Development of analytical methods for the acetylsalicylic acid, paracetamol and caffeine determination in solid matrix by fluorescence spectroscopy

Orientador: Lauro Tatsuo KubotaTese (doutorado) - Universidade Estadual de Campinas, Instituto de QuimicaResumo: Neste trabalho são descritos o desenvolvimento dos métodos analíticos para a determinação de ácido acetilsalicílico (AAS), paracetamol (PA) e cafeína (CF) em fase sólida por espectroscopia de fluorescência. A fluorescência nativa do PA no estado sólido foi demonstrada pela primeira vez. Todos os estudos realizados neste trabalho foram desenvolvidos visando principalmente a aplicação no controle de qualidade em indústrias químicas e farmacêuticas. Os estudos foram direcionados ao desenvolvimento de métodos analíticos para a determinação de AAS e PA, individualmente. Também foram desenvolvidos métodos para a determinação simultânea das misturas (CF e AAS) e (CF e PA) usando como ferramenta estatística a calibração multivariada para a construção dos modelos, empregando o algoritmo de regressão por mínimos quadrados parciais (PLSR-1). Foram otimizadas a quantidade de amostra colocada no porta amostra e a distância desta da fibra óptica para todos os métodos analíticos desenvolvidos neste trabalho, e as melhores condições foram de 25 mg e 0,9 cm, respectivamente. Os métodos desenvolvidos para a determinação individual de AAS e PA em amostras sólidas apresentaram boa precisão, exatidão e alta freqüência analítica, podendo chegar a 300 determinações por hora. A exatidão foi checada comparando os valores obtidos pelo método desenvolvido com os procedimentos adotados pela farmacopéia britânica e os resultados foram estatisticamente o mesmo a nível de 95% de confiança. Para a determinação simultânea das misturas, os modelos construídos apresentaram excelente desempenho de previsão. Os resíduos foram inferiores a 10% para a maior parte das amostras usadas nos conjuntos de validação externa. A qualidade dos modelos foi avaliada através do coeficiente de variabilidade (CV), o qual variou entre 4 e 7% para todos os modelos. Desta maneira, os métodos desenvolvidos neste trabalho são uma boa alternativa aos métodos tradicionais descritos na literatura, devido suas características favoráveis como elevada freqüência analítica, possibilidade de monitoramento on line em linha de produção e principalmente por serem não destrutivos, não gerarem resíduos e serem de baixo custo.Abstract: In this work are described the development of analytical method for acetylsalicylic acid (AAS), paracetamol (PA) and caffeine (CF) determinations in solid phase by fluorescence spectroscopy. The native fluorescence of PA was demonstrated in the solid state for the first time. All studies performed here were developed seeking mainly the application in the quality control in chemical and pharmaceutical industries. The studies were addressed to the development of analytical methods for the AAS and PA determination, individually. Methods for the simultaneous determination (CF and AAS) and (CF and PA) using as statistical tool the multivariate calibration for the models construction, employing the partial least squares regression (PLSR-1) algorithm were also developed. The amount of sample placed in the sample compartment and the distance between the fiber optic and sample were optimized for all analytical methods developed in this work and the better conditions were 25 mg and 0.9 cm, respectively. The developed methods for single determination of AAS and PA in samples gave good performance. A high analytical frequency, being able to reach 300 determinations per hour. The accuracy checked comparing the obtained values by the developed methods with the procedures adopted by the British Pharmacopoeia and the results were statistically the same at 95% confidence level. For the simultaneous determination of the mixtures, the built models presented excellent performance of prediction. The residuals were lower than 10% for most used samples in the external validation set. The quality of the models was evaluated through the coefficient of variability (CV), which changed between 4 and 7% for the models. Looking for innovative methods that generate no residue, quick, non-destructive, on line monitoration in production line and low cost is a good option to the traditional methods.DoutoradoQuimica AnaliticaDoutor em Quimic

Metal fluxes at the sediment-water interface in rivers in the Turvo/Grande drainage basin, So Paulo State, Brazil

