid modified electrode and its determination by square wave voltammetry

The voltammetric determination of rutin in 0.04 mol l(-1) B-R buffer (pH 4.0) by square wave voltammograms (+0.41 V vs. Ag/AgCl(sat.)) at a poly glutamic acid modified glassy carbon electrode was found to be several orders of magnitude lower than that on a bare glassy carbon electrode. Rutin can be preconcentrated on the films of poly glutamic acid and presented linear relationship from concentration of 7 x 10(-7) to 1 x 10(-5) mol l(-1) in 0.04 mol l(-1) B-R buffer pH 4.0. The method was successfully applied to the determination of rutin in pharmaceutical formulation without any pretreatment.

Voltammetric determination of persulfate anions using an electrode modified with a Prussian blue film

Prussian blue [PB, iron(III) hexacyanoferrate(II)] films are effective for the electrocatalysis of the persulfate (peroxodisulfate)/sulfate redox system. This has been exploited in the voltammetric determination of persulfate anions using a PB-modified platinum disc electrode. A linear correlation between electrocatalytic current and persulfate concentration was found for the range 5 x 10(-5) to 3 x 10(-3) mol dm(-3), using 0.100 mol dm(-3) potassium chloride as supporting electrolyte at pH 4. This analytical method has the advantages of speed and ease of operation in relation to traditional titrimetric methods for persulfate determination. The applicability of the method to the determination of persulfate in a commercial hair bleaching 'booster' product is demonstrated. (C) 2000 Elsevier B.V. B.V. All rights reserved.

SAXS study of formation and growth of tin oxide nanoparticles in the presence of complexing ligands

The effect of acetylacetone (acac) complexing ligand on the formation and growth of tin oxide-based nanoparticles during thermohydrolysis at 70 degreesC of a tin precursor SnCl4-n(acac)(n) (0 less than or equal to n less than or equal to 2) solution was analyzed by in situ small-angle X-ray scattering. A. transparent and stable sol was obtained after 2 h of thermohydrolysis at 70 degreesC, allowing the quantitative determination of the particle volume distribution function and its variation with the reaction time. The number of colloidal particles for equivalent thermohydrolysis temperature and time decreases as the [acac]/[Sn] ratio in initial solution increases from 0.5 to 6. Instead, the amount of soluble species remaining in solution increases for increasing [acac]/[Sn] ratio within the same range. This indicates that increasing amounts of Sn-acetylacetone complexes partially prevent the hydrolysis and consequent formation of colloidal particles. The N-2 adsorption isotherm characterization of freeze-dried powders demonstrates that the average pore size is approximately equal to the average size (approximate to9 Angstrom) of the colloidal primary particles in the sol, and that the porosity and surface area (approximate to200 m(2) g(-1)) are independent of the acac content in the initial solution.

Mesoproterozoic rapakivi granites of the Rondonia Tin Province, southwestern border of the Amazonian craton, Brazil - I. Reconnaissance U-Pb geochronology and regional implications

Rapakivi granites and associated mafic and ultramafic rocks in the Rondonia Tin Province, southwestern Amazonian craton, Brazil were emplaced during six discrete episodes of magmatism between ca 1600 and 970 Ma. The seven rapakivi granite suites emplaced at this time were the Serra da Providencia Intrusive Suite (U-Pb ages between 1606 and 1532 Ma); Santo Antonio Intrusive Suite(U-Pb age 1406 Ma), Teotonio Intrusive Suite (U-Pb age 1387 Ma); Alto Candeias Intrusive Suite (U-Pb ages between 1346 and 1338 Ma); Sao Lourenco-Caripunas Intrusive Suite (U-Pb ages between 1314 and 1309 Ma); Santa Clara Intrusive Suite (U-Pb ages between 1082 and 1074 Ma); and Younger Granites of Rondonia (U-Pb ages between 998 and 974 Ma). The Serra da Providencia Intrusive Suite intruded the Paleoproterozoic (1.80 to 1.70 Ga) Rio Negro-Juruena crust whereas the other suites were emplaced into the 1.50 to 1.30 Ga Rondonia-San Ignacio crust. Their intrusion was contemporaneous with orogenic activity in other parts of the southwestern Amazonian craton, except for the oldest, Serra da Providencia Intrusive Suite. Orogenic events coeval with emplacement of the Serra da Providencia Intrusive Suite are not clearly recognized in the region. The Santo Antonio, Teotonio, Alto Candeias and Sao Lourenco-Caripunas Intrusive Suites are interpreted to represent extensional anorogenic magmatism associated with the terminal stages of the Rondonian-San Ignacio orogeny. At least the Sao Lourenco-Caripunas rapakivi granites and coeval intra-continental rift sedimentary rocks may, in contrast, represent the products of extensional tectonics and rifting preceding the Sunsas/Aguapei orogeny (1.25 to 1.0 Ga). The two youngest rapakivi suites, the Santa Clara Intrusive Suite and Younger Granites of Rondonia, seemingly represent inboard magmatism in the Rondonian-San Ignacio Province during a younger episode of reworking in the Rio Negro-Juruena Province during the waning stages of the collisional 1.1 to 1.0 Ga Sunsas/Aguapei orogeny. The six intra-plate rapakivi granite episodes in the southwestern part of the Amazonian craton form three broad periods of anorogenic magmatism that have age-correlative events composed of similar rocks and geologic environments in eastern Laurentia and Baltica, although the exact timing of magmatism appears slightly different. Recognition of lithologic and chronological correlations between various cratons provide important constraints to models explaining the interplay between rapakivi granite magmatism and deep crustal evolution of an early Mesoproterozoic supercontinent. They are, furthermore, important to plate tectonic models for the assembly, dispersal and reassembly of Amazonia, Laurentia and Baltica in the Mesoproterozoic and Neoproterozoic. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Influence of the oxygen adsorbed on tin varistors doped with Co, Mn and Cr oxides

