Electroanalytical determination of oxadiazon and characterization of its base-catalyzed ring-opening products

The electrochemical behavior of the hydrolysis products of oxadiazon was studied by cyclic and square-wave voltammetry using a glassy carbon electrode. Maximum currents were obtained at pH 12.8 in an aqueous electrolyte solution containing 30% ethanol and the current did not decrease with time showing that there was little adsorption of the reaction products on the electrode surface. The hydrolysis products of oxadiazon were identi®ed, after isolation and puri®cation, as 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl)-2-ethoxycarbonylhydrazine (Oxa1) and 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) with redox potentials 0.6Vand 70.1V (vs. Ag=AgCl), respectively. Based on the electrochemical behavior of 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) a simple electroanalytical procedure was developed for the determination of oxadiazon in commercial products used in the treatment of rice crops in Portugal that contain oxadiazon as the active ingredient. The detection limit was 161074 M, the mean content and relative standard deviation obtained for seven samples of two different commercial products by the electrochemical method were 28.4 0.8% (Ronstar) and 1.9 0.2% (Ronstar GR), and the recoveries were 100.3 5.4% and 101.1 5.3 %, respectively.

Electrochemical determination of citalopram by adsorptive stripping voltammetry–determination in pharmaceutical products

The electrochemical behavior of citalopram was studied by square-wave and square-wave adsorptive-stripping voltammetry (SWAdSV). Citalopram can be reduced and accumulated at a mercury drop electrode, with a maximum peak current intensity being obtained at a potential of approximately -1.25V vs. AgCl/Ag, in an aqueous electrolyte solution of pH 12. A SWAdSV method has been developed for the determination of citalopram in pharmaceutical preparations. The method shows a linear range between 1.0x10-7 and 2.0x10-6 mol L-1 with a limit of detection of 5x10-8 mol L-1 for an accumulation time of 30 s. The precision of the method was evaluated by assessing the repeatability and intermediate precision, achieving good relative standard deviations in all cases (≤2.3%). The proposed method was applied to the determination of citalopram in five pharmaceutical products and the results obtained are in good agreement with the labeled values.

Citrate selective electrodes for the flow injection analysis of soft drinks, beers and pharmaceutical products

Aiming the establishment of simple and accurate readings of citric acid (CA) in complex samples, citrate (CIT) selective electrodes with tubular configuration and polymeric membranes plus a quaternary ammonium ion exchanger were constructed. Several selective membranes were prepared for this purpose, having distinct mediator solvents (with quite different polarities) and, in some cases, p-tert-octylphenol (TOP) as additive. The latter was used regarding a possible increase in selectivity. The general working characteristics of all prepared electrodes were evaluated in a low dispersion flow injection analysis (FIA) manifold by injecting 500µl of citrate standard solutions into an ionic strength (IS) adjuster carrier (10−2 mol l−1) flowing at 3ml min−1. Good potentiometric response, with an average slope and a repeatability of 61.9mV per decade and ±0.8%, respectively, resulted from selective membranes comprising additive and bis(2-ethylhexyl)sebacate (bEHS) as mediator solvent. The same membranes conducted as well to the best selectivity characteristics, assessed by the separated solutions method and for several chemical species, such as chloride, nitrate, ascorbate, glucose, fructose and sucrose. Pharmaceutical preparations, soft drinks and beers were analyzed under conditions that enabled simultaneous pH and ionic strength adjustment (pH = 3.2; ionic strength = 10−2 mol l−1), and the attained results agreed well with the used reference method (relative error < 4%). The above experimental conditions promoted a significant increase in sensitivity of the potentiometric response, with a supra-Nernstian slope of 80.2mV per decade, and allowed the analysis of about 90 samples per hour, with a relative standard deviation <1.0%.

