Environmental factors, clipping and fire: effects on cerrado (Brazilian savanna) native and invasive grasses

The Brazilian Cerrado houses a hugely diverse biota and is considered a conservation hotspot. One of the greatest threats to the integrity of this ecosystem is introduced African grasses, which can competitively exclude native grasses and cause changes in the microclimate and other disturbances. The Cerrado is a mosaic vegetation that provides different combinations, both spatially and temporally, of conditions that can become natural stressors to the herbaceous vegetation (water, nutrient and light availability). These mosaics are reflected in differences in relationships among native and invasive species, affecting competition and creating situations (place/season) that are more, or less, susceptible to invasion. The present study aimed to identify the different biological responses of native (Aristida recurvata, Aristida setifolia, Axonopus barbigerus, Echinolaena inflexa, Gymnopogon spicatus, Paspalum gardnerianum, Paspalum stellatum, Schizachyrium microstachyum, Schizachyrium sanguineum) and invasive (Melinis minutiflora and Andropogon gayanus) grasses to variations in natural stressors and to disturbance (fire and clipping), in order to understand changes in ecosystem functioning and competition processes between the grasses, and to understand invasion dynamics in this ecosystem. The presence of invasive species proved to affect the ecosystem functioning by increasing soil feeding activity. These differences were no longer observed in the dry season or when fires were frequent, showing that water availability and fire are more detrimental to soil feeding activity than is the vegetation. Laboratory experiments showed that both drought and flood simulated scenarios damaged both species, although the invasive species performed better under all watering conditions and responded better to fertilization. Underlying mechanisms such as the efficiency of photosynthesis and antioxidant mechanisms helped to explain this behavior. The invasive species grew faster and showed less cellular damage and a healthier photosystem, reflected in higher assimilation rates under stress. These differences between the native and invasive species were reduced with clipping, especially in dry soil with no fertilization, where the native species recovered better in relation to the pre-clipping levels. Flooding was as stressful as drought, but the invasive species can bypass this issue by growing an extensive root system, especially in the better-drained soils. Fire is more detrimental than clipping, with a slower recovery, while post-fire temperatures affect the germination of both invasive and native seeds and may be an important factor influencing the persistence of a diverse biota. This approach will finally contribute to the choice of the appropriate management techniques to preserve the Cerrado’s biodiversity.

Evaluation of the matabolic response of osteosarcoma cells to conventional and new anticancer drugs by NMR metabolomics

The main scope of this work was to evaluate the metabolic effects of anticancer agents (three conventional and one new) in osteosarcoma (OS) cells and osteoblasts, by measuring alterations in the metabolic profile of cells by nuclear magnetic resonance (NMR) spectroscopy metabolomics. Chapter 1 gives a theoretical framework of this work, beginning with the main metabolic characteristics that globally describe cancer as well as the families and mechanisms of action of drugs used in chemotherapy. The drugs used nowadays to treat OS are also presented, together with the Palladium(II) complex with spermine, Pd2Spm, potentially active against cancer. Then, the global strategy for cell metabolomics is explained and the state of the art of metabolomic studies that analyze the effect of anticancer agents in cells is presented. In Chapter 2, the fundamentals of the analytical techniques used in this work, namely for biological assays, NMR spectroscopy and multivariate and statistical analysis of the results are described. A detailed description of the experimental procedures adopted throughout this work is given in Chapter 3. The biological and analytical reproducibility of the metabolic profile of MG-63 cells by high resolution magic angle spinning (HRMAS) NMR is evaluated in Chapter 4. The metabolic impact of several factors (cellular integrity, spinning rate, temperature, time and acquisition parameters) on the 1H HRMAS NMR spectral profile and quality is analysed, enabling the definition of the best acquisition parameters for further experiments. The metabolic consequences of increasing number of passages in MG-63 cells as well as the duration of storage are also investigated. Chapter 5 describes the metabolic impact of drugs conventionally used in OS chemotherapy, through NMR metabolomics studies of lysed cells and aqueous extracts analysis. The results show that MG-63 cells treated with cisplatin (cDDP) undergo a strong up-regulation of lipid contents, alterations in phospholipid constituents (choline compounds) and biomarkers of DNA degradation, all associated with cell death by apoptosis. Cells exposed to doxorubicin (DOX) or methotrexate (MTX) showed much slighter metabolic changes, without any relevant alteration in lipid contents. However, metabolic changes associated with altered Krebs cycle, oxidative stress and nucleotides metabolism were detected and were tentatively interpreted at the light of the known mechanisms of action of these drugs. The metabolic impact of the exposure of MG-63 cells and osteoblasts to cDDP and the Pd2Spm complex is described in Chapter 6. Results show that, despite the ability of the two agents to bind DNA, the metabolic consequences that arise from exposure to them are distinct, namely in what concerns to variation in lipid contents (absent for Pd2Spm). Apoptosis detection assays showed that, differently from what was seen for MG-63 cells treated with cDDP, the decreased number of living cells upon exposure to Pd2Spm was not due to cell death by apoptosis or necrosis. Moreover, the latter agent induces more marked alterations in osteoblasts than in cancer cells, while the opposite seemed to occur upon cDDP exposure. Nevertheless, the results from MG-63 cells exposure to combination regimens with cDDP- or Pd2Spm-based cocktails, described in Chapter 7, revealed that, in combination, the two agents induce similar metabolic responses, arising from synergy mechanisms between the tested drugs. Finally, the main conclusions of this thesis are summarized in Chapter 8, and future perspectives in the light of this work are presented.

