Test and development of microcapsules for rigid polyurethane foam

Tese de mestrado em Química Tecnológica, apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2016

Development of polyaniline microarray electrodes for cadmium analysis

Disposable screen-printed electrodes (SPCE) were modified using a cosmetic product to partially block the electrode surface in order to obtain a microelectrode array. The microarrays formed were electropolymerized with aniline. Scanning electron microscopy was used to evaluate the modified and polymerized electrode surface. Electrochemical characteristics of the constructed sensor for cadmium analysis were evaluated by cyclic and square-wave voltammetry. Optimized stripping procedure in which the preconcentration of cadmium was achieved by depositing at –1.20 V (vs. Ag/AgCl) resulted in a well defined anodic peak at approximately –0.7 V at pH 4.6. The achieved limit of detection was 4 × 10−9 mol dm−3. Spray modified and polymerized microarray electrodes were successfully applied to quantify cadmium in fish sample digests.

Tratamento de superfícies metálicas por nanotecnologia

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Acompanhamento da reabilitação estrutural da ETA de Morgavel

Relatório de Estágio para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

ECO: argamassas de cal hidráulica para reabilitação de edifícios

Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

Human effector CD8+ T lymphocytes express TLR3 as a functional coreceptor.

TLR are evolutionarily conserved molecules that play a key role in the initiation of innate antimicrobial immune responses. Through their influence on dendritic cell maturation, these receptors are also thought to indirectly shape the adaptive immune response. However, no data are currently available regarding both TLR expression and function in human CD8+ T cell subsets. We report that a subpopulation of CD8+ T cells, i.e., effector, but neither naive nor central memory cells, constitutively expresses TLR3. Moreover, the ligation of the receptor by a specific agonist in TLR3-expressing CD8+ T cells increased IFN-gamma secretion induced by TCR-dependent and -independent stimulation, without affecting proliferation or specific cytolytic activity. These results thereby suggest that TLR3 ligands can not only indirectly influence the adaptive immune response through modulation of dendritic cell activation, but also directly increase IFN-gamma production by Ag-specific CD8+ T cells. Altogether, the present work might open new perspectives for the use of TLR ligands as adjuvants for immunotherapy.

Potential approaches for more successful dendritic cell-based immunotherapy.

INTRODUCTION: Dendritic cells (DCs) are the most important antigen-presenting cell population for activating antitumor T-cell responses; therefore, they offer a unique opportunity for specific targeting of tumors. AREAS COVERED: We will discuss the critical factors for the enhancement of DC vaccine efficacy: different DC subsets, types of in vitro DC manufacturing protocol, types of tumor antigen to be loaded and finally different adjuvants for activating them. We will cover potential combinatorial strategies with immunomodulatory therapies: depleting T-regulatory (Treg) cells, blocking VEGF and blocking inhibitory signals. Furthermore, recommendations to incorporate these criteria into DC-based tumor immunotherapy will be suggested. EXPERT OPINION: Monocyte-derived DCs are the most widely used DC subset in the clinic, whereas Langerhans cells and plasmacytoid DCs are two emerging DC subsets that are highly effective in eliciting cytotoxic T lymphocyte responses. Depending on the type of tumor antigens selected for loading DCs, it is important to optimize a protocol that will generate highly potent DCs. The future aim of DC-based immunotherapy is to combine it with one or more immunomodulatory therapies, for example, Treg cell depletion, VEGF blockage and T-cell checkpoint blockage, to elicit the most optimal antitumor immunity to induce long-term remission or even cure cancer patients.

Nanocarriers for DNA Vaccines: Co-Delivery of TLR-9 and NLR-2 Ligands Leads to Synergistic Enhancement of Proinflammatory Cytokine Release