Innovative manufacturing process for hybrid pultruded products based on cork and polymeric pre-shapes

Pultruded products are being targeted by a growing demand due to its excellent mechanical properties and low chemical reactivity, ensuring a low level of maintenance operations and allowing an easier assembly operation process than equivalent steel bars. In order to improve the mechanical drawing process and solve some acoustic and thermal insulation problems, pultruded pipes of glass fibre reinforced plastics (GFRF) can be filled with special products that increase their performance regarding the issues previously referred. The great challenge of this work was drawing a new equipment able to produce pultruded pipes filled with cork or polymeric pre-shaped bars as a continuous process. The project was carried out successfully and the new equipment was built and integrated in the pultrusion equipment already existing, allowing to obtain news products with higher added-value in the market, covering some needs previously identified in the field of civil construction.

Significance of Biogenic Amines in Cold-Smoked Fish and Their Relation to Microbiological Characteristics of Products Available in Portuguese Retail Markets

Studies on microbial characterization of cold-smoked salmon and salmon trout during cold storage were performed on samples available in the Portuguese market. Samples were also classified microbiologically according to guidelines for ready-to-eat (RTE) products. Further investigations on sample variability and microbial abilities to produce tyramine and histamine were also performed. The coefficient of variation for viable counts of different groups of microorganisms of samples collected at retail market point was high in the first 2 wk of storage, mainly in the Enterobacteriaceae group and aerobic plate count (APC), suggesting that microbiological characteristics of samples were different in numbers, even within the same batch from the same producer. This variation seemed to be decreased when storage and temperature were controlled under lab conditions. The numbers of Enterobacteriaceae were influenced by storage temperature, as indicated by low microbial numbers in samples from controlled refrigeration. Lactic acid bacteria (LAB) and Enterobacteriaceae were predominant in commercial products, a significant percentage of which were tyramine and less histamine producers. These results might be influenced by (1) the technological processes in the early stages of production, (2) contamination during the smoking process, and (3) conditions and temperature fluctuations during cold storage at retail market point of sale.

Otimização do processo de injeção de ZAMAK

A indústria automóvel necessita aumentar a produtividade de forma sistemática, com vista à redução de custos e incremento da competitividade. A otimização dos produtos e processos é uma constante. O presente trabalho foi solicitado pela empresa FicoCables, do Grupo FICOSA, tendo em vista a otimização do processo de injeção de pequenas peças injetadas em ZAMAK, que constituem o bloqueio na extremidade de cada cabo metálico inserido nos automóveis para abertura da mala, portas, travão de mão, reservatório de combustível, capô, etc. A empresa possui cerca de 52 equipamentos de injeção de ZAMAK, cuja temperatura dos bicos era mantida com base numa chama de gás. Os sucessivos problemas de controlo do sistema ditaram uma mudança estratégica no aquecimento desses bicos, passando a ser usadas resistências elétricas anelares. No entanto, esta mudança veio a apresentar problemas inesperados, os quais se vieram inclusivamente a tornar em problemas de segurança, devido ao desgaste interior prematuro dos bicos, os quais apresentaram esmo problema de rotura. Paralelamente, todos os parâmetros relacionados com este processo de fabrico estavam também estudados de forma algo incipiente, pelo que se tornou necessário compreender e dissecar todas as variáveis relacionadas com o processo e implementar sistemas que impedissem o ajuste não controlado dos parâmetros por parte dos operadores. Também os moldes foram alvo de ações de melhoria, com vista a evitar problemas na zona de contacto do bico com o molde. O processo foi analisado em pormenor, permitindo um controlo muito mais apurado do mesmo. Os resultados fizeram sentir-se de forma imediata, graças ao trabalho desenvolvido neste estudo e à abertura demonstrada pela empresa para implementar todas as soluções propostas. O resultado final traduz-se num incremento significativo da segurança para os operadores, num controlo muito mais apurado de todos os parâmetros envolvidos no processo, numa maior garantia da qualidade nos produtos injetados em ZAMAK e em ganhos financeiros significativos para a empresa.