Extension of electrochemically active sites in SOFCs and SOECs

Solid oxide fuel (SOFCs) and electrolyzer (SOECs) cells have been promoted as promising technologies for the stabilization of fuel supply and usage in future green energy systems. SOFCs are devices that produce electricity by the oxidation of hydrogen or hydrocarbon fuels with high efficiency. Conversely, SOECs can offer the reverse reaction, where synthetic fuels can be generated by the input of renewable electricity. Due to this similar but inverse nature of SOFCs and SOECs, these devices have traditionally been constructed from comparable materials. Nonetheless, several limitations have hindered the entry of SOFCs and SOECs into the marketplace. One of the most debilitating is associated with chemical interreactions between cell components that can lead to poor longevities at high working temperatures and/or depleted electrochemcial performance. Normally such interreactions are countered by the introduction of thin, purely ionic conducting, buffer layers between the electrode and electrolyte interface. The objective of this thesis is to assess if possible improvements in electrode kinetics can also be obtained by modifying the transport properties of these buffer layers by the introduction of multivalent cations. The introduction of minor electronic conductivity in the surface of the electrolyte material has previously been shown to radically enhance the electrochemically active area for oxygen exchange, reducing polarization resistance losses. Hence, the current thesis aims to extend this knowledge to tailor a bi-functional buffer layer that can prevent chemical interreaction while also enhancing electrode kinetics.The thesis selects a typical scenario of an yttria stabilized zirconia electrolyte combined with a lanthanide containing oxygen electrode. Gadolinium, terbium and praseodymium doped cerium oxide materials have been investigated as potential buffer layers. The mixed ionic electronic conducting (MIEC) properties of the doped-cerium materials have been analyzed and collated. A detailed analysis is further presented of the impact of the buffer layers on the kinetics of the oxygen electrode in SOFC and SOEC devices. Special focus is made to assess for potential links between the transport properties of the buffer layer and subsequent electrode performance. The work also evaluates the electrochemical performance of different K2NiF4 structure cathodes deposited onto a peak performing Pr doped-cerium buffer layer, the influence of buffer layer thickness and the Pr content of the ceria buffer layer. It is shown that dramatic increases in electrode performance can be obtained by the introduction of MIEC buffer layers, where the best performances are shown to be offered by buffer layers of highest ambipolar conductivity. These buffer layers are also shown to continue to offer the bifunctional role to protect from unwanted chemical interactions at the electrode/electrolyte interface.