Adjuvants enhance immunogenicity of vaccines through either targeted antigen delivery or stimulation of immune receptors. Three cationic nanoparticle formulations were evaluated for their potential as carriers for a DNA vaccine, and muramyl dipeptide (MDP) as immunostimulatory agent, to induce and increase immunogenicity of Mycobacterium tuberculosis antigen encoding plasmid DNA (pDNA). The formulations included (1) trimethyl chitosan (TMC) nanoparticles, (2) a squalene-in-water nanoemulsion, and (3) a mineral oil-in-water nanoemulsion. The adjuvant effect of the pDNA-nanocomplexes was evaluated by serum antibody analysis in immunized mice. All three carriers display a strong adjuvant effect, however, only TMC nanoparticles were capable to bias immune responses towards Th1. pDNA naturally contains immunostimulatory unmethylated CpG motifs that are recognized by Toll-like receptor 9 (TLR-9). In mechanistic in vitro studies, activation of TLR-9 and the ability to enhance immunogenicity by simultaneously targeting TLR-9 and NOD-like receptor 2 (NLR-2) was determined by proinflammatory cytokine release in RAW264.7 macrophages. pDNA in combination with MDP was shown to significantly increase proinflammatory cytokine release in a synergistic manner, dependent on NLR-2 activation. In summary, novel pDNA-Ag85A loaded nanoparticle formulations, which induce antigen specific immune responses in mice were developed, taking advantage of the synergistic combinations of TLR and NLR agonists to increase the adjuvanticity of the carriers used.

Graffiti, memory and contested space : mnemonic initiatives following trauma and/or repression in Buenos Aires, Argentina

Graffiti, Memory and Contested Space: Mnemonic Initiatives Following Periods of Trauma and/or Repression in Buenos Aires, Argentina This thesis concerns the popular articulation ofmemory following periods or incidents of trauma in Argentina. I am interested in how groups lay claim to various public spaces in the city and how they convert these spaces into mnemonic battlegrounds. In considering these spaces of trauma and places of memory, I am primarily interested in how graffiti writing (stencils, spray-paint, signatures, etchings, wall-paintings, murals and installations) is used to make these spaces transmit particular memories that impugn official versions of the past. This thesis draws on literatures focused on popular/public memory. Scholars argue that memory is socially constructed and thus actively contested. Marginal initiatives such as graffiti writing challenge the memory projects of the state as well as state projects that are perceived by citizens to be 'inadequate,' 'inappropriate,' and/or as promoting the erasure of memory. Many of these initiatives are a reaction to the proreconciliation and pro-oblivion strategies of previous governments. I outline that the history of silences and impunity, and a longstanding emphasis on reconciliation at the expense of truth and justice has created an environment of vulnerable memory in Argentina. Popular memory entrepreneurs react by aggressively articulating their memories in time and in space. As a result of this intense memory work, the built landscape in Buenos Aires is dotted with mnemonic initiatives that aim to contradict or subvert officially sanctioned memories. I also suggest that memory workers in Argentina persistently and carefially use the sites of trauma as well as key public spaces to ensure official as well as popular audiences . The data for this project was collected in five spaces in Buenos Aires, the Plaza de Mayo, Plaza Congreso, La Republica Cromanon nightclub, Avellaneda Train Station and El Olimpo, a former detention centre from the military dictatorship.

Analyses, persistence an degradation of the synthetic pyrethroid insecticides permethrin and fenvalerate

Studies on persistence and degradation of the synthetic pyrethroid insecticides, permethrin and fenvalerate, were carried out under natural environmental conditions of the Niagara Peninsula. Permethrin and fenvalerate were treated on apple foliage atrat~s of 0.21 kg(AI)!ha and 0.14 kg(AI)/ha, respectively. The initial cis- and trans-permethrin spray deposits were found to be 13.5 ppm and 19.2 ppm, respectively and 38.0 ppm was observed for the fenvalerate treated sample. Twenty-three days and 84 days after spray application, permethrin residues were 4.0 ppm and 2.7 ppm for the cis-isomer, whereas they were 7.9 ppm and 4.7 ppm for the trans-isomer, respectively. Residues of fenvalerate 23 days and 84 days after spray application were 13.4 ppm and 8.0 ppm, respectively. The values of observed half-life of cis-permethrin, trans-permethrin and fenvalerate were found to be 42 days, 46 days and 51 days, respectively. Studies were extended to quantitatively determine some of the major degradation compounds of permethrin and fenvalerate, which were expected to be produced as results of ester cleavage of the parent compounds. A permethrin treated sample, 84 days after initial spray application, showed 0.25 and 0.8 ppm of cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (C12CA (18), respectively. These two acids were not found as free acids, but found as conjugated compounds. The other expected degradation compounds, 3-phenoxybenzyl alcohol (PBalc (~)),3-phenoxybenz.aldehyde (PBald (38)) and 2- (4-chlorophenyl) isovaleric acid (CPIA (31)) were not detected by the methods employed in this study. The results indicate that these degradation compounds were not present, or, if they were present, their concentrations were too low to detect by the methods used.

