Pharmaceutical drugs as emerging pollutants in aqueous media of Northeast Portugal

Emerging pollutants are potentially toxic substances that although found in very small concentrations can produce hazard effects to the environment. Due to their very small concentrations they are not yet included in the water quality monitoring programs neither in national or international environmental control regulations. Pharmaceutical and Personal Care Products (PPCPs) represent an important group of emerging pollutants owing to increased worldwide consumption and to their inherent capacity to induce physiological harmful effects in very low doses, which raises several concerns related with the potential adverse effects on humans, animals and environmental systems. In this work, it will be presented the development and validation of a complete experimental methodology proposed for the monitoring of pharmaceutical drugs. The method is based on solid phase extraction (SPE) followed by analysis with high performance liquid chromatography with a diode array detector (HPLC-DAD). Experimental results obtained with two different columns will be presented. An analytical Nucleosil 100-5 C18 column, 150 mm x 4.6 mm, obtained from Macherey-Nagel for compounds with lower pKa values and a SiliaChrom XT C18 column, 4.6 mm x 250 mm, obtained from SiliCycle for compounds with higher pKa values. The method is validated by the analysis of real aqueous matrices samples obtained from different water media sources, such as, swimming pools, rivers and wastewater treatment plants. To extend the scope of the analytical method and thus obtain a broader study, several drugs were selected, belonging to five different pharmacological classes: non-steroidal anti-inflammatory (ibuprofen, acetylsalicylic acid, ketoprofen, naproxen and diclofenac), analgesic (paracetamol), antibiotic (sulfamethoxazole), an anticonvulsant (carbamazepine) and a central nervous system stimulator (caffeine). These compounds were selected due to their high level of use and medical prescription and, consequently, leading to a high probability of environmental contamination.info:eu-repo/semantics/publishedVersio

Optimization and kinetic study of esterification reaction of oleic acid using [HMIM]HSO4 as catalyst

Biodiesel Biodiesel is an alternative fuel to petrodiesel. It can be produced from a wide range of raw materials such as vegetable oils and animal fats. Yet, the use of sources that do not compete with the food market, such as waste cooking oils - which usually feature high levels of free fatty acids (FFA’s), can lead to problems in the process of biodiesel production through alkaline transesterification. Therefore, new methodologies to successfully apply acidic oils need to be developed.info:eu-repo/semantics/publishedVersio

Study of Biodiesel Production through Esterification Catalysed by Imidazolium-based Ionic Liquids

Biodiesel is an alternative diesel fuel which is industrially produced from vegetable oils and animal fats, by transesterification reactions. Thus, currently most commercial biodiesel is produced from oils, using alkaline catalysts. On the other hand, conventional mineral acid catalysts like sulfuric acid, are commonly used for catalyzing esterification reactions of fatty acids which also produce biodiesel. However, Ionic Liquids (ILs) offer an alternative solution to classical homogeneous catalysts, because it can be recycled and reused in subsequent runs after recovery steps. An IL is a molten salt consisting of a cation and an anion, with low melting temperature. In this study, a Brønsted acidic IL, 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]) was used as a catalyst in the esterification of oleic acid with methanol into biodiesel. The effect of different operation parameters such as oleic acid to methanol molar ratio, amount of catalyst, reaction temperature, and reaction time were tested. The optimal conditions for esterification of oleic acid were experimentally determined at 1/10 for oleic acid/methanol molar ratio, 2.5 %wt for the amount of catalyst, a reaction time of 4 h and reaction temperature of 90oC. The Fatty Acid Methyl Esters (FAMEs) content was analyzed using Gas Chromatography.info:eu-repo/semantics/publishedVersio