Diopside-fluorapatite-wollastonite based bioactive glasses and glass-ceramics

Bioactive glasses and glass–ceramics are a class of biomaterials which elicit special response on their surface when in contact with biological fluids, leading to strong bonding to living tissue. This particular trait along with good sintering ability and high mechanical strength make them ideal materials for scaffold fabrication. The work presented in this thesis is directed towards understanding the composition-structure-property relationships in potentially bioactive glasses designed in CaOMgOP2O5SiO2F system, in some cases with added Na2O. The main emphasis has been on unearthing the influence of glass composition on molecular structure, sintering ability and bioactivity of phosphosilicate glasses. The parent glass compositions have been designed in the primary crystallization field of the pseudo-ternary system of diopside (CaO•MgO•2SiO2) – fluorapatite (9CaO•3P2O5•CaF2) – wollastonite (CaO•SiO2), followed by studying the impact of compositional variations on the structure-property relationships and sintering ability of these glasses. All the glasses investigated in this work have been synthesized via melt-quenching route and have been characterized for their molecular structure, sintering ability, chemical degradation and bioactivity using wide array of experimental tools and techniques. It has been shown that in all investigated glass compositions the silicate network was mainly dominated by Q2 units while phosphate in all the glasses was found to be coordinated in orthophosphate environment. The glass compositions designed in alkali-free region of diopside – fluorapatite system demonstrated excellent sintering ability and good bioactivity in order to qualify them as potential materials for scaffold fabrication while alkali-rich bioactive glasses not only hinder the densification during sintering but also induce cytotoxicity in vitro, thus, are not ideal candidates for in vitro tissue engineering. One of our bioglass compositions with low sodium content has been tested successfully both in vivo and in preliminary clinical trials. But this work needs to be continued and deepened. The dispersing of fine glass particles in aqueous media or in other suitable solvents, and the study of the most important factors that affect the rheology of the suspensions are essential steps to enable the manufacture of porous structures with tailor-made hierarchical pores by advanced processing techniques such as Robocasting.

Oxidation and glycoxidation of phosphatidylserine and their effect in immune response : a lipidomic approach

Phosphatidylserine (PS) is a member of the class of phospholipids, and is distributed among all cells of mammalians, playing important roles in diverse biological processes, including blood clotting and apoptosis. When externalized, PS is a ligand that is recognized on apoptotic cells. It has been considered that before externalization PS is oxidized and oxPS enhance the recognition by macrophages receptors, however the knowledge about oxidation of PS is still limited. PS, like others phospholipids, has two fatty acyl chains and one polar head group, in this case is the amino acid serine. The modifications in PS structure can occur by oxidation of the unsaturated fatty acyl chains and by glycation of the polar head group, due to free amine group, thus increasing the susceptibility to oxidative events. The main goal of this work was to characterize and identify oxidized and glycoxidized PS, contributing to the knowledge of the biological role of oxidation products of PS, as well as of glycated PS, in immune and inflammatory processes. To achieve this goal, PS standards (1-palmitoyl-2-oleoyl-sn-glycero-3-phospho- L-serine (POPS), 1,2-dipalmitoyl-sn-glycero-3-phospho-L-serine (DPPS), 1- palmitoyl-2-linoleoyl-sn-glycero-3-phospho-L-serine (PLPS) and 1-palmitoyl-2- arachidonoyl-sn-glycero-3-phospho-L-serine (PAPS)) and glycated PS (PAPS and POPS) were induced to oxidize in model systems, using different oxidant reagents: HO• and 2,2'-azobis-2-methyl-propanimidamide dihydrochloride (AAPH) . The detailed structural characterization of the oxidative products was performed by ESI-MS and MS/MS coupled to separation techniques such as off line TLC-MS and on line LC-MS, in order to obtained better characterization of the larger number of PS and glycated PS oxidation products. The results obtained in this work allowed to identify several oxidation products of PS and glycated PS with modifications in unsaturated fatty acyl chain. Also, oxidation products formed due to structural changes in the serine polar head with formation of terminal acetamide, terminal hydroperoxyacetaldehyde.and terminal acetic acid (glycerophosphacetic acid, GPAA) were identified. The mass spectrometric specific fragmentation pathway of each type of oxidation product was determined using different mass spectrometry approaches. Based on the identified fragmentation pathways, targeted lipidomic analysis was performed to detect oxidation products modified in serine polar head in HaCaT cell line treated with AAPH. The GPAA was detected in HaCaT cells treated with AAPH to induce oxidative stress, thus confirming that modifications in PS polar head is possible to occur in biological systems. Furthermore, it was found that glycated PS species are more prone to oxidative modifications when compared with non glycated PS. During oxidation of glycated PS, besides the oxidation in acyl chains, new oxidation products due to oxidation of the glucose moiety were identified, including PS advanced glycation end products (PSAGES). To investigate if UVA oxidative stress exerted changes in the lipidome of melanoma cell lines, particularly in PS profile, a lipidomic analysis was performed. The lipid profile was obtained using HILIC-LC-MS and GC-MS analysis of the total lipid extracts obtained from human melanoma cell line (SKMEL- 28) after UVA irradiation at 0, 2 and 24 hours. The results did not showed significant differences in PS content. At molecular level, only PS (18:0:18:1) decreased at the moment of irradiation. The most significant changes in phospholipids content occurred in phosphatidylcholines (PC) and phosphatidylinositol (PI) classes, with an increase of mono-unsaturated fatty acid (MUFA), similarly as observed for the fatty acid analysis. Overall, these data indicate that the observed membrane lipid changes associated with lipogenesis after UVA exposure may be correlated with malignant transformations associated with cancer development and progression. Despite of UVA radiation is associated with oxidative damage, in this work was not possible observe oxidation phospholipids. The anti/pro-inflammatory properties of the oxidized PLPS (oxPLPS) versus non-oxidized PLPS were tested on LPS stimulated RAW 264.7 macrophages. The modulation of intracellular signaling pathways such as NF-kB and MAPK cascades by oxPLPS and PS was also examined in this study. The results obtained from evaluation of anti/pro-inflammatory properties showed that neither PLPS or oxPLPS species activated the macrophages. Moreover only oxidized PLS were found to significantly inhibit NO production and iNOS and il1β gene transcription induced by LPS. The analysis at molecular level showed that this was the result of the attenuation of LPS-induced c-Jun-N-terminal kinase (JNK) and p65 NF-kB nuclear translocation. Overall these data suggest that oxPLPS, but not native PLPS, mitigates pro-inflammatory signaling in macrophages, contributing to containment of inflammation during apoptotic cell engulfment. The results obtained in this work provides new information on the modifications of PS, facilitating the identification of oxidized species in complex samples, namely under physiopathologic conditions and also contributes to a better understanding of the role of oxPS and PS in the inflammatory response, in the apoptotic process and other biological functions.

