Static and hydrodynamic monitoring of citalopram based on its electro-oxidation behavior at a glassy-carbon surface

The electrooxidative behavior of citalopram (CTL) in aqueous media was studied by cyclic voltammetry (CV) and square-wave voltammetry (SWV) at a glassy-carbon electrode. The electrochemical behaviour of CTL involves two electrons and two protons in the irreversible and diffusion controlled oxidation of the tertiary amine group. The maximum analytical signal was obtained in a phosphate buffer (pH ¼ 8.2). For analytical purposes, an SWV method and a flow-injection analysis (FIA) system with amperometric detection were developed. The optimised SWV method showed a linear range between 1.10 10 5–1.20 10 4 molL 1, with a limit of detection (LOD) of 9.5 10 6 molL 1. Using the FIA method, a linear range between 2.00 10 6–9.00 10 5 molL 1 and an LODof 1.9 10 6 molL 1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products.

Electrochemical oxidation of propanil and related N-substituted amides

The electrochemical behaviour of propanil and related N-substituted amides (acetanilide and N,N-diphenylacetamide) was studied by cyclic and square wave voltammetry using a glassy carbon electrode. Propanil has been found to have chemical stability under the established analytical conditions and showed an oxidation peak at +1.27V versus Ag/AgCl at pH 7.5. N,N-diphenylacetamide has a higher oxidation potential than the other compounds of +1.49V versus Ag/AgCl. Acetanilide oxidation occurred at a potential similar to that of propanil, +1.24V versus Ag/AgCl. These results are in agreement with the substitution pattern of the nitrogen atom of the amide. A degradation product of propanil, 3,4-dichloroaniline (DCA), was also studied, and showed an oxidation peak at +0.66V versus Ag/AgCl. A simple and specific quantitative electroanalytical method is described for the analysis of propanil in commercial products that contain propanil as the active ingredient, used in the treatment of rice crops in Portugal.

Eficiência de antioxidantes em biodiesel

Mestrado em Engenharia Química.Ramo optimização energética na indústria química

Remediação de solos contaminados com produtos farmacêuticos – oxidação / redução química

Actualmente, a poluição do ar, água e solo são problemáticas nas quais se têm centrado diversos estudos. Reduzir ou eliminar a concentração dos diversos poluentes presentes nestes meios é uma meta que se pretende atingir. Neste âmbito, têm sido desenvolvidos diversos estudos e trabalhos, utilizando diversas tecnologias, como químicas e biológicas, de forma a conseguir-se atingir este fim. Esta tese teve como principal objectivo estudar a remediação de solos contaminados com produtos farmacêuticos recorrendo à oxidação/redução química. Assim, começou por se estudar a remediação de água contaminada com ibuprofeno, uma vez, que a matriz líquida é mais fácil de estudar que o solo. Neste âmbito escolheram-se os seguintes reagentes para estudar a descontaminação da água: permanganato de potássio, reagente de Fenton e nanopartículas de ferro zero valente. Analisando os resultados obtidos nestas análises, verificou-se que o permanganato de potássio não foi capaz de reduzir a concentração de ibuprofeno presente na água. No entanto, o reagente de Fenton e as nanopartículas produzidas a partir do extracto da casca de castanha e do chá conseguirem reagir com o ibuprofeno, apresentando taxas de degradação de 90 % e 77 %, respectivamente, nas melhores condições experimentadas. Com os resultados obtidos, passou-se a analisar solos contaminados com o ibuprofeno, utilizando o reagente de Fenton e as nanopartículas produzidas a partir de um extracto de chá. Verificou-se que estes reagentes conseguiram reduzir a concentração de ibuprofeno presente no solo (areia) para valores residuais, obtendo-se taxas de degradação acima de 95 % após 5 dias de reacção. Conclui-se que, o objectivo principal desta tese foi cumprido pois foi reduzida, e quase eliminada, a concentração do ibuprofeno presente no solo, recorrendo à oxidação/redução química.

