New oxomolybdenum(VI) hybrid materials

In this thesis, 2,2’-bipyridine (bipy), di-tert-butyl-2,2’-bipyridine (di-t-Bubipy), 2,2’-bipyridine-5,5’-dicarboxylic acid (H2bpdc), 2-[3(5)-pyrazolyl]pyridine (pzpy) and 2-(1-pentyl-3-pyrazolyl)pyridine (pent-pp) ligands were used as the N,N-chelate ligands in the formation of discrete [MoO2Cl2L]-type complexes. These complexes were employed as precursors for the preparation in aqueous media of oxomolybdenum(VI) products with a wide range of structural diversity. Three distinct heating methods were studied: hydrothermal, reflux or microwave-assisted synthesis. An alternative reaction with the inorganic molybdenum(VI) trioxide (MoO3) and the ligands di-t-Bu-bipy, H2bpdc and pzpy was also investigated under hydrothermal conditions. The distinct nature of the N,N-chelate ligands and/or the heating method employed promoted the isolation of a series of new oxomolybdenum(VI) hybrid materials that clearly reflected the strong structure-directing influence of these ligands. Thus, this thesis describes the synthesis and characterization of the discrete mononuclear [MoO2Cl2(pent-pp)], the dinuclear [Mo2O6(di-t-Bu-bipy)2] and the octanuclear [Mo8O22(OH)4(di-t-Bu-bipy)4] complexes as well as the highly unique polymeric materials {[MoO3(bipy)][MoO3(H2O)]}n, (DMA)[MoO3(Hbpdc)]·nH2O, [Mo3O9(pzpy)]n and [Mo2O6(pent-pp)]n (fine structural details of compound [Mo2O6(pent-pp)]n are presently unknown; however, characterization data strongly pointed toward a polymeric oxide hybrid compound). The catalytic behaviour of the discrete complexes and the polymeric compounds was tested in olefin epoxidation reactions. Compounds [Mo3O9(pzpy)]n and [Mo2O6(pent-pp)]n acted as sources of soluble active species that where identified as the oxodiperoxido complexes [MoO(O2)2(pzpy)] and [MoO(O2)2(pent-pp)], respectively. The majority of the compounds here presented were fully characterized by using solid-state techniques, namely elemental analyses, thermogravimetry, FT-IR, solid-state NMR, electron microscopy and powder X-ray diffraction (both from laboratory and/or synchrotron sources).

Receptores de aniões baseados em azacalix[4]arenos e isoftalamidas

Nesta tese, desenvolvida no âmbito do Programa Doutoral em Química da Universidade de Aveiro, foram desenvolvidos novos receptores sintéticos construídos a partir da plataforma macrocíclica tetraazacalix[2]areno[2]triazina ou do fragmento de isoftalamida. Ambas as unidades estruturais foram decora-das com grupos de reconhecimento molecular baseados em grupos amida e/ou ureia com o objectivo de actuarem como receptores selectivos de aniões com importância biológica ou farmacológica, incluindo acetato, oxalato, malo-nato, succinato, glutarato, diglicolato, L- e D-NHBoc-alanina, (S)- e (R)-fenilpro-panoato, (S,S)- e (R,R)-tartarato, fumarato, maleato, Cl-, HCO3-, H2PO4-, HSO4- e SO42-. No Capítulo 1 é efectuada uma revisão bibliográfica dos desenvolvimentos recentes na síntese, caracterização estrutural e aplicações de receptores fun-cionais relacionados com os desenvolvidos no âmbito desta tese, com especial incidência para aqueles que foram estudados como receptores de aniões. Neste domínio, enquanto que receptores derivados da isoftalamida têm sido bastante estudados ao longo das últimas décadas, o desenvolvimento de receptores de aniões inspirados em heteracalix[2]areno[2]triazinas ainda se encontra a dar os primeiros passos. No Capítulo 2 é apresentada a síntese de quatro novos macrociclos derivados de tetraazacalix[2]areno[2]triazina incorporando um ou dois braços de L-alanina (A1, A2) ou de L-leucina (L1, L2) nos anéis benzénicos, e derivados com grupos amida como unidades de reconhecimento. Adicionalmente, são também apresentados dois novos azacalix[2]areno[2]triazinas contendo um (U1) ou dois (U2) braços com grupos ureia substituídos com um grupo (S)-metilbenzílico. Foram ainda preparados os macrociclos A2Me4 e U2Me4 por metilação dos átomos de azoto em ponte de A2 e U2, os quais foram posterior-mente utilizados em estudos de associação. Os compostos sintetizados foram caracterizados através de técnicas espectroscópicas, complementadas por difracção de raios X de cristal único no caso de U2Me4. O Capítulo 3 contempla os estudos de reconhecimento molecular entre os macrociclos A2Me4 e U2Me4 e os aniões derivados de ácidos mono- e dicarbo-xílicos alifáticos, ácidos carboxílicos isoméricos (enantiómeros e isómeros geométricos), aminoácidos e polioxaniões acima referidos, excepto HCO3-. Os estudos de associação foram realizados através de técnicas de titulação por RMN 1H com determinação das respectivas constantes de afinidade. Todas as associações estudadas apresentaram uma estequiometria receptor-substrato 1:1 com excepção das associações formadas entre A2Me4 e U2Me4 com H2PO4- (1:2). Os complexos A2Me4∙SO42- e U2Me4∙(H2PO4-)2 são os mais estáveis com constantes de associação de 7,4 × 104 M-1 e superior a 105 M-2, respectivamente. O reconhecimento dos dicarboxilatos ocorreu através dos dois braços do macrociclo, com os aniões com grupos carboxilato separados por cadeias alifáticas mais compridas (glutarato e diglicolato) apresentando um melhor ajuste aos braços de A2Me4 e U2Me4. Não foi observado reconheci-mento enantiosselectivo de aniões. Em contraste, as constantes de afinidade para as associações com os aniões dos isómeros cis (maleato) e trans (fumarato) do ácido but-2-enodióico, de 89 e 4920 M-1 para A2Me4 e 481 e 4007 M-1 para U2Me4, respectivamente, sugerem selectividade de ambos os receptores para o fumarato. No Capítulo 4 é descrita a síntese de nove receptores acíclicos incorporando a unidade de isoftalamida (Iso-1 a Iso-9) e braços laterais com grupos de reconhecimento de aniões. Enquanto que o receptor Iso-1 possui como unida-des de reconhecimento apenas grupos amida, os receptores Iso-2, Iso-3, Iso-5, Iso-6, Iso-7 e Iso-9 possuem grupos amida e ureia, e os derivados Iso-4 e Iso-8 grupos amida e sulfonilureia. Em cada um destes compostos, os grupos de reconhecimento estão separados por uma cadeia etilénica cuja flexibilidade confere um melhor ajuste com os aniões. Os derivados de isoftalamida preparados foram caracterizados através de técnicas espectroscópicas. No Capítulo 5 são apresentados os estudos de associação realizados por técnicas de titulação por RMN 1H entre Iso-1, Iso-2, Iso-4, Iso-6 e Iso-8 com os aniões H2PO4-, HCO3-, Cl- e oxalato. Os receptores Iso-1, Iso-2 e Iso-6 apresentaram maior afinidade para o dianião, com valores de Kass de 6100, 7800 e 9800 M-1 respectivamente, e menor para Cl- (17 < Kass < 19 M-1). Foram sempre formadas associações mais estáveis com H2PO4- (294 < Kass < 427 M-1) comparativamente a HCO3-, sendo que a associação mais forte com este últi-mo foi determinada com Iso-2 (Kass = 95 M-1). As moléculas de Iso-4 e Iso-8 sofreram desprotonação dos grupos sulfonilureia na presença de todos os aniões excepto de Cl-. No Capítulo 6 apresentam-se as conclusões gerais e no Capítulo 7 descrevem-se os procedimentos experimentais e também os dados espectroscópicos dos produtos obtidos.

