Electrometric studies on formation of cerium vanadates as a function of pH

The precise nature of the reaction between nitric acid and sodium ortho-vanadate solutions has been studied by means of electrometric techniques involving potentiometric and conductometric titrations. The well defined inflections and breaks in the titration curves confirm the existence of the anions, pyro-V2O7(4-), meta-VO3- and poly-H2V10O28(4-) corresponding to the ratios of VO4(3-):H+ as 1:1, 1:2 and 1:2.6 in the neighborhood of pH 10.5, 7.4 and 3.6, respectively. The interaction of cerium(III) nitrate with sodium vanadate solutions, at specific pH levels 12.4, 10.5, 7.4 and 3.6 was also studied by potentiometric and conductometric titrations between the reactants. The end-points obtained from the sharp inflections in the titration curves provide definite evidence for the formation and precipitation of cerium ortho-Ce2O3.V2O5, pyro-2Ce2O3.3V2O5 and meta-Ce2O3.3V2O5 vanadates in the neighborhood of pH 7.4, 6.2 and 4.8, respectively. Analytical investigations on the precipitates formed confirm the results of the electrometric study.

Kinetic evaluation of the dehydration of Yb(III) Lu(III) and Y(III) 4-chlorobenzylidenepyruvate by thermogravimetry (TG)

The dehydration kinetic of Yb, Lu and Y 4-chlorobenzylidenepyruvate was studied by using thermogravimetry and the kinetics parameters obtained by Flynn and Wall method suggest that the dehydration step follows a first order mechanism. The activation energies calculated were 103.6, 96.6 and 97.2 kJ/mol and the lifetime considering the temperature of 31 and 101 º C for the dehydration of these compounds were 23, 26, 31 minutes and 0.6, 1.3 and 1.4 seconds, respectively. The results have similar values and suggest that the water is attached in the same way.

Determinação de chumbo em álcool combustível por voltametria de redissolução anódica utilizando um eletrodo de pasta de carbono modificado com resina de troca iônica Amberlite IR 120

Um método envolvendo a pré-concentração e redissolução anódica em condições de voltametria de pulso diferencial empregando um eletrodo de pasta de carbono modificado (EPCM) com uma resina de troca iônica Amberlite IR120 foi proposto para a determinação de íons chumbo em álcool combustível. O procedimento é baseado em um pico de oxidação do analito observado em -0,53 V(vs. Ag/AgCl) em solução de HCl. As melhores condições experimentais encontradas foram: 5% (m/m) da Amberlite IR120 para a construção do eletrodo, solução de HCl 0,1 mol L-1, velocidade de varredura de 10 mVs-1, tempo de pré-concentração de 15 min e amplitude de pulso de 100 mV. Utilizando essas condições, o EPCM apresentou uma resposta linear entre a corrente de pico anódica e a concentração de íons chumbo para o intervalo entre 9,9 x 10-9 e 1,2 x 10-6 mol L-1 e um limite de detecção de 7,2 x 10-9 mol L-1. Valores de recuperação entre 96 % e 102 % foram encontrados para amostras de álcool combustível enriquecidas com Pb2+ em níveis de 10-7 mol L-1. O efeito da presença de outros íons concomitantes sobre a resposta voltamétrica do eletrodo também foi avaliado.

A water soluble 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octanechloride silsesquioxane grafted onto Al/SiO2 surface: chromium adsorption study

The water soluble material, 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octanechloride silsesquioxane (dabcosil silsesquioxane) was obtained. The dabcosil silsesquioxane was grafted onto a silica surface, previously modified with aluminum oxide. The resulting solid, dabcosil-Al/SiO2, presents 0.15 mmol of dabco groups per gram of material. The product of the grafting reaction was analyzed by infrared spectroscopy and N2 adsorption-desorption isotherms. The dabcosil-Al/SiO2 material was used as sorbent for chromium (VI) adsorption in aqueous solution.

Prochloraz residue levels in ginger submitted to Sportak 450 CE" postharvest treatment

A preliminary study was conducted to determine the residue levels of prochloraz in ginger samples treated with Sportak 450 CE® (prochloraz as active ingredient) under laboratory conditions and cold-storage for 15 days at 10°C and 89% RH. Sampling was carried out at 10 and 15 days after Sportak 450 CE® dip treatment (450 and 900 µg mL-1). Pesticide residues were determined by GCECD. During the study, residue levels in ginger ranged between 3.6 and 10.6 mg Kg-1 for prochloraz.

