Coupling organic substrate removal to methane production in a fully biological microbial electrolysis cell

Microbial electrolysis cells (MECs) are an innovative and emerging technique based on the use of solid-state electrodes to stimulate microbial metabolism for wastewater treatment and simultaneous production of value-added compounds (such as methane). This research studied the performance of a two-chamber MEC in terms of organic matter oxidation (at the anode) and methane production (at the cathode). MEC‟s anode had been previously inoculated with an activated sludge, whereas the cathode chamber inoculum was an anaerobic sludge (containing methanogenic microorganisms). During the experimentation, the bioanode was continuously fed with synthetic solutions in anaerobic basal medium, at an organic load rate (OLR) of around 1 g L-1 d-1, referred to the chemical oxygen demand (COD). At the beginning (Run I), the feeding solution contained acetate and subsequently (Run II) it was replaced with a more complex solution containing soluble organic compounds other than acetate. For both conditions, the anode potential was controlled at -0.1 V vs. standard hydrogen electrode, by means of a potentiostat. During Run I, over 80% of the influent acetate was anaerobically oxidized at the anode, and the resulting electric current was recovered as methane at the cathode (with a cathode capture efficiency, CCE, accounting around 115 %). The average energy efficiency of the system (i.e., the energy captured into methane relative to the electrical energy input) under these conditions was over 170%. However, reactor‟s performance decreased over time during this run. Throughout Run II, a substrate oxidation over 60% (on COD basis) was observed. The electric current produced (57% of coulombic efficiency) was also recovered as methane, with a CCE of 90%. For this run the MEC‟s average energy efficiency accounted for almost 170 %. During all the experimentation, a very low biomass growth was observed at the anode whereas ammonium was transferred through the cationic membrane and concentrated at the cathode. Tracer experiments and scanning electron microscopy analyses were also carried out to gain a deeper insight into the reactor performance and also to investigate the possible reasons for partial loss of performance. In conclusion, this research suggests the great potential of MEC to successfully treat low-strength wastewaters, with high energy efficiency and very low sludge production.

Therapeutics bioconjugates: evaluation of iminoboronates as payload delivery system for cancer

The advent of bioconjugation impacted deeply the world of sciences and technology. New biomolecules were found, biological processes were understood, and novel methodologies were formed due to the fast expansion of this area. The possibility of creating new effective therapies for diseases like cancer is one of big applications of this now big area of study. Off target toxicity was always the problem of potent small molecules with high activity towards specific tumour targets. However, chemotherapy is now selective due to powerful linkers that connect targeting molecules with affinity to interesting biological receptors and cytotoxic drugs. This linkers must have very specific properties, such as high stability in plasma, no toxicity, no interference with ligand affinity nor drug potency, and at the same time, be able to lyse once inside the target molecule to release the therapeutic warhead. Bipolar environments between tumour intracellular and extracellular medias are usually exploited by this linkers in order to complete this goal. The work done in this thesis explores a new model for that same task, specific cancer drug delivery. Iminoboronates were studied due to its remarkable selective stability towards a wide pH range and endogenous molecules. A fluorescence probe was design to validate this model by creating an Off/On system and determine the payload release location in situ. A process was optimized to synthetize the probe 8-(1-aminoethyl)-7-hydroxy-coumarin (1) through a reductive amination reaction in a microwave reactor with 61 % yield. A method to conjugate this probe to ABBA was also optimized, obtaining the iminoboronate in good yields in mild conditions. The iminoboronate model was studied regarding its stability in several simulated biological environments and each half-life time was determined, showing the conjugate is stable most of the cases except in tumour intracellular systems. The construction of folate-ABBA-coumarin bioconjugate have been made to complete this evaluation. The ability to be uptaken by a cancer cell through endocytosis process and the conjugation delivery of coumarin fluorescence payload are two features to hope for in this construct.