Effects of environmental factors on the toxicity of pesticides to zebrafish embryos

During the last century mean global temperatures have been increasing. According to the predictions, the temperature change is expected to exceed 1.5ºC in this century and the warming is likely to continue. Freshwater ecosystems are among the most sensitive mainly due to changes in the hydrologic cycle and consequently changes in several physico-chemical parameters (e.g. pH, dissolved oxygen). Alterations in environmental parameters of freshwater systems are likely to affect distribution, morphology, physiology and richness of a wide range of species leading to important changes in ecosystem biodiversity and function. Moreover, they can also work as co-stressors in environments where organisms have already to cope with chemical contamination (such as pesticides), increasing the environmental risk due to potential interactions. Therefore, the objective of this work was to evaluate the effects of climate change related environmental parameters on the toxicity of pesticides to zebrafish embryos. The following environmental factors were studied: pH (3.0-12.0), dissolved oxygen level (0-8 mg/L) and UV radiation (0-500 mW/m2). The pesticides studied were the carbamate insecticide carbaryl and the benzimidazole fungicide carbendazim. Stressors were firstly tested separately in order to derive concentration- or intensity-response curves to further study the effects of binary combinations (environmental factors x pesticides) by applying mixture models. Characterization of zebrafish embryos response to environmental stress revealed that pH effects were fully established after 24 h of exposure and survival was only affected at pH values below 5 and above 10. Low oxygen levels also affected embryos development at concentrations below 4 mg/L (delay, heart rate decrease and edema), and at concentrations below 0.5 mg/L the survival was drastically reduced. Continuous exposure to UV radiation showed a strong time-dependent impact on embryos survival leading to 100% of mortality after 72 hours of exposure. The toxicity of pesticides carbaryl and carbendazim was characterized at several levels of biological organization including developmental, biochemical and behavioural allowing a mechanistic understanding of the effects and highlighting the usefulness of behavioural responses (locomotion) as a sensitive endpoint in ecotoxicology. Once the individual concentration response relationship of each stressor was established, a combined toxicity study was conducted to evaluate the effects of pH on the toxicity of carbaryl. We have shown that pH can modify the toxicity of the pesticide carbaryl. The conceptual model concentration addition allowed a precise prediction of the toxicity of the jointeffects of acid pH and carbaryl. Nevertheless, for alkaline condition both concepts failed in predicting the effects. Deviations to the model were however easy to explain as high pH values favour the hydrolysis of carbaryl with the consequent formation of the more toxic degradation product 1- naphtol. Although in the present study such explanatory process was easy to establish, for many other combinations the “interactive” nature is not so evident. In the context of the climate change few scenarios predict such increase in the pH of aquatic systems, however this was a first approach focused in the lethal effects only. In a second tier assessment effects at sublethal level would be sought and it is expectable that more subtle pH changes (more realistic in terms of climate changes scenarios) may have an effect at physiological and biochemical levels with possible long term consequences for the population fitness.