Produção de hidrogénio através da gasificação da biomassa

A procura de uma forma limpa de combustível, aliada à crescente instabilidade de preços dos combustíveis fósseis verificada nos mercados faz com que o hidrogénio se torne num combustível a considerar devido a não resultar qualquer produto poluente da sua queima e de se poder utilizar, por exemplo, desperdícios florestais cujo valor de mercado não está inflacionado por não pertencer à cadeia alimentar humana. Este trabalho tem como objetivo simular o processo de gasificação de biomassa para produção de hidrogénio utilizando um gasificador de leito fluidizado circulante. O oxigénio e vapor de água funcionam como agentes gasificantes. Para o efeito usou-se o simulador de processos químicos ASPEN Plus. A simulação desenvolvida compreende três etapas que ocorrem no interior do gasificador: pirólise, que foi simulada por um bloco RYIELD, combustão de parte dos compostos voláteis, simulada por um bloco RSTOIC e, por fim, as reações de oxidação e gasificação do carbonizado “char”, simuladas por um bloco RPLUG. Os valores de rendimento dos compostos após a pirólise, obtidos por uma correlação proposta por Gomez-Barea, et al. (2010), foram os seguintes: 20,33% “char”, 22,59% alcatrão, 36,90% monóxido de carbono, 16,05%m/m dióxido de carbono, 3,33% metano e 0,79% hidrogénio (% em massa). Como não foi possível encontrar valores da variação da composição do gás à saída do gasificador com a variação da temperatura, para o caso de vapor de água e oxigénio, optou-se por utilizar apenas vapor na simulação de forma a comparar os seus valores com os da literatura. Às temperaturas de 700, 770 e 820ºC, para um “steam-to-biomass ratio”, (SBR) igual a 0,5, os valores da percentagem molar de monóxido de carbono foram, respetivamente, 56,60%, 55,84% e 53,85%, os valores de hidrogénio foram, respetivamente, 17,83%, 18,25% e 19,31%, os valores de dióxido de carbono foram, respetivamente, 16,40%, 16,85% e 17,93% e os valores de metano foram, respetivamente, 9,00%, 8,95% e 8,83%. Os valores da composição à saída do gasificador, à temperatura de 820ºC, para um SBR de 0,5 foram: 53,85% de monóxido de carbono, 19,31% de hidrogénio, 17,93% de dióxido de carbono e 8,83% de metano (% em moles). Para um SBR de 0,7 a composição à saída foi de 54,45% de monóxido de carbono, 19,01% de hidrogénio, 17,59% de dióxido de carbono e 8,87% de metano. Por fim, quando SBR foi igual a 1 a composição do gás à saída foi de 55,08% de monóxido de carbono, 18,69% de hidrogénio, 17,24% de dióxido de carbono e 8,90% de metano. Os valores da composição obtidos através da simulação, para uma mistura de ar e vapor de água, ER igual a 0,26 e SBR igual a 1, foram: 34,00% de monóxido de carbono, 14,65% de hidrogénio, 45,81% de dióxido de carbono e 5,41% de metano. A simulação permitiu-nos ainda dimensionar o gasificador e determinar alguns parâmetros hidrodinâmicos do gasificador, considerando que a reação “water-gas shift” era a limitante, e que se pretendia obter uma conversão de 95%. A velocidade de operação do gasificador foi de 4,7m/s e a sua altura igual a 0,73m, para um diâmetro de 0,20m.

New insights into the oxidation pathways of apomorphine

A detailed study of the oxidative behaviour of apomorphine in aqueous media is reported. Resorting to the synthesis of apomorphine derivatives it was possible to identify all the anodic oxidation peaks of apomorphine, which are related to the oxidation of the catechol and tertiary amine groups. These findings were revealed to be important since they could lead to a better understanding of the biological interactions of apomorphine and gain insight into its metabolic pathways. During the voltammetric studies, it was also found that apomorphine forms a complex with borate through the catechol group leading to an increase of its oxidation potential. This property could be very useful with regard to the stabilization of apomorphine solutions since it could drastically reduce its autoxidation.

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.

Voltammetric oxidation of drugs of abuse I. Morphine and metabolites

A detailed study of the electrochemical oxidative behavior of morphine in aqueous solution is reported. Through the synthesis of several metabolites and derivatives, pseudomorphine, morphine N-oxide, normorphine, dihydromorphine and 2-(N,N-dimethylaminomethyl)morphine, and their voltammetric study it was possible to identify the oxidation peaks for morphine. The anodic waves are related with the oxidation of phenolic and tertiary amine groups. It is also possible to verify that a poorly defined peak observable during morphine oxidation is not a consequence of further oxidation of pseudomorphine but due to formation of a dimer during phenolic group oxidation. The results obtained and especially those regarding the formation of a new polymer based on a C O coupling could be useful for clarifying the discoloration phenomenon occurring during storage of morphine solutions as well as leading to a better understanding of its oxidative metabolic pathways.