The non-ohmic properties of the 98.90% SnO2+(1-x)%CoO+0.05% Cr2O3+0.05% Nb2O5+x% MnO2 varistor system (all of them in mol %), as well as the influence of the oxidizing and reducing atmosphere on this system were studied in this work. Experimental evidence indicates that the electrical properties of the varistor depend on the defects that occur at the grain boundary and on the adsorbed oxygen species such as O''(2), O'(2), O in this region. Thermal treatments at 900 degreesC in oxygen and nitrogen atmospheres indicated such a dependence with the values of the non-linearity coefficient (alpha) increasing under oxygen atmosphere, being reduced in nitrogen atmosphere and restored after a new treatment in oxygen atmosphere, presenting a reversibility in the process. EDS analysis accomplished by SEM showed the distribution of the oxides in the varistor matrix. (C) 2002 Kluwer Academic Publishers.

Application of a glassy carbon electrode modified with poly(glutamic acid) in caffeic acid determination

Glassy carbon electrodes were coated with films of poly( glutamic acid) ( PG), and the modified electrode proved to be very effective in the oxidation of caffeic acid. The performance of the film was also tested with ascorbic acid, coumaric acid, ferulic acid, sinapic acid and chlorogenic acid. At pH 5.6, all the hydroxycinnamic acids yield a higher peak current intensity when oxidized after incorporation in the PG-modified electrode, and only the oxidation of ascorbic acid exhibits overpotential reduction. At pH 3.5 only caffeic and chlorogenic acid are incorporated in the modified electrode and exhibit a well-defined oxidation wave at +0.51 V and +0.48 V, which is the base for their determination. Linear calibration graphs were obtained from 9 x 10(-6) mol L-1 to 4 x 10(-5) mol L-1 caffeic acid by linear voltammetric scan and from 4 x 10(-6) mol L-1 to 3 x 10(-5) mol L-1 by square wave voltammetric scan. The method was successfully applied to the determination of caffeic acid in red wine samples without interference from other hydroxycinnamic acids or ascorbic acid.

Evaluation of a highly sensitive amperometric biosensor with low cholinesterase charge immobilized on a chemically modified carbon paste electrode for trace determination of carbamates in fruit, vegetable and water samples

A highly sensitive amperometric biosensor for determination of carbamate pesticides directly in water, fruit and vegetable samples has been evaluated, electrochemically characterized and optimized. The biosensor strip was fabricated in screen printed technique on a ceramic support using silver-based paste for reference electrode, and platinum-based paste for working and auxiliary electrodes. The working electrode was modified by a layer of carbon paste mixed with cobalt(II) phthalocyanine and acetylcellulose. Cholinesterase (ChE) enzymes with low enzymatic charge were immobilized on this layer. The operational simplicity of the biosensor consists in that a small drop (similar to 50 mu l) of substrate or sample is deposited on a horizontally positioned biosensor strip representing the microelectrochemical cell. The working potential of the biosensor was 370 mV versus Ag/AgI on a ship reference electrode preventing the interference of electroactive species which are oxidable at more positive potentials. The biosensor was applied to investigate the degradation of two reference ChE inhibitors in freeze dried water under different storage conditions and for direct determination of some N-methylcarbamates (NMCs) in fruit and vegetable samples at ppb concentration levels without any sample pretreatment. A comparison of the obtained results for the total carbamate concentration was done against those obtained using HPLC measurements. (C) 1999 Elsevier B.V. B.V. All rights reserved.