Determinação amperométrica de iodeto em soluções expectorantes orais com análise por injeção em fluxo usando a reação iodeto/nitrito

Neste trabalho foi desenvolvido um sistema de injeção em fluxo visando à determinação amperométrica de íons iodeto em soluções expectorantes. O método é baseado na reação do iodeto com íons nitrito em meio ácido. O iodo formado é monitorado por amperometria no potencial de +200 mV vs. Ag/AgCl (3 mol L-1), usando um eletrodo de trabalho de disco de platina (RDE) com raio = 0,75 mm adaptado a uma célula eletroquímica "wall-jet". O sistema em fluxo foi usado com o carregador impulsionado pela pressão gravitacional dos reagentes (carregador: solução 2 x 10-4 mol L-1 em NaNO2 e 0,2 mol L-1 em H2SO4), na vazão de 4 mL min-1. O método é rápido (acima de 100 injeções h-1) e preciso (RSD = 1,9%; n=10 e C I 8 x 10-6 mol L-1), apresentando um limite de detecção de 20 ng I- ou 8 x 10-7 mol L-1 (3SD). A validação do método proposto foi realizada seguindo as normas USP, ou seja, titulação potenciométrica com AgNO3 0,100 mol L-1 e os resultados obtidos mostraramse concordantes com os valores de referência do fabricante.

Comparison of some properties of Cu(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

The physico-chemical properties and thermal stability in air of Cu(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates were compared and the influence of the position of -OCH3 substituent on their thermal stability was investigated. The complexes are crystalline, hydrated salts with blue colour. The carboxylate ion is a bidentate chelating or bridging group. The thermal stability of analysed Cu(II) dimethoxybenzoates was studied in the temperature range of 293-1173 K. The positions of methoxy- groups in benzene ring influence the thermal properties of studied complexes. Their different thermal properties are markedly connected with the various influence of inductive, mesomeric and steric effects of -OCH3 substituent on the electron density in benzene ring. The magnetic susceptibilities of the complexes were measured over the range of 76-300 K and the magnetic moments were calculated. The results show that they form dimers.

Analysis of the structure and vibrational spectra of glucose and fructose

Molecular modelling using semiempirical methods AM1, PM3, PM5 and, MINDO as well as the Density Functional Theory method BLYP/DZVP respectively were used to calculate the structure and vibrational spectra of d-glucose and d-fructose in their open chain, alpha-anomer and beta-anomer monohydrate forms. The calculated data show that both molecules are not linear; ground state and the number for the point-group C is equal to 1. Generally, the results indicate that there are similarities in bond lengths and vibrational modes of both molecules. It is concluded that DFT could be used to study both the structural and vibrational spectra of glucose and fructose.

Sorption kinetics and intrapaticulate diffusivity of As(III) bioremediation from aqueous solution, using modified and unmodified coconut fiber

The pollution and toxicity problems posed by arsenic in the environment have long been established. Hence, the removal and recovery remedies have been sought, bearing in mind the efficiency, cost effectiveness and environmental friendliness of the methods employed. The sorption kinetics and intraparticulate diffusivity of As (III) bioremediation from aqueous solution using modified and unmodified coconut fiber was investigated. The amount adsorbed increased as time increased, reaching equilibrium at about 60 minutes. The kinetic studies showed that the sorption rates could be described by both pseudo-first order and pseudo-second order process with the later showing a better fit with a value of rate constant of 1.16 x 10-4 min-1 for the three adsorbent types. The mechanism of sorption was found to be particle diffusion controlled. The diffusion and boundary layer effects were also investigation. Therefore, the results show that coconut fiber, both modified and unmodified is an efficient sorbent for the removal of As (III) from industrial effluents with particle diffusion as the predominant mechanism.

Sensitive bromatometric assay methods for finasteride in pharmaceuticals

Three sensitive spectrophotometric methods are presented for the determination of finasteride in bulk and in tablets. The methods rely on the use of bromate-bromide reagent and three dyes namely, methyl orange, indigocarmine and thymol blue as reagents. They involve the addition of a measured excess of bromate-bromide reagent to finasteride in acid medium, and after the bromination reaction is judged to be complete, the unreacted bromine is determined by reacting with a fixed amount of either methylorange and measuring the absorbance at 520 nm (method A) or indigocarmine and measuring the absorbance at 610 nm (method B) or thymol blue and measuring the absorbance at 550 nm (method C). In all the methods, the amount of insitu generated bromine reacted corresponds to the amount of finasteride. The absorbance measured at the respective wavelength is found increase linearly with the concentration of finasteride. Beer's law is obeyed in the ranges 0.25- 2.0, 0.5-6.0 and 1-12 µg mL-1 for method A, method B and method C, respectively. The calculated molar absorptivity values are 5.7x10(4), 3.12x10(4) and 1.77x10(4) L mol-1 cm-1 respectively, for method A, method B and method C, and the corresponding Sandell sensitivity values are 0.0065, 0.012 and 0.021 µg cm-2. The limits of detection (LOD) and quantification (LOQ) are also reported for all the methods. Accuracy and, intra-day and inter-day precisions of the methods were established according to the current ICH guidelines. The methods were successfully applied to the determination of finasteride in commercially available tablets and the results were found to closely agree with the label claim. The results of the methods were statistically compared with those of a reference method by applying Student's t-test and F-test. The accuracy and reliability of the methods were further confirmed by performing recovery tests via standard addition procedure.