Voltammetric oxidation of drugs of abuse II. Codeine and metabolites

The oxidation of codeine on glassy carbon electrodes has been studied in detail using differential pulse voltammetry. The results obtained using a glassy carbon electrode clearly show a much more complex oxidation mechanism than that previously reported when platinum and gold electrodes were used. To clarify the codeine oxidative profile, several metabolites and analogues of this alkaloid, codeine N-oxide, norcodeine, dihydrocodeine, acetylcodeine and 6- chlorodesoxycodeine, were synthesized and studied. It was deduced that the anodic waves observed in codeine oxidation are related to the presence of methoxy, hydroxy and tertiary amine groups. Due to the similarity of potentials at which these oxidative processes take place, at some pHs an overlap of peaks occurs and only one anodic wave is observed.

Voltammetric oxidation of drugs of abuse III. Heroin and metabolites

The oxidative behavior of heroin in aqueous solution is reported. In order to identify its oxidation peaks, several metabolites, 6-monoacetylmorphine, 3-monoacetylmorphine and norheroin, were synthesized and their electrochemical behavior studied using differential pulse voltammetry. The anodic waves observed for heroin correspond to the oxidation of the tertiary amine group and its follow-up product (secondary amine), and to the oxidation of the phenolic group obtained from hydrolysis, at alkaline pHs, of the 3-acetyl group. The results enabled a new oxidative mechanism for heroin to be proposed in which a secondary amine, norheroin, and an aldehyde are obtained. The voltammetric behavior of 6-monoacetylmorphine and morphine was found to be similar demonstrating that the presence of an acetyl substituent on the 6-hydroxy group does not have a relevant influence on the peak potential of the wave resulting from oxidation of the 3-phenolic group.

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%.

Determination of methiocarb and Its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction

The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LCPAD). Calibration curves were linear in the range of 0.5−10 mg L−1 for all compounds studied. The average recoveries, measured at 0.1 mg kg−1 wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

Electrochemical and spectroscopic studies of the oxidation mechanism of the herbicide propanil

Electrochemical oxidation of propanil in deuterated solutions was studied by cyclic, differential pulse, and square wave voltammetry using a glassy carbon microelectrode. The oxidation of propanil in deuterated acid solutions occurs at the nitrogen atom of the amide at a potential of +1.15 V vs Ag/ AgCl. It was also found that, under the experimental conditions used, protonation at the oxygen atom of propanil occurs, leading to the appearance of another species in solution which oxidizes at +0.60 V. The anodic peak found at +0.79 V vs Ag/AgCl in deuterated basic solutions is related to the presence of an anionic species in which a negative charge is on the nitrogen atom. The electrochemical data were confirmed by the identification of all the species formed in acidic and basic deuterated solutions by means of NMR spectroscopy. The results are supported by electrochemical and spectroscopic studies of acetanilide in deuterated solutions.

Electrochemical oxidation of tamoxifen revisited

Tamoxifen is a selective estrogen receptor modulator that is used as an adjuvant and/or chemotherapeutic agent for the treatment of all stages of hormone-dependent breast cancer. Currently there is a deep interest in the study of tamoxifen biotransformation and identification of metabolites since they can significantly contribute to the overall pharmacological or adverse effects of the drug. Accordingly, the study of the electrochemical behavior of tamoxifen in aqueous solution is reported. To clarify the occurring oxidative process and to assess the influence of the functional groups on the oxidation mechanism, the voltammetric assessment was extended to the study of tamoxifen’s analogues (E)-tamoxifen and dihydrotamoxifen, and to its main phase I oxidative metabolite, N-desmethyl tamoxifen. The data found shows that the oxidative processes occurring in tamoxifen are essentially related with the two chemical moieties present in the molecule: the substituted aromatic nucleus and the tertiary amine group. Moreover, the results obtained suggest that the ethylenic linkage is not critical for tamoxifen’s oxidation although it could play an important role in the course of the oxidation process. These results could contribute to highlight some remaining questions regarding tamoxifen’s metabolic behavior and to the development of new analytical strategies, based on electrochemical approaches.