Development of sulfur based polymers for rechargeable lithium batteries

Lithium-ion (Li-ion) batteries are in the front edge of recent achievements concerning energy storage. However, Li-ion devices are reaching their maximum regarding energy density storage which restricts their appiicatíon in systems with large power needs, such as electric vehicles. Driven by this shortcoming, in the last few years, Lithium-Sulfur (Li-S) batteries are being considered as an alternative for the exploitatíon of energy storage and conversion systems with improved performance. Indeed, to the S cathodes is associated a theoretical specifíc capacity of 1672 mA h g-1 and a specifíc energy of 2600 W h kg-\ which are several times higher than the correspondent to other possible systems. The relative low atomic weight of S in comparison with other elements (e.g. cobalt) and the multí-electron transfer reactíons in the pair Li/S are at the source ofthis superior theoretícal performance of Li-S batteries.Este trabalho foi financiado por: projeto POCI-01-0145-FEDER-006984 - Laboratório Associado LSRE-LCM - financiado pelo Fundo Europeu de Desenvolvimento Regional (FEDER), através do COMPETE2020 – Programa Operacional Competitividade e Internacionalização (POCI)info:eu-repo/semantics/publishedVersio

Biodiesel production through esterification using ionic liquids as catalysts

There is a growing interest in the development of alternative technologies to the oil economy, based on renewable energy sources. Biodiesel is an alternative fuel that can be produced from a wide range of raw materials such as vegetable oils and animal fats. Yet, the use of sources that do not compete with the food market, such as waste cooking oils - which usually feature high levels of free fatty acids (FFA’s) -, can lead to problems in the process of biodiesel production through alkaline transesterification. Ionic liquids (ILs) could be employed in the biodiesel production to partially overcome these problems; since they are able to catalyze the esterification reaction of FFA’s to biodiesel (FAMEs) as well as the transesterification reaction of triglycerides. Ionic liquids are also viable due to the fact that they can be easily recovered and recycled, decreasing their cost. Experimental results concerning the recyclability of the ionic liquid 1-butyl-3-methylimidazolium hydrogen sulfate [BMIM][HSO4] and its influence on the conversion of organic acids to biodiesel and the content of FAMEs will be presentedinfo:eu-repo/semantics/publishedVersio

Produção de biodiesel através de esterificação catalisada por líquidos iónicos

A contribuição dos combustíveis fósseis para o aumento da poluição ambiental, nomeadamente no que diz respeito à emissão de gases com efeito de estufa, o constante aumento dos preços do petróleo e a limitação das reservas destes combustíveis, têm incentivado a investigação de fontes alternativas de energia. No setor dos transportes, os biocombustíveis são uma das respostas ao problema energético e ambiental. O biodiesel, constituído por uma mistura de ésteres metílicos de ácidos gordos (FAME), é utilizado como substituto do diesel convencional, constituindo uma forma de independência para os países que não possuem reservas de petróleo, podendo ser produzido a partir de matérias-primas variadas, como óleos vegetais, gorduras animais, óleos alimentares usados e algas. Neste trabalho estuda-se a utilização de novos catalisadores, nomeadamente os Líquidos Iónicos (LI), como alternativa aos catalisadores tradicionais no processo de esterificação de ácidos gordos livres. A influência da utilização dos LI no processo de esterificação é estudada através da monitorização das propriedades do biodiesel produzido, pela determinação do índice de acidez por titulação ácido-base, e do teor de FAME através de cromatografia gasosa (GC-FID). Apresentam-se resultados experimentais obtidos com Metanossulfonato de 1-butil-3-metilimidazólio ([BMIM][CH3SO3]) e Cloreto de 1-butil-3-metilimidazólio ([BMIM][Cl]), modificados por incorporação de cloreto férrico, e utilizando diferentes proporções ácido oleico(AO)/metanol(M), 1/5, 1/10 e 1/15. Para ambos os LI estudados, verifica-se um aumento do rendimento da reação com o aumento da razão AO/M. Os valores dos rendimentos obtidos, variam entre 86.6% e 94.4% para o [BMIM][Cl] e entre 87.2% e 98.8% para o [BMIM][CH3SO3].info:eu-repo/semantics/publishedVersio