Seleção das estruturas calcificadas para determinação da idade da piracatinga Calophysus macropterus Lichtenstein (Siluriformes: Pimelodidae) na Amazônia Central, Brasil

O objetivo deste trabalho foi identificar a estrutura calcificada mais adequada para a determinação da idade da piracatinga (Calophysus macropterus). Foram analisados 440 indivíduos procedentes da pesca comercial e experimental do Baixo Solimões. Deste total, foram analisados opérculos, otólitos (asteriscus) e vértebras de uma sub-amostra de 130 indivíduos. Para a observação dos anéis de crescimento nos otólitos, foram testadas duas técnicas de clarificação e quatro técnicas de coloração nas vértebras. A análise das estruturas calcificada demonstrou que os otólitos são estruturas pouco translúcidas e apresentam dificuldades para a observação das marcas de crescimento. Por outro lado os opérculos não apresentaram marcas visíveis de crescimento, e nas vértebras foi observado um padrão nítido e estável de marcação de anéis de crescimento. Portanto, as vértebras foram as estruturas mais adequadas para determinar a idade da piracatinga, além de apresentar uma relação linear significativa entre o raio total das vértebras e o comprimento do peixe (r=0,91; P<0,05). Entre os métodos testados para a visualização dos anéis nas vértebras de peixes teleosteos, a técnica nova a de Hiper-oxidação e Descalcificação Química (HDQ), mostrou ser a melhor. As marcas de crescimentos em vértebras foram validadas utilizando o método de incremento marginal relativo. A piracatinga forma duas marcas de crescimento por ano nas vértebras; o primeiro durante a vazante (agosto) e o segundo durante a enchente (janeiro).

Infecção natural por tripanosomatídeos (Kinetoplastida: Trypanosomatidae) em Lutzomyia umbratilis (Diptera: Psychodidae) em áreas de leishmaniose tegumentar americana no Amazonas, Brasil

Durante o período de 2002 a 2003 foram realizadas coletas de flebotomíneos em duas áreas do estado do Amazonas (Base de treinamento militar - BI1 e Tarumã Mirim). Nessas coletas foram capturadas um total de 1.440 fêmeas de Lutzomyia (Nyssomyia) umbratilis. Lu.umbratilis é a principal responsável pela transmissão da Leishmaniose Tegumentar Americana (LTA) ao norte do Rio Amazonas. Do total coletado apenas 15 espécimens (ou 1,04%) apresentaram infecção natural por tripanosomatídeos, sendo 12 na BI1 e 3 em Tarumã-Mirim. Isso representou uma taxa de infecção de 1,66% (12 dos 720 capturados em BI1) e 0,42% (3 dos 720 em Tarumã-Mirim). Estes resultados confirmam as informações prévias por outros autores de reduzidos valores de infecção natural por tripanosomatídeos em flebotomíneos, mesmo em áreas altamente endêmicas para leishmaniose.

Aminobenzocoumarinylmehtyl esters as photoactive precursors for the release of butyric acid

The evaluation of the photorelease of a carboxylic acid drug, using butyric acid as a representative model, was carried out by using 7-amino-4-chloromethyl-2-oxo-2Hnaphtho[1,2-b] pyran, an aminobenzocoumarin, and its mono- and di-methylated or ethylated derivatives. This study was intended to improve the release of butyric acid from benzocoumarins by the addition of an amino group to the heterocycle by applying the knowledge of second-generation coumarinylmethyl-based photoremovable protecting groups. Photolysis studies were performed on the resultant ester cages by irradiation in a photochemical reactor at 254, 300, 350 and 419 nm, using methanol/HEPES buffer 80:20 solutions as solvent. The data obtained showed that these new fluorescent aminobenzocoumarins are superior to all the previously tested benzocoumarins with the same or different ring fusions. As well as the photolysis, the photophysics of the compounds were characterised by both steady state and time-resolved methods.