A direct potentiometric titration study of the dissociation of humic acid with selectively blocked functional groups

A direct potentiometric titration method was applied to commercial and soil humic acids in order to determine their carboxyl and phenol group concentrations and apparent and intrinsic pK. In that context, acid-base properties of humic acids are interpreted by selective blocking of carboxylic and phenolic groups by esterification and acetylation. Differences in underivatized and derivatized HA's acid-base properties are ascribed to carboxyl and phenol groups influence on total humic acidity. Potentiometric data were treated with the modified Henderson-Hasselbalch equation. Infra red results, the acidic group contents and the average values of apparent and intrinsic pK for underivatized and derivatized HAs confirmed the selectivity of esterification derivatization method. After blocking of the functional groups, the values of acidic group contents decreased, while the value of apparent pK increased after derivatization. Phenol groups cannot be specifically identified by the acetylation method, due to low selectivity of the acetylation method.

Avaliação da confiabilidade analítica das determinações de carbono orgânico total (COT)

Observando a literatura pode ser verificado um crescente número de trabalhos que determinam potenciais contaminantes presentes em matrizes de interesse ambiental. É importante ressaltar que quando se estuda o ambiente, os dados analíticos são uma das ferramentas usadas para se avaliar a extensão dos problemas observados que conseqüentemente influenciam as tomadas de decisão. Assim a confiabilidade desses dados é de extrema importância. Neste contexto, este trabalho visa avaliar a confiabilidade analítica das determinações de Carbono Orgânico Total (COT), ferramenta empregada no monitoramento da matéria orgânica em diversos estudos ambientais. Para essa avaliação foram analisados alguns parâmetros de desempenho como limite de detecção e quantificação, repetibilidade e linearidade.

Magnetic, thermal and spectral properties of Ni(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

Complexes of Ni(II) 2,3-, 3,5- and 2,6-dimethoxybenzoates have been synthesized, their physico-chemical properties have been compared and the influence of the position of -OCH3 substituent on their properties investigated. The analysed compounds are crystalline, hydrated salts with green colour. The carboxylate ions show a bidentate chelating or bridging coordination modes. The thermal stabilities of Ni(II) dimethoxybenzoates were investigated in air in the range of 293-1173 K. The complexes decompose in three steps, yelding the NiO as the final product of decomposition. Their solubilities in water at 293 K are in the order of 10-2-10-4 mol×dm-3. The magnetic susceptibilities for the analysed dimethoxybenzoates of Ni(II) were measured over the range of 76-303 K and the magnetic moments were calculated. The results reveal that the complexes are the high-spin ones and the ligands form the weak electrostatic field in the octahedral coordination sphere of the central Ni(II) ion. The various position -OCH3 groups in benzene ring cause the different steric, mesomeric and inductive effects on the electron density in benzene ring.

Callus cell culture of Pothomorphe umbellata (L.) under stress condition leads to high content of peroxidase enzyme

Pothomorphe umbellata (L.) known on Brazil as Caapeba has a number of popular medicinal use, and it has been studied in relation to its pharmacological activity. Peroxidase specific activity (units/mg protein) was evaluated in callus cell culture samples of the P.umbellata, grown in two different MS medium (media 1 and media 2), submitted to 16 hours photoperiod or kept in darkness. Cell growth rate curve showed that the best growth indices were observed when media 2 submitted to the photoperiod regime was used, followed by the same media kept in darkness (stress condition). The results obtained also showed that the cell culture grown under stress conditions (darkness) lead to high content of peroxidase enzyme (an increase of 700% was observed). Kinetic constant values of 3.3 mmol.L-1 and 2,8 sec-1 were obtained for kM and v max,, respectively, using guaiacol as enzyme substrate.

Sensitive spectrophotometric determination of lansoprazole in pharmaceuticals using ceric ammonium sulphate based on redox and complex formation reactions

Two simple sensitive and cost-effective spectrophotometric methods are described for the determination of lansoprazole (LPZ) in bulk drug and in capsules using ceric ammonium sulphate (CAS), iron (II), orthophenanthroline and thiocyanate as reagents. In both methods, an acidic solution of lansoprazole is treated with a measured excess of CAS followed by the determination of unreacted oxidant by two procedures involving different reaction schemes. The first method involves the reduction of residual oxidant by a known amount of iron(II), and the unreacted iron(II) is complexed with orthophenanthroline at a raised pH, and the absorbance of the resulting complex measured at 510 nm (method A). In the second method, the unreacted CAS is reduced by excess of iron (II), and the resulting iron (III) is complexed with thiocyanate in the acid medium and the absorbance of the complex measured at 470 nm (method B). In both methods, the amount CAS reacted corresponds to the amount of LPZ. In method A, the absorbance is found to increase linearly with the concentration of LPZ where as in method B a linear decrease in absorbance occurs. The systems obey Beer's law for 2.5-30 and 2.5-25 µg mL-1 for method A and method B, respectively, and the corresponding molar absorptivity values are 8.1×10³ and 1.5×10(4) L mol-1cm-1 . The methods were successfully applied to the determination of LPZ in capsules and the results tallied well with the label claim. No interference was observed from the concomitant substances normally added to capsules.