Desenvolvimento de métodos electroquímicos de quantificação de fármacos em amostras de água contaminadas

Este trabalho teve como objectivo, o desenvolvimento de um método electroquímico, para quantificação do fármaco carbamazepina (CBZ) em águas contaminadas. Neste trabalho foram utilizados quatro métodos voltamétricos: a voltametria cíclica, a voltametria de varrimento linear, a voltametria de onda quadrada e a voltametria de impulso diferencial. Os eléctrodos de trabalho utilizados foram, o eléctrodo de mercúrio de gota suspensa, o eléctrodo de carbono vítreo clássico e um eléctrodo de carbono vítreo modificado com um filme de nanotubos de carbono de paredes múltiplas (MWCNTs). O eléctrodo de mercúrio de gota suspensa permitiu o estudo da redução da CBZ numa região de potencial mais catódico, e os eléctrodos de carbono vítreo, com e sem modificação, permitiram o estudo da oxidação da CBZ numa região de potencial mais anódico. Nas condições experimentais estudadas, o eléctrodo de mercúrio de gota suspensa revelou ser um sensor voltamétrico pouco eficaz na determinação quantitativa da carbamazepina, em amostras com uma matriz complexa. Entre os eléctrodos de carbono vítreo, o eléctrodo de carbono vítreo modificado com os MWCNTs revelou ser o sensor voltamétrico mais eficaz e sensível, na detecção e determinação da carbamazepina. Modificado com um filme de nanotubos de carbono de paredes múltiplas, que previamente foram dispersos em dihexadecilhidrogenofosfato (DHP) e água, este novo eléctrodo permitiu obter uma resposta electroquímica da CBZ, consideravelmente superior ao eléctrodo não modificado. Utilizando a voltametria de varrimento linear e as condições experimentais consideradas óptimas, o eléctrodo nanoestruturado permitiu obter uma relação linear entre o sinal medido e a concentração da CBZ no intervalo 0.13- 1.60 M (30.7- 378 g -1), com os limites de detecção e quantificação mais baixos, até à data reportados com métodos electroquímicos (0.04 e 0.14M, respectivamente). O eléctrodo modificado foi aplicado na quantificação da CBZ, em formulações farmacêuticas, em águas naturais tratadas e em amostras de águas residuais, ambas dopadas, obtendo-se taxas de recuperação consideravelmente elevadas (100.6%, 98.0%,95.8%, respectivamente). Os resultados obtidos, na análise da CBZ em amostras ambientais, com o eléctrodo modificado, foram comparados com resultados obtidos por HPLC-UV e LC­ ESI-MS/MS, validando o método electroquímico desenvolvido neste trabalho. ABSTRACT: The aim of this work was to develop a new electrochemical method for the quantification of carbamazepine (CBZ) in contaminated waters. ln this study, four voltammetric methods were used: cyclic voltammetry, linear sweep voltammetry, square wave voltammetry and differential pulse voltammetry. the working electrodes used were the hanging mercury drop electrode (HMDE), the classical glassy carbon electrode (GCE), and a glassy carbon electrode modified with a film of multi-walled carbon nanotubes (MWCNls). Using HMDE, the reduction of CBZ was studied in the cathodic potential region. the CGE sensors, with or without modification, allowed the study of CBZ oxidation in the anodic potential region. ln the tested conditions, the results obtained for the quantification of CBZ using the HMDE sensor were not very satisfactory, especially when more complex samples were analysed. When the MWCNls-dihexadecyl hydrogen phosphate (DHP) film­ coated GCE was used for the voltammetric determination of CBZ, the results obtained showed that this modified electrode exhibits excellent enhancement effects on the electrochemical oxidation of CBZ. the oxidation peak current of CBZ at this film­ modified electrode increased significantly, when compared with that at a bare glassy carbon electrode. The enhanced electrooxidation and voltammetry of CBZ at the surface of MWCNTs-DHP film coated GCE in phosphate buffer solution (pH 6.71) was attributed to the unique properties of MWCNTs such as large specific surface area and strong adsorptive properties providing more reaction sites. The proposed method was applied to the quantification of CBZ in pharmaceutical formulations, drinking water and wastewater samples with good recoveries and low limits of detection and quantification (0.04 and 0.14 M, respectively), and was positively compared with chromatographic techniques usually used in the quantification of pharmaceutical compounds in environmental samples. HPLC-UV and LC-ESI-MS/MS were also used in the quantification of CBZ in pharmaceutical formulations and wastewater samples to prove the importance and accuracy of his voltammetric method.

ABSTINENCE AND ALCOHOL CONSUMPTION AMONG STUDENTS: THE INFLUENCE OF PERSONAL, FAMILY AND SOCIO-CULTURAL SPHERES

Introduction: Among young people, regular or alcohol abuse seems to ally with individual factors, which congregate to other generators behaviors health risk, in social environment, including family and school. The consumption of alcoholic beverages in the younger age groups, according to the World Development Report goes beyond 60%. In the Portuguese case, the Alentejo is the region that recorded higher consumption among schoolchildren. Objectives: This study aims to know the personal inluences of family, of belonging to the group and the school environment, on the withdrawal and consumption habits among young people. Methods: A qualitative nature of research, using comprehensive semi-structured interviews. The study was developed in a school district of Evora, Portugal. The sample consists of ten students from the 8th school grade, ive non-consumers-ive consumers aged between 13 and 15 years old. Results: The trial takes place between 12 and 14 years old as a result of curiosity, explicit or tacit motivation, “give style”, the environment, entertainment and observing behavior. Among the effects of intake indicated as motivators consumption highlight the joy of reaching states and willingness. Family members tend to encourage moderate drinking on festive occasions. family models exaggerated consumption repudiate ingestion. The elements of the group of belonging tend to motivate explicitly, the intake among consumers students. The school promotes initiatives on the theme, punctually. Conclusions: The consumption of alcohol among young people suffer the personal, family and belonging group inluences. The initiatives in school tend to have no effect.

Oral food perception and polyphenol-rich foods acceptance - the importance of knowing individuals saliva characteristics for promoting consumption

Polyphenols are widely present in fruits, vegetables, cereals and beverages. Their study gained scientific interest because of their beneficial effects on health. Although there is currently no official dietary recommendation for polyphenol intake, health professionals recommend the consumption of 5-8 daily portions of fruits and vegetables. This is not always achieved and, despite possible causes associated to practical schedule difficulties, the aversive bitter and astringent sensations associated to polyphenols may also lead to avoidance. As such, a better understanding on mechanisms responsible for differences among people, in polyphenol oral perception, is needed for promoting healthier choices. Saliva has been linked to polyphenol consumption. We have previously observed, in animal models, changes in salivary proteome induced by tannin-enriched diets. Moreover, differences in astringency perception were attributed to differences in salivary protein composition. In a recent experiment, we observed differences among individuals with dissimilar tannic-acid perception: people with high sensitivity for the oral sensations elicited by tannins have higher amounts of salivary cystatins and lower capacity to maintain their levels after tannic-acid ingestion. Additionally, and similarly to previous studies, salivary amylase was observed to be involved in tannin perception. In this presentation, oral cavity characteristics influencing the perception of polyphenol-containing foods will be discussed.