Micro/nanoreservoirs for controlled release of active species in smart functional coatings

This work reports one possible way to develop new functional coatings used to increase the life time of metallic structures. The functionalities selected and attributed to model coatings in the frame of this work were corrosion protection, self-sensing and prevention of fouling (antifouling). The way used to confer those functionalities to coatings was based on the encapsulation of active compounds (corrosion inhibitors, pH indicators and biocides) in micro and nanocontainers followed by their incorporation into the coating matrices. To confer active corrosion protection, one corrosion inhibitor (2-mercaptobenzothiazole, MBT) was encapsulated in two different containers, firstly in silica nanocapsules (SiNC) and in polyurea microcapsules (PU-MC). The incorporation of both containers in different models coatings shows a significant improvement in the corrosion protection of aluminum alloy 2024 (AA2024). Following the same approach, SiNC and PU-MC were also used for the encapsulation of phenolphthalein (one well known pH indicator) to introduce sensing properties in polymeric coatings. SiNC and PU-MC containing phenolphthalein acted as corrosion sensor, showing a pink coloration due to the beginning of cathodic reaction, resulting in a pH increase identified by those capsules. Their sensing performance was proved in suspension and when integrated in coatings for aluminium alloy 2024 and magnesium alloy AZ31. In a similar way, the biocide activity (antifouling) was assigned to two polymeric matrices using SiNC for encapsulation of one biocide (Dichloro-2-octyl-2H-isothiazol-3-one, DCOIT) and also SiNC-MBT was tested as biocide. The antifouling activity of those two encapsulated compounds was assessed through inhibition and consequent decrease in the bioluminescence of modified E. coli. That effect was verified in suspension and when incorporated in coatings for AISI 1008 carbon steel. The developed micro and nanocontainers presented the desired performance, allowing the introduction of new functionalities to model coatings, showing potential to be used as functional additives in the next generation of multifunctional coatings.