Estudo dos processos eletroquímicos: eletrooxidação e eletrocoagulação

O tratamento físico-químico de águas residuais, de origem industrial, mais comum é o tratamento baseado na adição de coagulante e floculante a um efluente. No entanto, o tratamento eletroquímico é um tipo de tratamento que tem vindo a ser explorado e estudado com mais ênfase ao longo dos últimos anos. O tratamento eletroquímico é uma tecnologia AOP (Processos de Oxidação Avançada) e divide-se em eletrólise direta (oxidação e redução) e indireta (eletrocoagulação-flotação e eletrooxidação). A eletrocoagulação e eletrooxidação divergem apenas pelo tipo de reações que ocorrem, devido ao material que constitui os elétrodos. São processos complexos com uma multiplicidade de mecanismos que operam sinergicamente para remover poluentes da água. Tendo em conta a sua complexidade e ainda dificuldade de compreensão, existem na literatura diferentes versões acerca de quais os mecanismos chave, assim como diversas configurações geométricas de reatores e elétrodos. Atualmente, este tipo de tratamento tem vindo a evoluir, tornando-se num método economicamente viável para o tratamento de uma grande variedade de águas residuais, nomeadamente, aquelas que possuem compostos recalcitrantes na sua composição. O presente trabalho foi realizado nas instalações da VentilAQUA S.A. e, tendo em conta a sua área de especialidade, o trabalho exposto focou-se no desenvolvimento de soluções técnicas de AOP, nomeadamente na área eletroquímica (eletrocoagulação e eletrooxidação),para estudo dos parâmetros operacionais numa nova configuração geométrica para os elétrodos. Tendo por base os contributos da revisão bibliográfica, o estudo incidiu num reator tubular, com elétrodos de inox dispostos de forma concêntrica, à mesma distância entre si. Com este reator foram executados variados testes, com diferentes efluentes, que permitiram obter resultados operacionais de otimização de funcionamento, tendo em vista a remoção de poluentes. O estudo financeiro associado permitiu concluir que a eletrooxidação é significativamente mais económica que o tratamento físico-químico, nas condições operacionais e para os efluentes tratados. Relativamente ao Acompanhamento e Gestão de ETAR’s (Capítulo 4) foi possível verificar que todos os casos em estudo apresentam uma boa eficiência de remoção de matéria orgânica, permitindo a descarga do seu efluente com uma carga poluente que cumpre com os requisitos legais de descarga em meio hídrico.

Catalytic routes to convert saccharides to furanic aldehydes

The conversion of plant biomass-derived carbohydrates (preferably non-edible) into added-value products is envisaged to be at the core of the future biorefineries. Carbohydrates are the most abundant natural organic polymers on Earth. This work deals with the chemical valorisation of plant biomass, focusing on the acid-catalysed conversion of carbohydrates (mono and polysaccharides) to furanic aldehydes, namely 2-furaldehyde (Fur) and 5-hydroxymethyl-2-furaldehyde (Hmf), which are valuable platform chemicals that have the potential to replace a variety of oil derived chemicals and materials. The investigated reaction systems can be divided into two types depending on the solvent used to dissolve the carbohydrates in the reaction medium: water or ionic liquid-based systems. The reaction temperatures were greater than 150 ºC when the solvent was water, and lower than 150 º C in the cases of the ionic liquid-based catalytic systems. As alternatives to liquid acids (typically used in the industrial production of Fur), solid acid catalysts were investigated in these reaction systems. Aiming at the identification of (soluble and insoluble) reaction products, complementary characterisation techniques were used namely, FT-IR spectroscopy, liquid and solid state NMR spectroscopy, TGA, DSC and GC´GC-ToFMS analyses. Complex mixtures of soluble reaction products were obtained and different types of side reactions may occur. The requirements to be put on the catalysts for these reaction systems partly depend on the type of carbohydrates to be converted and the reaction conditions used. The thermal stability is important due to the fact that formation of humins and catalyst coking phenomena are characteristically inherent to these types of reactions systems leading to the need to regenerate the catalyst which can be effectively accomplished by calcination. Special attention was given to fully inorganic nanoporous solid acids, amorphous or crystalline, and consisting of nano to micro-size particles. The investigated catalysts were silicoaluminophosphates, aluminosilicates and zirconium-tungsten mixed oxides which are versatile catalysts in that their physicochemical properties can be fine-tuned to improve the catalytic performances in the conversion of different substrates (e.g. introduction of mesoporosity and modification of the acid properties). The catalytic systems consisting of aluminosilicates as solid acids and water as solvent seem to be more effective in converting pentoses and related polysaccharides into Fur, than hexoses and related polysaccharides into Hmf. The investigated solid acids exhibited fairly good hydrothermal stabilities. On the other hand, ionic liquid-based catalytic systems can allow reaching simultaneously high Fur and Hmf yields, particularly when Hmf is obtained from D-fructose and related polysaccharides; however, catalyst deactivation occurs and the catalytic reactions take place in homogeneous phase. As pointed out in a review of the state of the art on this topic, the development of truly heterogeneous ionic liquid-based catalytic systems for producing Fur and Hmf in high yields remains a challenge.