Searches for heavy long-lived charged particles with the ATLAS detector in proton--proton collisions at s√ = 8 TeV

Searches for heavy long-lived charged particles are performed using a data sample of 19.8 fb−1 from proton--proton collisions at a centre-of-mass energy of s√ = 8 TeV collected by the ATLAS detector at the Large Hadron Collider. No excess is observed above the estimated background and limits are placed on the mass of long-lived particles in various supersymmetric models. Long-lived tau sleptons in models with gauge-mediated symmetry breaking are excluded up to masses between 440 and 385 GeV for tan(beta) between 10 and 50, with a 290 GeV limit in the case where only direct tau slepton production is considered. In the context of simplified LeptoSUSY models, where sleptons are stable and have a mass of 300 GeV, squark and gluino masses are excluded up to a mass of 1500 and 1360 GeV, respectively. Directly produced charginos, in simplified models where they are nearly degenerate to the lightest neutralino, are excluded up to a mass of 620 GeV. R-hadrons, composites containing a gluino, bottom squark or top squark, are excluded up to a mass of 1270, 845 and 900 GeV, respectively, using the full detector; and up to a mass of 1260, 835 and 870 GeV using an approach disregarding information from the muon spectrometer.

Comparison of oleate conversion under microaerophilic and anaerobic conditions

Excessive accumulation of Long Chain Fatty Acids (LCFA) in methanogenic bioreactors is the cause of process failure associated to a severe decrease in methane production. In particular, fast and persistent accumulation of palmitate is critical and still not elucidated. Aerobes or facultative anaerobes were detected in those reactors, raising new questions on LCFA biodegradation. To get insight into the influence of oxygen, two bioreactors were operated under microaerophilic and anaerobic conditions, with oleate at 1 and 4 gCOD/(L d). Palmitate accumulated up to 2 and 16 gCOD/L in the anaerobic and microaerophilic reactor, respectively, which shows the importance of oxygen in this conversion. A second experiment was designed to understand the dynamics of oleate to palmitate conversion. A CSTR and a PFR were assembled in series and fed with oleate under microaerophilic conditions. HRT from 6 to 24 h were applied in the CSTR, and 14 to 52 min in the PFR. In the PFR a biofilm was formed where palmitate accounted for 82% of total LCFA. Pseudomonas was the predominant genus (42 %) in this biofilm, highlighting the role of aerobic and facultative anaerobic bacteria in LCFA bioconversion.

Pró-fármacos fotoativáveis do péptido AAPV: síntese e avaliação da libertação controlada por luz

Dissertação de mestrado em Bioquímica Aplicada (área de especialização em Biomedicina)

Libertação fotocontrolada de moléculas bioativas a partir de conjugados de cumarinas

Dissertação de mestrado em Química Medicinal

Questões de género nas revistas generalistas de informação em Portugal: cruzamentos temáticos na Sábado e Visão

As revistas de informação generalista configuram uma interseção entre as representações socioeconómicas, políticas e culturais e os quotidianos da população. Neste artigo apresentamos uma análise temática das revistas de informação generalista Sábado e Visão, as mais lidas do segmento em Portugal. O corpus de análise foi composto por 440 peças jornalísticas de 104 edições que correspondem a todos os números editados em 2011 por estas duas publicações. O estudo empírico, realizado com recurso ao software NVivo 10, revela uma transversalidade da abordagem aos temas político-económicos, espelho da conjuntura nacional e internacional no ano de 2011. As diferenças mais visíveis entre as duas revistas revelam uma maior opção pelos temas Sexualidades e Relações de Intimidade e Jet set na Sábado e Saúde, Lazer e bem-estar na Visão. Além disso, no que concerne às representações de género, presentes em vários temas, surgem na generalidade assentes num binarismo que transpõe o olhar da dimensão de género para o sexo biológico e que opõe as representações tradicionais da feminilidade e masculinidade, condicionando o surgimento de representações alternativas.

Carbon materials as new generation of new electron shuttles for the anaerobic degradation of environmental xenobiotics

Tese de Doutoramento em Engenharia Química e Biológica

Remoção fotocatalítica de micropoluentes em meios porosos funcionalizados

Dissertação de mestrado integrado em Engenharia Civil

Aortic stenosis. Gender influence on left ventricular geometry and function in patients under 70 years of age