Purpose The Turvo/Grande drainage basin (TGDB), located in the northwestern region of So Paulo state, covers an area of 15,983 km(2). The region is typically regarded as agricultural by the So Paulo State Environmental Agency, but the industrial area is expanding, and some studies have shown that metal concentrations in water can be higher than the values regulated by Brazilian law. Therefore, the aim of this study was to assess the role of sediments as a source or a sink of metals for drainage basin management.Materials and methods Interstitial water from different sediment depths (0-42 cm) and the sediment-water interface and sediment core samples were collected in February and July 2010 from the Preto, Turvo, and Grande rivers. Quantification of Cr, Cu, Fe, Mn, Ni, and Pb in these samples was performed by graphite furnace or flame atomic absorption spectrometry. Metal diffusive flux estimation from sediment into the overlying water was calculated by Fick's First Law of Diffusion.Results and discussion The fluxes of all metals for the three rivers were positive, indicating diffusion into the overlying water. Ni and Pb showed the lowest diffusive fluxes, which ranged from 2.4 to 3,978 mu g m(-2) day(-1) for Ni and from -0.1 to 1,597 mu g m(-2) day(-1) for Pb. In turn, Cu and Cr were subject to the largest transfer to water, especially in the dry season (Cr, 4.5-7,673 mu g m(-2) day(-1); Cu, 1.3-14,145 mu g m(-2) day(-1)). The Preto River (urban area) showed smaller fluxes than the Grande River (agricultural area), and the values of the latter were higher than those found in other impacted areas of the world.Conclusions The diffusive fluxes indicate that sediments from the TGDB act as a source of metals for the water column, with increased export of metals, particularly Cr and Ni, from the sediment into the overlying water during the dry season.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

DISPONIBILIDADE DE NUTRIENTES E CARBONO ORGÂNICO EM SOLOS CONTENDO CARVÃO HIDROTÉRMICO LAVADO E NÃO LAVADO E COMPARAÇÃO COM SOLOS ANTROPOGÊNICOS

Hydrochar washed (1.0, 2.5, 5.0 and 10.0 %) and not washed (10.0%) produced by hydrothermal carbonization using vinasse and sugarcane bagasse was applied in sand, ultisol and oxisol columns, and the release of NO3-, Orthophosphate, SO42-, Total Organic Carbon (TOC), H+ were evaluated for 30 days. These results were compared with the release of these parameters from experiments conducted with anthropogenic soils. The results demonstrated that higher amounts of nutrients were released for the experiments conducted with hydrochar not washed. With higher rates of hydrochar washed, higher the amount of nutrients released. TOC and SO42- were released throughout the experiment, which is beneficial from the agricultural point of view. Low values of orthophosphate and nitrate release in the leachates were observed for ultisol and oxisol due to the clay and iron and manganese oxides contents. Principal components analysis confirmed the observations and demonstrated that SO42- and TOC preferentially influence the oxisol, being that nitrate and pH influenced the columns containing Terra Mulata and sand. The results allow to conclude that it is possible to adjust the application rate of hydrochar in soils with lower fertility in order to increase it as observed for anthropogenic soils

Avaliação do efeito da piscicultura em sistemas aquáticos em Assis e Cândido Mota, São Paulo, por indicador de qualidade da água e análise estatítica multivariada

In this work, the impact of fish farming activities on the Queixada, Macuco and Pari-Veado Rivers in the Paranapanema watershed was evaluated. Physical, chemical and microbiological parameters were quantified in these aquatic systems followed by application of multivariate statistical analysis (MSA) and water quality index (WQI) tools. Watersheds where fish farming activities are predominant presented WQI > 52 indicating good quality, whereas MSA demonstrated bad quality for these aquatic bodies. The results showed that the degradation in this watershed follows the fish farming activity. The MSA index is more restricted than the National Foundation Sanitation (NFS) index routinely used to infer water quality.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Aplicação e avanços da espectroscopia de luminescência em análises farmacêuticas

This paper provides a review on the latest advances and applications of the luminescence spectroscopy for the development of pharmaceuticals analyses methods, basically based on the photo- and chemiluminescence. The different forms of the drugs determination on pharmaceuticals through the fluorescence and chemiluminescence are discussed. The analyses include the drugs native fluorescence (liquid and solid-phases); the fluorescence from the oxidizing or reducing forms of the drug; the fluorescence from the chemical derivatization and their photochemistry and hydrolysis reactions. The quenching of luminescence and chemiluminescence generation for the pharmaceutical quantification are also shown. Finally, the trends and future perspectives of the luminescence spectroscopy in the field of the pharmaceutical research are discussed