An HPLC method for simultaneous determination of residual benomyl and MBC on apple foliage without cleanup

A simple High Performance Liquid Chromatograph (HPLC) method has been developed to identify benamyl (methyl 1- (butylcarbamoyl)-2-benzimidazole carbamate) and MBC (methyl 2-benzimidazole carbamat~ residues on apple leaves without cleanup. Sample leaves are freeze dried in a Mason jar and residues are then extracted by tumbling them in chloroform containing 5,000 microgram per milliliter of n-propyl isocyanate (PIC) at 10 C. To the extract, n-butyl isocyanate (BIC) was added at 5,000 microgram per milliliter and 20 microliter of this mixture injected onto the HPLC system. Separation is accomplished by the use of a Brownlee LiChrosorb silica gel column with a guard column and' operated with a mixed mobile phase consisting of chloroform and hexane (4:1) saturated with water. MBC, a degradation product of benomyl is identified if present as methyl l-(npropyl carbamoyl)-2-benzimidazole carbamate (MBC-n-PIC). Both benomyl and MBC-n-PIC can be detected with aKUltraviolet (UV) detector (280nm) at a concentration as low as 0.2 microgram per milliliter in apple leaves. The fate of benomyl on apple foliage after spray application of benomyl (Ben late 50 per cent wettable powder) was investigated by the method thus described. Benomyl quickly dissipated during the first 3-7 days, but the dissipatio'n sltowed down thereafter. In contrast, the concentration of MBC in leaves gradually increased after repeated applications of Benlate.

Development and characterization of concentric capillary nebulizer used in inductively coupled plasma analysis /

A simple, low-cost concentric capillary nebulizer (CCN) was developed and evaluated for ICP spectrometry. The CCN could be operated at sample uptake rates of 0.050-1.00 ml min'^ and under oscillating and non-oscillating conditions. Aerosol characteristics for the CCN were studied using a laser Fraunhofter diffraction analyzer. Solvent transport efficiencies and transport rates, detection limits, and short- and long-term stabilities were evaluated for the CCN with a modified cyclonic spray chamber at different sample uptake rates. The Mg II (280.2nm)/l\/lg 1(285.2nm) ratio was used for matrix effect studies. Results were compared to those with conventional nebulizers, a cross-flow nebulizer with a Scott-type spray chamber, a GemCone nebulizer with a cyclonic spray chamber, and a Meinhard TR-30-K3 concentric nebulizer with a cyclonic spray chamber. Transport efficiencies of up to 57% were obtained for the CCN. For the elements tested, short- and long-term precisions and detection limits obtained with the CCN at 0.050-0.500 ml min'^ are similar to, or better than, those obtained on the same instrument using the conventional nebulizers (at 1.0 ml min'^). The depressive and enhancement effects of easily ionizable element Na, sulfuric acid, and dodecylamine surfactant on analyte signals with the CCN are similar to, or better than, those obtained with the conventional nebulizers. However, capillary clog was observed when the sample solution with high dissolved solids was nebulized for more than 40 min. The effects of data acquisition and data processing on detection limits were studied using inductively coupled plasma-atomic emission spectrometry. The study examined the effects of different detection limit approaches, the effects of data integration modes, the effects of regression modes, the effects of the standard concentration range and the number of standards, the effects of sample uptake rate, and the effect of Integration time. All the experiments followed the same protocols. Three detection limit approaches were examined, lUPAC method, the residual standard deviation (RSD), and the signal-to-background ratio and relative standard deviation of the background (SBR-RSDB). The study demonstrated that the different approaches, the integration modes, the regression methods, and the sample uptake rates can have an effect on detection limits. The study also showed that the different approaches give different detection limits and some methods (for example, RSD) are susceptible to the quality of calibration curves. Multicomponents spectral fitting (MSF) gave the best results among these three integration modes, peak height, peak area, and MSF. Weighted least squares method showed the ability to obtain better quality calibration curves. Although an effect of the number of standards on detection limits was not observed, multiple standards are recommended because they provide more reliable calibration curves. An increase of sample uptake rate and integration time could improve detection limits. However, an improvement with increased integration time on detection limits was not observed because the auto integration mode was used.