OBJECTIVE: To verify if adaptive left ventricle (LV) characteristics are also present in individuals under 70 years of age with severe aortic stenosis (AS). METHODS: The study comprised 40 consecutive patients under 70 years of age with AS and no associated coronary artery disease, referred for valve surgery. Out of the 40 patients, 22 were men and 18 women, and the mean age was 49.8±14.3 years. Cardiac symptoms, presence of systemic hypertension (SH), functional class according to the New York Heart Association (NYHA), and valve lesion etiology were considered. LV cavity dimensions, ejection fraction (EF), fractional shortening (FS), mass (MS), and relative diastolic thickness (RDT) were examined by Doppler echocardiography. RESULTS: Fourteen (63.6%) men and 11 (61.6%) women were classified as NYHA class III/IV (p=0.70). There was no difference in the frequency of angina, syncope or dyspnea between genders. The incidence of SH was greater in women than in men (10 versus 2, p=0.0044). Women had a smaller LV end-diastolic diameter index (32.1±6.5 x 36.5±5.3mm/m², p=0.027), LV end-systolic diameter index (19.9±5.9 x 26.5±6.4mm/m², p=0.0022) and LV mass index (MS) (211.4±71.1 x 270.9±74.9g/m², p=0.017) when compared with men. EF (66.2±13.4 x 52.0±14.6%, p=0.0032), FS (37.6±10.7 x 27.9±9.6%, p=0.0046) and RDT (0.58±0.22 x 0.44±0.09, p=0.0095) were significantly greater in women than in men. CONCLUSION: It is the patient gender rather than age that influences left ventricular adaptive response to AS.

In-stent restenosis. Acute and long-term outcomes after excimer laser coronary angioplasty

OBJETIVE: With the increased use of intracoronary stents, in-stent restenosis has become a clinically significant drawback in invasive cardiology. We retrospectively assessed the short- and long-term outcomes after excimer laser coronary angioplasty of in-stent restenosis. METHODS: Twenty-five patients with 33 incidents of in-stent restenosis treated with excimer laser coronary angioplasty (ELCA) were analyzed. Sixty-six percent were males, mean age of 73±11 years, and 83% were functional class III-IV (NYHA). ELCA was performed using 23 concentric and 10 eccentric catheters with a diameter of 1.6-2.2 mm, followed by balloon angioplasty (PTCA) and ultrasound monitoring. The procedure was performed in the following vessels: left anterior descending artery, 10; left circumflex artery, 8; right coronary artery, 6; left main coronary artery, 2; and venous bypass graft, 7. RESULTS: The ELCA was successful in 71% of the cases, and PTCA was 100% successful. The diameter of the treated vessels was 3.44±0.5mm; the minimal luminal diameter (MLD) increased from 0.30mm pre-ECLA to 1.97mm post-ELCA, and to 2.94mm post-PTCA (p<0.001). The percent stenosis was reduced from 91.4±9.5% before ECLA to 42.3±14.9% after ELCA and to 14.6 ± 9.3% after PTCA (p<0.001). Seventeen (68%) patients were asymptomatic at 6 months and 15 (60%) at 1 year. New restenosis rates were 8/33 (24.2%) at 6 months and 9 /33 (27.3%) at 12 months. CONCLUSION: ELCA is safe and effective for the treatment of in-stent restenosis. In the present sample, a slight increase in new restenotic lesions between 6 and 12 months was found.

In vivo imaging of glycol chitosan-based nanogel biodistribution

The preclinical development of nanomedicines raises several challenges and requires a comprehensive characterization. Among them is the evaluation of the biodistribution following systemic administration. In previous work, the biocompatibility and in vitro targeting ability of a glycol chitosan (GC) based nanogel have been validated. In the present study, its biodistribution in the mice is assessed, using near-infrared (NIR) fluorescence imaging as a tool to track the nanogel over time, after intravenous administration. Rapid whole body biodistribution of both Cy5.5 labeled GC nanogel and free polymer is found at early times. It remains widespreadly distributed in the body at least up to 6 h postinjection and its concentration then decreases drastically after 24 h. Nanogel blood circulation half-life lies around 2 h with the free linear GC polymer presenting lower blood clearance rate. After 24 h, the blood NIR fluorescence intensity associated with both samples decreases to insignificant values. NIR imaging of the organs shows that the nanogel had a body clearance time of 48 h, because at this time point a weak signal of NIR fluorescence is observed only in the kidneys. Hereupon it can be concluded that the engineered GC nanogel has a fairly long blood circulation time, suitable for biomedical applications, namely, drug delivery, simultaneously allowing efficient and quick body clearance.