Characterization of water-soluble organic matter from urban aerosols

Water-soluble organic matter (WSOM) from atmospheric particles comprises a complex array of molecular structures that play an important role on the physic-chemical properties of atmospheric particles and, therefore, are linked to several global-relevant atmospheric processes which impact the climate and public health. Due to the large variety of sources and formation processes, adequate knowledge on WSOM composition and its effects on the properties of atmospheric aerosol are still limited. Therefore, this thesis aims at providing new insights on the molecular composition of WSOM from fine atmospheric aerosols typical of an urban area (Aveiro, Portugal). In a first step, adsorption phenomena of semivolatile organic compounds on quartz fibre filters employed in the collection of atmospheric aerosols were assessed. Afterwards, atmospheric aerosol samples were collected during fifteen months, on a weekly basis. A mass balance of aerosol samples was performed in order to set the relative contribution of elemental carbon, WSOM and water-insoluble organic matter to the aerosol mass collected at the urban area of Aveiro, with a special focus on the assessment of the influence of different meteorological conditions. In order to assess the chemical complexity of the WSOM from urban aerosols, their structural characteristics were studied by means of Fourier transform infrared infrared - Attenuated Total Reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning 13C nuclear magnetic resonance (CPMAS 13C NMR) spectroscopies, as well as their elemental composition. The structural characterization of aerosol WSOM samples collected in the urban area highlighted a highly complex mixture of functional groups. It was concluded that aliphatic and aromatic structures, hydroxyl groups and carboxyl groups are characteristic to all samples. The semi-quantitative assessment of the CPMAS 13C NMR data showed different distributions of the various functional groups between the aerosol samples collected at different seasons. Moreover, the presence of signals typical of lignin-derived structures in both CPMAS 13C NMR and FTIR-ATR spectra of the WSOM samples from the colder seasons, highlights the major contribution of biomass burning processes in domestic fireplaces, during low temperature conditions, into the bulk chemical properties of WSOM from urban aerosols. A comprehensive two-dimensional liquid chromatography (LC x LC) method, on-line coupled to a diode array, fluorescence, and evaporative light scattering detectors, was employed for resolving the chemical heterogeneity of the aerosol WSOM samples and, simultaneously, to map the hydrophobicity versus the molecular weight distribution of the samples. The LC x LC method employed a mixed-mode hydrophilic interaction column operating under aqueous reversed phase mode in the first dimension, and a size-exclusion column in the second dimension, which was found to be useful for separating the aerosol WSOM samples into various fractions with distinct molecular weight and hydrophobic features. The estimative of the average molecular weight (Mw) distribution of the urban aerosol WSOM samples ranged from 48 to 942 Da and from 45 to 1241 Da in terms of UV absorption and fluorescence detection, respectively. Findings suggest that smaller Mw group fractions seem to be related to a more hydrophobic nature.

Novos materiais com polioxotungstatos substituídos com metais d e f

The present work reports studies on the new compounds obtained by the combination of polyoxoanions derived from the Keggin and Lindquist structures with several cations. The studies were first focused on the monolacunary Keggin polyoxoanions [PW11O39M(H2O)]n- (M = FeIII, MnIII and n = 4; M = CoII and n = 5) and its combination with the organic cation 1-butyl-3-methylimidazolium (Bmim+). The association of Bmim+ cation with the polyoxoanion [PW11O39Fe(H2O)]4- allowed to isolate for the first time both the monomeric and the dimeric [PW11O39Fe)2O]10- anions, with the same cation and using simple bench techniques by pH manipulation. Studies regarding the stability of these inorganic species in solution indicated that both species are present in solution in equilibrium. However, the inability to up until now isolate the dimeric unit through simple bench methods, lead to the hypothesis that the cation had a role to play in the selective precipitation of either the monomer or the dimer. Repetition of the same procedures with the polyoxoanions [SiW11O39Fe(H2O)]5- and [PW11O39M(H2O)]n- (M = FeIII, MnIII and n = 4; M = Co and n = 5), afforded only the corresponding monomeric compounds, (Bmim)5[SiW11O39FeIII(H2O)]· 4H2O (3), (Bmim)5[PW11O39CoII(H2O)]· 0.5 H2O, (4) and (Bmim)5[PW11O39MnIII(H2O)]· 0.5 H2O (5). Moreover, the combination of Bmim+ and the polyoxotungstate [PW11O39Co(H2O)]5- afforded two different crystal structures, depending on the synthetic conditions. Thus, a ratio Bmim+:POM of 5:1 and the presence of K+ cations (due to addition of KOH) led to a formula Na2K(Bmim)2[PW11.2O39Co0.8(H2O)]·7H2O (4a), whilst a ratio Bmim:POM of 7:1 led to the formation of a crystal with the chemical formula Na2(Bmim)8[PW11O39Co(H2O)]2·3H2O (4b). Electrochemical studies were performed with carbon paste electrodes modified with BmimCl to investigate the influence of the Bmim+ cation in the performance of the electrodes. The voltametric measurements obtained from solutions containing the anions [PW11O39]7- and [SiW11O39]8- are presented. Results pointed to an improvement of the acquired voltametric signal with a slight addition of BmimCl (up to 2.5% w/w), specially in the studies regarding pH variation. Additional synthesis were carried out with both the cations Omim+ and THTP+.