Niagara from the distant Tower, U.S.A.

The image is described as "(7) Niagara and its great cloud of rising Spray - from the distant tower, U.S.A.".

Maid of the Mist, Niagara, U.S.A.

The description of the image is "(6) Majestically Grand - the Falls from the 'Maid of the Mist,' Niagara, U.S.A.". The reverse of the image reads "You are on the deck of the small but sturdy little steamer that runs along near the foot of the falls. At this moment you are pretty nearly mid-stream, looking south. The American shore are up over your left shoulder. That tall, dark cliff at the extreme left of what you see is Goat Island. The people up there outlined against the sky look like dolls and no wonder; they are more than 160 feet above your head. Some of them are looking off over the unspeakable grandeurs of the Horseshoe Fall there at the right; some are without doubt looking down at the very boat and remarking that the passengers look like dolls. It is an awesome experience to go so near that never-ceasing downpour of waters from the sky. The air is full of the roar and iridescent spray, and it seems as if the boat must be drawn in under the overwhelming floods never to rise again. Yet, curiously enough, the river right around the boat is not so madly excited as you might expect. It seems more like some great creature, dazed, bewildered, stunned by some incredible experience and not yet quite aware of what has happened. (When it gets down into the Whirlpool Rapids, two miles below here, it is dramatically alive to its situation!) The gigantic curve of the cliffs, reaching in up-stream straight ahead, makes a contour line of over 3000 feet before it comes up against the Canadian banks on the west (right). Geologists say that the Falls ages ago must have been at least seven miles farther down the river (behind you) and have gradually won their way back. Even now the curve of the Horseshoe is worn away from two to four feet in a year. No wonder; 12, 000, 000 cubic feet of water (about 375, 000 tons) sweep over the rocks in one minute, and the same the next minute and the next and the next. See Niagara through the Stereoscope, with special maps locating all the landmarks about the Falls.

View of Falls from Steel Bridge, Niagara, U.S.A.

The description of the image reads "(4)-8972-General view of Falls from new steel bridge - Maid of the Mist at landing - Niagara, U.S.A." The reverse of the image includes the description, "We are standing on the new steel bridge over Niagara River, 190 feet above the water and looking a little west of south, up the river towards Lake Erie. The high cliff at the extreme left, on the American side, is Prospect Point, where a crowd is gathered at this moment to view the Falls that we see just beyond Prospect Point. That dark, tree-covered mass of rock beyond is Goat Island; and just this side of Goat Island we see a bit of its precipice has been cut off separate from the rest by the powerful current of the waters - the smaller portion is Luna Island, and the Luna Falls go pouring down between the two islands. The face of the precipice curves inward beneath the Luna Falls leaving behind the 160 foot sheet of water the unearthly hollow known as the Cave of the Winds. Beyond Goat Island we see the gigantic curve of the Horseshoe Falls, 3,010 feet long and 158 feet high, reaching around through the clouds of spray to the farther Canadian shore. (The boundary line between British and American territory is in mid-stream.) It has been estimated that every minute 375,000 tons of water pour over these Horseshoe Falls, and they are wearing away the cliffs, moving back up the stream at the rate of 2.4 feet per year. It was probably only about a thousand years ago that they took their plunge just about where we stand now. Down there below us, at the wharf is the Maid of the Mist at the American landing taking on passengers who have come down the steep bank by the inclined railway. Its course takes it through those clouds of spray almost to the very foot of both Falls, - waters falling from 167 feet overhead, and water surging at least as many feet deep under the staunch little vessel. See special 'keyed' maps of Niagara pub. by Underwood and Underwood, also the Niagara Book by Mark Twain, W.D. Howells and others."