Piezoelectricity and ferroelectricity in amino acid glycine

Bioorganic ferroelectrics and piezoelectrics are becoming increasingly important in view of their intrinsic compatibility with biological environment and biofunctionality combined with strong piezoelectric effect and switchable polarization at room temperature. Here we study piezoelectricity and ferroelectricity in the smallest amino acid glycine, representing a broad class of non-centrosymmetric amino acids. Glycine is one of the basic and important elements in biology, as it serves as a building block for proteins. Three polymorphic forms with different physical properties are possible in glycine (α, β and γ), Of special interest for various applications are non-centrosymmetric polymorphs: β-glycine and γ-glycine. The most useful β-polymorph being ferroelectric took much less attention than the other due to its instability under ambient conditions. In this work, we could grow stable microcrystals of β-glycine by the evaporation of aqueous solution on a (111)Pt/Ti/SiO2/Si substrate as a template. The effects of the solution concentration and Pt-assisted nucleation on the crystal growth and phase evolution were characterized by X-ray diffraction analysis and Raman spectroscopy. In addition, spin-coating technique was used for the fabrication of highly aligned nano-islands of β-glycine with regular orientation of the crystallographic axes relative the underlying substrate (Pt). Further we study both as-grown and tip-induced domain structures and polarization switching in the β-glycine molecular systems by Piezoresponse Force Microscopy (PFM) and compare the results with molecular modeling and computer simulations. We show that β-glycine is indeed a room-temperature ferroelectric and polarization can be switched by applying a bias to non-polar cuts via a conducting tip of atomic force microscope (AFM). Dynamics of these in-plane domains is studied as a function of applied voltage and pulse duration. The domain shape is dictated by both internal and external polarization screening mediated by defects and topographic features. Thermodynamic theory is applied to explain the domain propagation induced by the AFM tip. Our findings suggest that β-glycine is a uniaxial ferroelectric with the properties controlled by the charged domain walls which in turn can be manipulated by external bias. Besides, nonlinear optical properties of β-glycine were investigated by a second harmonic generation (SHG) method. SHG method confirmed that the 2-fold symmetry is preserved in as-grown crystals, thus reflecting the expected P21 symmetry of the β-phase. Spontaneous polarization direction is found to be parallel to the monoclinic [010] axis and directed along the crystal length. These data are confirmed by computational molecular modeling. Optical measurements revealed also relatively high values of the nonlinear optical susceptibility (50% greater than in the z-cut quartz). The potential of using stable β-glycine crystals in various applications are discussed in this work.

Concentration of tumor biomarkers using aqueous biphasic systems

According to the World Health Organization, around 8.2 million people die each year with cancer. Most patients do not perform routine diagnoses and the symptoms, in most situations, occur when the patient is already at an advanced stage of the disease, consequently resulting in a high cancer mortality. Currently, prostate cancer is the second leading cause of death among males worldwide. In Portugal, this is the most diagnosed type of cancer and the third that causes more deaths. Taking into account that there is no cure for advanced stages of prostate cancer, the main strategy comprises an early diagnosis to increase the successful rate of the treatment. The prostate specific antigen (PSA) is an important biomarker of prostate cancer that can be detected in biological fluids, including blood, urine and semen. However, the commercial kits available are addressed for blood samples and the commonly used analytical methods for their detection and quantification requires specialized staff, specific equipment and extensive sample processing, resulting in an expensive process. Thus, the aim of this MSc thesis consisted on the development of a simple, efficient and less expensive method for the extraction and concentration of PSA from urine samples using aqueous biphasic systems (ABS) composed of ionic liquids. Initially, the phase diagrams of a set of aqueous biphasic systems composed of an organic salt and ionic liquids were determined. Then, their ability to extract PSA was ascertained. The obtained results reveal that in the tested systems the prostate specific antigen is completely extracted to the ionic-liquid-rich phase in a single step. Subsequently, the applicability of the investigated ABS for the concentration of PSA was addressed, either from aqueous solutions or urine samples. The low concentration of this biomarker in urine (clinically significant below 150 ng/mL) usually hinders its detection by conventional analytical techniques. The obtained results showed that it is possible to extract and concentrate PSA, up to 250 times in a single-step, so that it can be identified and quantified using less expensive techniques.

Concentration of tumor biomarkers using aqueous biphasic systems

According to the World Health Organization, around 8.2 million people die each year with cancer. Most patients do not perform routine diagnoses and the symptoms, in most situations, occur when the patient is already at an advanced stage of the disease, consequently resulting in a high cancer mortality. Currently, prostate cancer is the second leading cause of death among males worldwide. In Portugal, this is the most diagnosed type of cancer and the third that causes more deaths. Taking into account that there is no cure for advanced stages of prostate cancer, the main strategy comprises an early diagnosis to increase the successful rate of the treatment. The prostate specific antigen (PSA) is an important biomarker of prostate cancer that can be detected in biological fluids, including blood, urine and semen. However, the commercial kits available are addressed for blood samples and the commonly used analytical methods for their detection and quantification requires specialized staff, specific equipment and extensive sample processing, resulting in an expensive process. Thus, the aim of this MSc thesis consisted on the development of a simple, efficient and less expensive method for the extraction and concentration of PSA from urine samples using aqueous biphasic systems (ABS) composed of ionic liquids. Initially, the phase diagrams of a set of aqueous biphasic systems composed of an organic salt and ionic liquids were determined. Then, their ability to extract PSA was ascertained. The obtained results reveal that in the tested systems the prostate specific antigen is completely extracted to the ionic-liquid-rich phase in a single step. Subsequently, the applicability of the investigated ABS for the concentration of PSA was addressed, either from aqueous solutions or urine samples. The low concentration of this biomarker in urine (clinically significant below 150 ng/mL) usually hinders its detection by conventional analytical techniques. The obtained results showed that it is possible to extract and concentrate PSA, up to 250 times in a single-step, so that it can be identified and quantified using less expensive techniques.