Analysis of the organic matter associated to sea salt : definition of potential molecular markers based on the volatile composition and presence of glycosidic derivatives and polysaccharides

Sea salt is a natural product obtained from the evaporation of seawater in saltpans due to the combined effect of wind and sunlight. Nowadays, there is a growing interest for protection and re-valorisation of saltpans intrinsically associated to the quality of sea salt that can be evaluated by its physico-chemical properties. These man-made systems can be located in different geographical areas presenting different environmental surroundings. During the crystallization process, organic compounds coming from these surroundings can be incorporated into sea salt crystals, influencing their final composition. The organic matter associated to sea salt arises from three main sources: algae, surrounding bacterial community, and anthropogenic activity. Based on the hypothesis that sea salt contains associated organic compounds that can be used as markers of the product, including saltpans surrounding environment, the aim of this PhD thesis was to identify these compounds. With this purpose, this work comprised: 1) a deep characterisation of the volatile composition of sea salt by headspace solid phase microextraction combined with comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME/GCGC–ToFMS) methodology, in search of potential sea salt volatile markers; 2) the development of a methodology to isolate the polymeric material potentially present in sea salt, in amounts that allow its characterisation in terms of polysaccharides and protein; and 3) to explore the possible presence of triacylglycerides. The high chromatographic resolution and sensitivity of GC×GC–ToFMS enabled the separation and identification of a higher number of volatile compounds from sea salt, about three folds, compared to unidimentional chromatography (GC–qMS). The chromatographic contour plots obtained revealed the complexity of marine salt volatile composition and confirmed the relevance of GC×GC–ToFMS for this type of analysis. The structured bidimentional chromatographic profile arising from 1D volatility and 2D polarity was demonstrated, allowing more reliable identifications. Results obtained for analysis of salt from two locations in Aveiro and harvested over three years suggest the loss of volatile compounds along the time of storage of the salt. From Atlantic Ocean salts of seven different geographical origins, all produced in 2007, it was possible to identify a sub-set of ten compounds present in all salts, namely 6-methyl-5-hepten-2-one, 2,2,6-trimethylcyclohexanone, isophorone, ketoisophorone, β-ionone-5,6-epoxide, dihydroactinidiolide, 6,10,14-trimethyl-2-pentadecanone, 3-hydroxy-2,4,4-trimethylpentyl 2-methylpropanoate, 2,4,4-trimethylpentane-1,3-diyl bis(2-methylpropanoate), and 2-ethyl-1-hexanol. These ten compounds were considered potential volatile markers of sea salt. Seven of these compounds are carotenoid-derived compounds, and the other three may result from the integration of compounds from anthropogenic activity as metabolites of marine organisms. The present PhD work also allowed the isolation and characterisation, for the first time, of polymeric material from sea salt, using 16 Atlantic Ocean salts. A dialysis-based methodology was developed to isolate the polymeric material from sea salt in amounts that allowed its characterisation. The median content of polymeric material isolated from the 16 salts was 144 mg per kg of salt, e.g. 0.014% (w/w). Mid-infrared spectroscopy and thermogravimetry revealed the main occurrence of sulfated polysaccharides, as well as the presence of protein in the polymeric material from sea salt. Sea salt polysaccharides were found to be rich in uronic acid residues (21 mol%), glucose (18), galactose (16), and fucose (13). Sulfate content represented a median of 45 mol%, being the median content of sulfated polysaccharides 461 mg/g of polymeric material, which accounted for 66 mg/kg of dry salt. Glycosidic linkage composition indicates that the main sugar residues that could carry one or more sulfate groups were identified as fucose and galactose. This fact allowed to infer that the polysaccharides from sea salt arise mainly from algae, due to their abundance and composition. The amino acid profile of the polymeric material from the 16 Atlantic Ocean salts showed as main residues, as medians, alanine (25 mol%), leucine (14), and valine (14), which are hydrophobic, being the median protein content 35 mg/g, i.e. 4,9 mg per kg of dry salt. Beside the occurrence of hydrophobic volatile compounds in sea salt, hydrophobic non-volatile compounds were also detected. Triacylglycerides were obtained from sea salt by soxhlet extraction with n-hexane. Fatty acid composition revealed palmitic acid as the major residue (43 mol%), followed by stearic (13), linolenic (13), oleic (12), and linoleic (9). Sea salt triacylglycerides median content was 1.5 mg per kg of dry salt. Both protein and triacylglycerides seem to arise from macro and microalgae, phytoplankton and cyanobacteria, due to their abundance and composition. Despite the variability resulting from saltpans surrounding environment, this PhD thesis allowed the identification of a sea salt characteristic organic compounds profile based on volatile compounds, polysaccharides, protein, and triacylglycerides.