Biodiesel production through esterification using ionic liquids as catalysts

There is a growing interest in the development of alternative technologies to the oil economy, based on renewable energy sources. A possible solution is a biofuel usable in compression-ignition engines, produced from biomass rich in fats and oils. Biodiesel is an alternative fuel that can be produced from a wide range of raw materials such as vegetable oils and animal fats. Yet, the use of sources that do not compete with the food market, like waste cooking oils - which usually feature high levels of free fatty acids (FFA’s) -, can lead to problems in the process of biodiesel production through alkaline transesterification. Ionic liquids (ILs) could be employed in the biodiesel production to partially overcome these problems; since they are able to catalyze the esterification reaction of FFA’s to biodiesel. In this work, experimental results will be presented concerning the study of the influence of ILs in the catalysis of esterification reactions of organic acids to the corresponding methyl esters. Different imidazolium-based ILs were tested for biodiesel production through an esterification reaction of oleic acid, using a previously optimized reaction methodology [1]: 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]), 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium methyl sulfate, 1-metylimidazolium hydrogen sulfate ([HMIM][HSO4]) and tributylmethylammonium methylsulfate. The experimental values obtained for the conversion of the oleic acid through an esterification reaction showed that the ionic liquid ([BMIM][HSO4]) would be one of the most promising catalysts. The recovery of the selected [BMIM][HSO4] ionic liquid was studied for different catalyst loading: 10, 15 and 20 wt% - relative to the mass of oleic acid. The reaction yield was determined by acidity using a titrimetric method (EN 14104). The composition characterization of the biodiesel samples (identification of fatty acid methyl esters) was evaluated by gas chromatography with FID detector (EN 14103). The obtained results confirm that it is possible to reuse [BMIM][HSO4] ionic liquid in successive reactions without great loss of yield and, thereafter, to significantly reduce the costs associated with the use of ILs as catalysts. Moreover, the esterification reaction with the [HMIM][HSO4] IL was also studied and further comparison of the methyl esters content obtained with each catalyst will be possible.info:eu-repo/semantics/publishedVersio

Monitoring of emerging micropollutants in hydric media in Bragança district

Emerging Micropollutants are a subclass of Pollutants and they can be classified as Persistent Organic Pollutants, Endocrine Disrupting Compounds and Pharmaceuticals and Personal Care Products (PPCP´s). These compounds may cause undesired effects to health or to the environment when used in high quantities or wrong ways. Generally, a pharmaceutical drug is prescribed to cause the desired therapeutic effect. However after their use, even at low concentrations they can retain their physicochemical properties [1]. Because of these effects, among others, PPCP’s are substances excreted in relevant quantities by the human body and are not effectively removed from water in sewage treatment plants [2].info:eu-repo/semantics/publishedVersio

Extraction and quantification of pharmaceutical drugs in aqueous matrices

The increasing production and use of chemical compounds, coupled with inefficient sewage treatment systems, results in an inadequate release of all types of pollutants into the environment. Emerging pollutants are potentially toxic substances normally found in very small concentrations but that can produce harmful effects on the environment. These compounds are not yet included in water quality monitoring programs nor in environmental control legislation standards. Pharmaceutical and Personal Care Products (PPCPs) are an important group of emerging pollutants due to their continuing increase in world consumption and their inherent capacity to induce physiological effects at very low doses, raising concerns about potential adverse effects in humans, animals and environmental systems.info:eu-repo/semantics/publishedVersio

Production and characterization of biodiesel obtained by transesterification catalyzed by the ionic liquid Choline Hydroxide

UNIFACSBiodiesel is a mixture of alkyl esters derived from vegetable oils or animal fat, formed by triglycerides that can be converted into biofuels by different forms, being transesterification the most common used method. In the transesterification process, the most used alcohol is methanol and the byproduct of this reaction is glycerol.info:eu-repo/semantics/publishedVersio