Detection of non-steroidal anti-inflammatory drugs in aqueous effluents using ionic liquids

Significant improvements in human health have been achieved through the increased consumption of pharmaceutical drugs. However, most of these active pharmaceutical ingredients (APIs) are excreted by mammals (in a metabolized or unchanged form) into the environment. The presence of residual amounts of these contaminants was already confirmed in aqueous streams since treatment processes either wastewater treatment plants (WWTPs) or sewage treatment plants (STPs) are not specifically designed for this type of pollutants. Although they are present in aqueous effluents, they are usually at very low concentrations, most of the times below the detection limits of analytical equipment used for their quantification, hindering their accurate monitoring. Therefore, the development of a pre-concentration technique in order to accurately quantify and monitor these components in aqueous streams is of major relevance. This work addresses the use of liquid-liquid equilibria, applying ionic liquids (ILs), for the extraction and concentration of non-steroidal anti-inflammatory drugs (NSAIDs) from aqueous effluents. Particularly, aqueous biphasic systems (ABSs) composed of ILs and potassium citrate were investigated in the extraction and concentration of naproxen, diclofenac and ketoprofen from aqueous media. Both the extraction efficiency and concentration factor achievable by these systems was determined and evaluated. Within the best conditions, extraction efficiencies of 99.4% and concentration factors up to 13 times were obtained.

Participação parental : papel da web social numa comunidade educativa com surdos

A inclusão de crianças com surdez pode ser potenciada pelo recurso às ferramentas da web social, destacando-se, neste processo, a importância da construção de relações de colaboração entre toda a comunidade educativa, sendo fundamental valorizar o papel das famílias como potenciadoras de aprendizagem nos diferentes contextos para além da escola. Com o estudo apresentado na presente tese pretende-se compreender de que forma a web social é facilitadora do desenvolvimento de comunidades de partilha que potenciem a aprendizagem de novas competências nos pais, nos alunos e nos profissionais envolvidos. Através de uma metodologia de investigação-ação, ao longo de dois ciclos de investigação, foram analisadas as dinâmicas evolutivas de uma comunidade online desenvolvida numa Escola de Referência para a Educação Bilingue de Alunos Surdos e identificados fatores de mudança e melhoria. Houve evidências de melhoria das competências de literacia digital dos vários grupos de participantes e da mais valia da utilização da comunidade online para a comunicação entre pais e profissionais e entre pais e filhos, gerando um maior suporte à aprendizagem das crianças com surdez. Os resultados indicaram haver ainda a necessidade de promover uma maior formação para profissionais e famílias sobre a implementação de dinâmicas de participação parental e sobre a utilização das ferramentas da web social para a personalização de atividades para as crianças com surdez e para a maior comunicação entre casa e escola. A realização deste estudo contribuiu para identificar dinâmicas promotoras da participação parental, alertando para a necessidade de incluir as famílias como parceiros ativos, adequando e individualizando as práticas pedagógicas, onde as próprias crianças têm um papel essencial na aproximação família-escola.

Organic-walled dinoflagellate cysts in recent sediments from the Guadiana river estuary, South-East Portugal

Dissertação de Mestrado, Biologia Marinha, Faculdade de Ciências do Mar e do Ambiente, Universidade do Algarve, 2007

Optimisation of an aptamer-biosensor to detect C-reactive protein

Dissertação de Mestrado, Engenharia Biológica, Faculdade de Engenharia de Recursos Naturais, Universidade do Algarve, 2009

Estudos de reactividade em derivados de compostos heterocíclicos

Dissertação mest., Química Orgânica, Universidade do Algarve, 2008