Phthalocyanines : interaction with carbon structures and as PDT agents

This dissertation describes the synthesis and characterization of different phthalocyanine (Pc) derivatives, as well as some porphyrins (Pors), for supramolecular interaction with different carbon nanostructures, to evaluate their potential application in electronic nanodevices. Likewise, it is also reported the preparation and biological evaluation of interesting phthalocyanine conjugates for cancer photodynamic therapy (PDT) and microorganisms photodynamic inactivation (PDI). The phthalonitrile precursors were prepared from commercial phthalonitriles by nucleophilic substitution of -NO2, -Cl, or -F groups, present in the phthalonitrile core, by thiol or pyridyl units. After the synthesis of these phthalonitriles, the corresponding Pcs were prepared by ciclotetramerization using a metallic salt as template at high temperatures. A second strategy involved the postfunctionalization of hexadecafluorophthalocyaninato zinc(II) through the adequate substituents of mercaptopyridine or cyclodextrin units on the macrocycle periphery. The different compounds were structurally characterized by diverse spectroscopic techniques, namely 1H, 13C and 19F nuclear magnetic resonance spectroscopies (attending the elemental composition of each structure); absorption and emission spectroscopy, and mass spectrometry. For the specific photophysical studies were also used electrochemical characterization, femtosecond and raman spectroscopy, transmission electron and atomic force microscopy. It was highlighted the noncovalent derivatisation of carbon nanostructures, mainly single wall carbon nanotubes (SWNT) and graphene nanosheets with the prepared Pc conjugates to study the photophysical properties of these supramolecular nanoassemblies. Also, from pyridyl-Pors and ruthenium phthalocyanines (RuPcs) were performed Por-RuPcs arrays via coordination chemistry. The results obtained of the novel supramolecular assemblies showed interesting electron donor-acceptor interactions and might be considered attractive candidates for nanotechnological devices. On the other hand, the amphiphilic phthalocyanine-cyclodextrin (Pc-CD) conjugates were tested in biological trials to assess their ability to inhibit UMUC- 3 human bladder cancer cells. The results obtained demonstrated that these photoactive conjugates are highly phototoxic against human bladder cancer cells and could be applied as promising PDT drugs.

Expanded porphyrins and their evaluation as anion chemosensors

Expanded porphyrins are synthetic analogues of porphyrins, differing from the last ones and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core, with a minimum of 17 atoms, while retaining the extended conjugation features that are a tremendous feature of these biological pigments. The core expansion results in various systems with novel spectral and electronic features, often uniques. Most of these systems can also coordinate cations and/or anions, and in some cases they can bind more than one of these species. In many cases, these molecules display structural features, such as non-planar structures, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. This work will discuss several synthetic approaches for the synthesis of expanded porphyrins, namely the construction of new building blocks by Michael addition, as well as potential synthetic routes towards expanded porphyrins. The synthesis of smaller oligopyrrolic compounds namely, bipyrroles and dipyrromethanes, not only were developed for the synthesis of expanded porphyrins as they were also used in Knoevenagel condensations furnishing chromogenic compounds able to recognize different anions in solution. Also, an approach to the synthesis of novel expanded porphyrins namely sapphyrins has been done by aza-Michael additions. Several synthetic routes towards the synthesis of pyridyl and pyridinium N-Fused pentaphyrins and hexaphyrins have been explored in order to achieve compounds with potential applications in catalysis and PDI, respectively. Studies on the synthesis of compounds with potential anion binding properties, led to the structural characterization and NMR anion binding studies of [28]hexaphyrins functionalized with several diamines in the para position of their pentafluorophenyl groups. These compounds allow NH hydrogen bond interactions with various anions. All synthesized compounds were fully characterized by modern spectroscopic techniques.

Brazilian savanna forest : conservation, medicinal reservoir and bioprospecting

This study aimed to analyse the Brazilian savanna forest from a Legal Reserve (LR) area from a perspective of conservation, reservoir of organic carbon and medicinal biomass for a prospective use of native medicinal plants. An ethnobotanical and ethnopharmacological survey was carried out close to a community settled in the rural area in the south of Tocantins, being selected 9 of the most cited species (cajuí- Anacardium othonianum; inharé-Brosimum gaudichaudii; jatobá-Hymenaeae courbaril; jenipapo-Genipa americana, aroeira-Myracrodruon urundeuva; negramina-Siparuna guianensis; barbatimão- Stryphnodendron obovatum; assa peixe-Vernonia brasiliana, embaúba-Cecropia pachystachya). Crude foliar extracts were subjected to a preliminary phytochemical prospection and triage of secondary metabolites with antimicrobial activity of potential interest in health and familiar agriculture. Phenolic compounds, terpenes and flavonoids were detected in the extracts of most species, which suggests the presence of antimicrobial, antioxidant and anti-insect activities. It was evident the need to better know the LR as a reservoir of medicinal biomass in an area under ecological tension where 35% (610ha) of the property is LR and should be protected by law. Therefore, a forest inventory of live woody species was performed using the allometric or indirect method. This identified a rare remnant of Semidecidual Seasonal Forest amidst the largest world savannah, the Cerrado biome. An analysis of the forest average productivity per basal area (m².ha), aerial live biomass (ton.ha-1) and carbon stock was carried out. The forest fragment was considered relatively rich in species and diversity, although showing signs of disturbance and dominance by a few species. Its horizontal structure suggests biotic regeneration conditions. It is an important reservoir of medicinal plants. Of the families (57.5%) presenting medicinal species, 19 from a total of 33 are represented in the area and contain 44% (27) of the total species (61) and 63% (432) of the total individuals catalogued. Medicinal species have ecological importance for the equilibrium of the local flora and represent 80% of the 10 species with higher Importance Value Index (IVI): Tetragastris altissima, Chrysophyllum marginatum, Oenocarpus distichus, Sclerolobium paniculatum, Simarouba versicolor, Alibertia macrophylla, Siparuna guianensis, Maprounea guianensis, Licania parvifolia e Physocalymma scaberrimum. Medicinal productivity was high for this type of phytophysionomy: 183,2 ton. ha-1 of biomass and 91,51 ton. ha-1 of carbon representing 66% of the total biomass and carbon of this Cerrado forest. From this stage S. guianensis (Siparunaceae) was selected for performing bioassays in order to verify its biological activity against microorganisms of health and agricultural relevance. This is a native aromatic medicinal plant recommended as priority for conservation, with local popular medicinal validation and availability of medicinal feedstock (3300 Kg.ha-1), with the foliar fraction giving 38Kg/ha of crude extract and 5L/ha of essential oil. Foliar crude extracts and essential oil were obtained and tested in vitro using a disk diffusion bioassay. Different concentrations of these natural products were tested against gram-positive bacteria (Staphylococcus aureus ATCC 29213), gram-negative bacteria (Escherichia coli ATCC 25922 and ATCC 35218; Pseudomonas aeruginosa ATCC 10145) and fungi (Candida albicans ATCC 6258 e Fusarium oxysporum). The essential oil inhibited the growth of S. aureus in its crude concentration (380μg.mL-1), as well as diluted to half (190μg.mL-1) and a quarter strength (95μg.mL-1). It’s likely that such action is due to sesquiterpenes major components, such as bisabolol and bisabolene (10.35%), measured by gas chromatography (GC-MS, GC-FID). Extracts did not exhibit any antimicrobial activity against the microorganisms tested. The native medicinal plants prospective market is an alternative that favours the conservation of biodiversity while generating benefits for the development of sustainable family productive activities within local ecosystems instead of the current inappropriate uses. This strengthens conservation policies of Legal Reserve in rural settlements and is in agreement with public policy on global warming and climate changes.

Famílias envelhecidas: percursos e diversidade

O conhecimento sobre famílias envelhecidas é ainda escasso. Neste âmbito, a pesquisa tem incidido nos cuidados familiares a idosos dependentes, focando os problemas de saúde, dependência funcional e declínio cognitivo. Esta investigação pretende contribuir para aprofundar o conhecimento sobre as famílias envelhecidas, assumindo uma perspetiva normativa e desenvolvimental, e contemplando a diversidade de contextos de vida e envelhecimento. O capítulo 1 centra casais compostos por pessoas idosas, e tem por objetivos: caracterizar a estrutura, dinâmica e valores do agregado familiar dos casais idosos; evidenciar valores e dinâmica relacional dos casais idosos. A amostra compreende 136 participantes, a quem foi administrado um questionário sobre a fase última do ciclo de vida familiar (Cerveny,1997). A análise de dados efetuou-se com recurso ao programa de análise de dados estatística SPSS 17.1. Os resultados indicam que os casais vivem predominantemente em casal, com uma dinâmica relacional do agregado caracterizada pelo respeito, diálogo e carinho; dinâmica relacional do casal caracterizada por clima afetuoso, amizade e diálogo, e valores assentes no amor, diálogo e convívio familiar. A dinâmica relacional do casal é pautada por atividades de lazer realizadas em conjunto e vida sexual tão boa como antes; os valores dão ao casamento significados de realização pessoal e perpetuação através dos filhos na juventude, e adaptação e descoberta na velhice. O capítulo 2 foca a construção da integridade familiar considerando a diversidade de contextos socioeconómicos (pessoas idosas que viveram em contexto de pobreza ao longo da vida), socioculturais (ex-emigrantes portugueses) e novas formas de famílias (homens homossexuais). Foi aplicada uma entrevista semiestruturada (King & Wynne, 2004) a uma amostra de 12, 20 e 10 pessoas, respetivamente. A análise de dados foi efetuada com base na análise de conteúdo com recurso a juízes independentes baseada na grounded theory, contudo no caso do contexto socioeconómico recorreu-se ao programa de análise de dados qualitativa N-Vivo 7. Os resultados sugerem que a diversidade de contextos analisada coloca desafios à rutura familiar o que pode potenciar o caminho da desconexão e alienação. Contudo, o contexto das significações exerce um papel fundamental na construção da integridade familiar. A redefinição da identidade associada a uma filosofia de vida que enfatize as forças em vez dos fracassos parece determinar a construção da integridade familiar, contudo existem especificidades. Relativamente ao contexto socioeconómico: as pessoas idosas no caminho da integridade revelam um sentido de autovalorização (ter vivido uma vida significativa) apesar da pobreza; as pessoas idosas no caminho da desconexão/alienação alimentam sentimentos de insignificância devido à escassez de recursos económicos. Ainda neste contexto, os valores (princípios de conduta) reinterpretam a identidade ao longo da vida e permitem compreender que a integridade familiar ocorre quando ser pobre é encarado pelas conquistas; a desconexão/alienação emerge quando ser pobre incorpora sentimentos de desvalorização e inferioridade. No contexto sociocultural, as pessoas idosas ex-emigrantes cujo processo de emigração se desenvolveu em família (a família está envolvida no processo de emigração e funciona como um pilar desde a fase de decisão até ao regresso) desenvolveram uma filosofia de vida assente numa atitude ativa e solidária e estão em integridade familiar; as pessoas em desconexão relatam episódios de conflito familiar que marcam a trajetória de emigração, e uma atitude passiva na resolução desses conflitos até à atualidade; as pessoas em alienação familiar, cujo processo de emigração se desenrolou de forma solitária, desenvolvem uma filosofia de vida assente na luta solitária: a sua força e identidade estão em enfrentar tudo sem precisar de ninguém. Relativamente às novas formas de família, a integridade familiar evolui desde a revelação da homossexualidade (em idade jovem) e conclui-se na velhice quando a homossexualidade se torna um legado. A desconexão parece evoluir da luta constante da falha da aceitação da homossexualidade pela família e outras pessoas significativas. O capítulo 3 analisa as trajetórias de vida de homens homossexuais atualmente idosos, para compreender melhor a influência da homossexualidade e os principais eventos. Adotou-se a técnica da linha de acontecimentos de vida (Acquaviva et al., 2007), aplicada a 10 participantes com 60 anos ou mais. Os resultados sugerem que vários eventos de vida influenciam o curso de vida: i) o autoconhecimento da homossexualidade; ii) tentar passar por heterossexual; iii) assumir a homossexualidade (explicita ou implicitamente); iv) sentir limitações e desafios relacionados com o ser idoso e homossexual. O capítulo 4 procurou alargar a perspetiva do envelhecimento considerando uma abordagem transcultural. Assim, realizou-se um estudo numa comunidade indígena (Guarani Mbya, Brasil). Neste estudo analisase o modo de viver e ser idoso nessa comunidade. A amostra compreende 6 participantes a quem foi administrada uma entrevista aberta. Este estudo contemplou ainda a observação com registo etnográfico e realização de um diário de bordo. A análise de conteúdo efetuou-se com apoio do software de dados qualitativa WebQDA 1.4.3. Os resultados sugerem o papel das pessoas idosas na preservação de uma cultura ágrafa, garantindo que as tradições estejam presentes nas gerações atuais através da oralidade. A adoção de lentes normativas no estudo e compreensão das famílias envelhecidas permite compreender as tarefas desenvolvimentais e normativas no fim da vida.

Mercaptans extraction from jet-fuel streams using ionic liquids

Desulfurization is one of the most important processes in the refining industry. Due to a growing concern about the risks to human health and environment, associated with the emissions of sulfur compounds, legislation has become more stringent, requiring a drastic reduction in the sulfur content of fuel to levels close to zero (< 10 ppm S). However, conventional desulfurization processes are inefficient and have high operating costs. This scenario stimulates the improvement of existing processes and the development of new and more efficient technologies. Aiming at overcoming these shortcomings, this work investigates an alternative desulfurization process using ionic liquids for the removal of mercaptans from "jet fuel" streams. The screening and selection of the most suitable ionic liquid were performed based on experimental and COSMO-RS predicted liquid-liquid equilibrium data. A model feed of 1-hexanethiol and n-dodecane was selected to represent a jet-fuel stream. High selectivities were determined, as a result of the low mutual solubility between the ionic liquid and the hydrocarbon matrix, proving the potential use of the ionic liquid, which prevents the loss of fuel for the solvent. The distribution ratios of mercaptans towards the ionic liquids were not as favorable, making the traditional liquid-liquid extraction processes not suitable for the removal of aliphatic S-compounds due to the high volume of extractant required. This work explores alternative methods and proposes the use of ionic liquids in a separation process assisted by membranes. In the process proposed the ionic liquid is used as extracting solvent of the sulfur species, in a hollow fiber membrane contactor, without co-extracting the other jet-fuel compound. In a second contactor, the ionic liquid is regenerated applying a sweep gas stripping, which allows for its reuse in a closed loop between the two membrane contactors. This integrated extraction/regeneration process of desulfurization produced a jet-fuel model with sulfur content lower than 2 ppm of S, as envisaged by legislation for the use of ultra-low sulfur jet-fuel. This result confirms the high potential for development of ultra-deep desulfurization application.

The impact of biofuels for road traffic on air quality : a modelling approach

The selection of the energy source to power the transport sector is one of the main current concerns, not only relative with the energy paradigm but also due to the strong influence of road traffic in urban areas, which highly affects human exposure to air pollutants and human health and quality of life. Due to current important technical limitations of advanced energy sources for transportation purposes, biofuels are seen as an alternative way to power the world’s motor vehicles in a near-future, helping to reduce GHG emissions while at the same time stimulating rural development. Motivated by European strategies, Portugal, has been betting on biofuels to meet the Directive 2009/28/CE goals for road transports using biofuels, especially biodiesel, even though, there is unawareness regarding its impacts on air quality. In this sense, this work intends to clarify this issue by trying to answer the following question: can biodiesel use contribute to a better air quality over Portugal, particularly over urban areas? The first step of this work consisted on the characterization of the national biodiesel supply chain, which allows verifying that the biodiesel chain has problems of sustainability as it depends on raw materials importation, therefore not contributing to reduce the external energy dependence. Next, atmospheric pollutant emissions and air quality impacts associated to the biodiesel use on road transports were assessed, over Portugal and in particular over the Porto urban area, making use of the WRF-EURAD mesoscale numerical modelling system. For that, two emission scenarios were defined: a reference situation without biodiesel use and a scenario reflecting the use of a B20 fuel. Through the comparison of both scenarios, it was verified that the use of B20 fuels helps in controlling air pollution, promoting reductions on PM10, PM2.5, CO and total NMVOC concentrations. It was also verified that NO2 concentrations decrease over the mainland Portugal, but increase in the Porto urban area, as well as formaldehyde, acetaldehyde and acrolein emissions in the both case studies. However, the use of pure diesel is more injurious for human health due to its dominant VOC which have higher chronic hazard quotients and hazard indices when compared to B20.

Metabolic signature of lung cancer: a metabolomic study of human tissues and biofluids

This thesis reports the application of metabolomics to human tissues and biofluids (blood plasma and urine) to unveil the metabolic signature of primary lung cancer. In Chapter 1, a brief introduction on lung cancer epidemiology and pathogenesis, together with a review of the main metabolic dysregulations known to be associated with cancer, is presented. The metabolomics approach is also described, addressing the analytical and statistical methods employed, as well as the current state of the art on its application to clinical lung cancer studies. Chapter 2 provides the experimental details of this work, in regard to the subjects enrolled, sample collection and analysis, and data processing. In Chapter 3, the metabolic characterization of intact lung tissues (from 56 patients) by proton High Resolution Magic Angle Spinning (HRMAS) Nuclear Magnetic Resonance (NMR) spectroscopy is described. After careful assessment of acquisition conditions and thorough spectral assignment (over 50 metabolites identified), the metabolic profiles of tumour and adjacent control tissues were compared through multivariate analysis. The two tissue classes could be discriminated with 97% accuracy, with 13 metabolites significantly accounting for this discrimination: glucose and acetate (depleted in tumours), together with lactate, alanine, glutamate, GSH, taurine, creatine, phosphocholine, glycerophosphocholine, phosphoethanolamine, uracil nucleotides and peptides (increased in tumours). Some of these variations corroborated typical features of cancer metabolism (e.g., upregulated glycolysis and glutaminolysis), while others suggested less known pathways (e.g., antioxidant protection, protein degradation) to play important roles. Another major and novel finding described in this chapter was the dependence of this metabolic signature on tumour histological subtype. While main alterations in adenocarcinomas (AdC) related to phospholipid and protein metabolisms, squamous cell carcinomas (SqCC) were found to have stronger glycolytic and glutaminolytic profiles, making it possible to build a valid classification model to discriminate these two subtypes. Chapter 4 reports the NMR metabolomic study of blood plasma from over 100 patients and near 100 healthy controls, the multivariate model built having afforded a classification rate of 87%. The two groups were found to differ significantly in the levels of lactate, pyruvate, acetoacetate, LDL+VLDL lipoproteins and glycoproteins (increased in patients), together with glutamine, histidine, valine, methanol, HDL lipoproteins and two unassigned compounds (decreased in patients). Interestingly, these variations were detected from initial disease stages and the magnitude of some of them depended on the histological type, although not allowing AdC vs. SqCC discrimination. Moreover, it is shown in this chapter that age mismatch between control and cancer groups could not be ruled out as a possible confounding factor, and exploratory external validation afforded a classification rate of 85%. The NMR profiling of urine from lung cancer patients and healthy controls is presented in Chapter 5. Compared to plasma, the classification model built with urinary profiles resulted in a superior classification rate (97%). After careful assessment of possible bias from gender, age and smoking habits, a set of 19 metabolites was proposed to be cancer-related (out of which 3 were unknowns and 6 were partially identified as N-acetylated metabolites). As for plasma, these variations were detected regardless of disease stage and showed some dependency on histological subtype, the AdC vs. SqCC model built showing modest predictive power. In addition, preliminary external validation of the urine-based classification model afforded 100% sensitivity and 90% specificity, which are exciting results in terms of potential for future clinical application. Chapter 6 describes the analysis of urine from a subset of patients by a different profiling technique, namely, Ultra-Performance Liquid Chromatography coupled to Mass Spectrometry (UPLC-MS). Although the identification of discriminant metabolites was very limited, multivariate models showed high classification rate and predictive power, thus reinforcing the value of urine in the context of lung cancer diagnosis. Finally, the main conclusions of this thesis are presented in Chapter 7, highlighting the potential of integrated metabolomics of tissues and biofluids to improve current understanding of lung cancer altered metabolism and to reveal new marker profiles with diagnostic value.

Sustainable viticulture in Bairrada appellation: vineyard and harvest year effects on grapes oenological potential

The sustainable viticulture of a region passes, among other aspects, for maximizing the varieties potential minimizing subsequent interventions during winemaking, which should contribute to the production of quality wines maintaining their typicity and rationalizing costs. The detailed knowledge of each Appellation specificities, namely vineyard parcel (soil type and topographical peculiarities) and harvest climatic conditions is crucial for sustainability in this sector. Thus, in line with this current trend, the starting point for the development of this PhD thesis was to evaluate the oenological potential of different varieties cultivated throughout Bairrada Appellation (Portugal). During maturation several changes in grape varieties occur, namely berries become sweeter, less acidic, and they develop flavour, aroma and colour properties. The development of these characteristics is essential to define grapes oenological potential, i.e. to estimate the possibility of their usage to produce specific wines. A three years sampling plan was designed to evaluate the effect of harvest year and parcel characteristics on V. vinifera cv. Arinto, Bical, Sauvignon Blanc, Baga, Castelão, Touriga Nacional, and Sousão grapes composition. For each variety, 3 parcels with different characteristics were selected. Several physicochemical parameters were evaluated, during maturation: berry weight, pH, titratable acidity, sugar and phenolic contents, antiradical activity, and volatile composition (free fraction). Special attention was devoted to grapes at technologic maturity, since, besides these parameters, glycosidically-linked fraction was also considered. By using the results obtained at technologic maturity, a comprehensive approach was applied to identify the significance of harvest and parcel characteristics effects on each variety composition. Considering all the parameters under study, it may be highlighted some significant differences. According to the obtained results determined during maturation, it was possible to conclude that Arinto, Bical and Sauvignon Blanc grapes from parcels with clay-sandy and clay-calcareous soils have higher phenolic content and antiradical activity. Otherwise, Sauvignon Blanc presented similar volatile composition for grapes cultivated in the 3 parcels, while Arinto and Bical exhibited higher volatile content in grapes from claysandy and clay-calcareous soils. For Baga, Castelão and Touriga Nacional red varieties, grapes with higher phenolic content, antiradical activity, and volatile content were obtained from clayey and clay-calcareous soils. Furthermore, for Touriga Nacional, parcels altitude seems also to modulate grapes composition. Beyond parcel effect, harvest year conditions also influence grapes composition: 2011 harvest was related with lower phenolic and volatile contents, as well as lower antiradical activity.For grapes collected at technologic maturity, analysis of variance-simultaneous component analysis (ASCA) was applied combining all the parameters under study, in order to assess the influence of harvest and parcel characteristics on each variety oenological potential. The results obtained using this comprehensive approach is closely related with those observed during maturation and revealed that harvest was the main factor that influenced grapes composition (53% to 68% of the total data set variance) followed by parcel characteristics, explaining ca. 15-19% of the total data set variance. The oenological potential of each variety may be different from one parcel to another, i.e., clay-sandy and clay-calcareous related-environments seem to favour Arinto and Bical white grapes composition, but for the red varieties, grapes composition was favoured by clayey and clay-calcareous soils. Besides, also higher altitude seems to favour Touriga Nacional grapes composition. Sauvignon Blanc seems to be a variety well adapted to the different parcel characteristics. In order to go forward in the valuation of these varieties, the aroma properties of 6 monovarietal wines were studied based on an aroma network-approach, linking molecular data related to volatile composition and aroma data about the key odor active molecules. This approach allowed to identify different wine aroma properties and to infer about the consumer’s sensory perception. It was found that aroma properties differ from one wine variety to another: while Arinto and Sauvignon Blanc wine exhibited higher tree fruity, sweety and flowery aromas, related essentially with ester compounds and C13 norisoprenoids, the opposite was obtained for Bical wine, corroborating the aroma sensory perceptions of the trained panel. Sauvignon Blanc also exhibited higher toasted aromas (related with thiols, mainly with 2-methyl-3-furanthiol). Touriga Nacional red wine exhibited higher tree, tropical, and berry fruits notes (sensory described as sweet fruits), toasted and flowery aromas, while these are similar for the other red wines under study. Besides Portuguese Bairrada wines, this aroma network approach is a tool that can be used to explain the aroma properties of wines worldwide. The grape and wine data generated under the present PhD thesis, in the context of Bairrada Appellation, shows the unique character of each variety, and may be used by growers and wine producers as a support for decisionmaking based on objective criteria, increasing the sustainability in this sector. For instance, it is possible to take advantage of the natural resources and produce products with different characteristics obtained from the same variety, minimizing costs during the winemaking process.