Mechanochemical solvent-free synthesis of Sn-β Zeolite and Ag2O/TiO2 catalysts

Preparations of heterogeneous catalysts are usually complex processes that involve several procedures as precipitation, crystallization and hydrothermal treatments. This processes are really dependent by the operative conditions such as temperature, pH, concentration etc. Hence the resulting product is extremely affected by any possible variations in these parameters making this synthesis really fragile. With the aim to improve these operations has been decided to exploit a new possible strong environment-respectful process by mechanochemical treatment, which permits to carry out solvent free-solvent synthesis exploiting the Mixer Mill MM400 (Retsch) in order to have reproducible results. Two different systems have been studied in this kind of synthesis: a tin β -zeolite tested in a H-trasnfer reaction of cyclohexanone and a silver on titania catalyst used in the fluorination of 2,2 dimethyl glucaric acid. Each catalyst has been characterized by different techniques in order to understand the transformations involved in the mechanochemical treatment.

Optics-Based Quantum Information and Sensing Platforms Utilizing the Nitrogen-Vacancy Center in Diamond

Thesis (Ph.D.)--University of Washington, 2016-08

Criação de estabilidade numa linha de produção de argamassas em pó

Com as constantes mudanças de mercado, as empresas enfrentam cada vez mais obstáculos para se manterem competitivas e inovadoras, para isso procuram formas de sobreviver seguindo filosofias e utilizando ferramentas que permita atingir os seus objetivos. A filosofia Lean é uma filosofia seguida por muitas empresas que pretendam criar valor eliminando desperdícios. O objetivo deste projeto passa pela implementação de ferramentas Lean de modo a criar estabilidade no processo produtivo, eliminando desperdícios e criando valor. Com foco neste objetivo estudou-se as principais fontes de variabilidade no processo produtivo nos 4M’s (Máquina, Método, Mão-de-Obra e Máquina). Após essa análise foram implementadas ações de melhoria como os 5S, criação de sistemas visuais, redução do tempos de setup e tempos de espera, introdução de kanbans e padronização dos métodos de trabalho.Com a implementação destas medidas foi possível tornar o processo produtivo mais estável e flexível, com capacidade para responder às constantes alterações de mercado.

Peer Relationships in School-Age Children with Autism: Concurrent and Longitudinal Predictors

Thesis (Ph.D.)--University of Washington, 2016-08

Extração de blocos graníticos nas pedreiras de Cinza Ariz e Amarelo Macieira da empresa Polimagra – Granitos, S.A

A perfuração em maciços rochosos desempenha um papel fundamental na área da exploração e extração de rocha ornamental, nomeadamente em granitos. Para esse efeito, e como irá ser abordado neste trabalho, são utilizados pela empresa Polimagra – Granitos, S.A, nas pedreiras que explora, dois sistemas de perfuração: perfuração hidráulica e perfuração pneumática. Sendo um dos objetivos deste trabalho perceber qual o tipo de perfuração que apresenta maior rentabilidade, torna-se importante perceber as principais características dos dois sistemas de perfuração em estudo. Para isso, com a realização deste estágio curricular na empresa Polimagra – Granitos, S.A, foi possível comparar as principais diferenças dos dois sistemas utilizados, através do acompanhamento dos trabalhos de lavra em pedreiras, da cronometragem de tempos de perfuração em maciço rochoso granítico e da realização de um estudo de fracturação nas pedreiras de Cinza Ariz e Amarelo Macieira. Durante este tempo do estágio foi ainda possível acompanhar os diferentes métodos de transformação utilizado sobre os diferentes granitos obtidos, nas instalações fabris da empresa Polimagra – Granitos, S.A. De destacar ainda, e dentro da área da transformação do granito, a utilização de um sistema robótico de tecnologia de ponta, para corte, acabamento e embalamento de produtos em granito.

Rearing effect of biofloc on antioxidant and antimicrobial transcriptional response in Litopenaeus stylirostris shrimp facing an experimental sub-lethal hydrogen peroxide stress

This study compares the antioxidant and antimicrobial transcriptional expression of blue shrimps reared according to two different systems, BioFloc Technology (BFT) and Clear sea Water (CW) and their differential responses when facing an experimental sublethal hydrogen peroxide stress. After 30 days of rearing, juvenile shrimps were exposed to H2O2 stress at a concentration of 30 ppm during 6 hours. The oxidative stress caused by H2O2 was examined in the digestive glands of the shrimp, in which antioxidant enzyme (AOE) and antimicrobial peptide (AMP) gene expression were analysed by quantitative real-time PCR. Results showed that rearing conditions did not affect the expression of genes encoding AOEs or AMPs. However, H2O2 stress induced a differential response in expression between shrimps from the two rearing treatments (BFT and CW). Comparative analysis of the expression profiles indicates that catalase transcripts were significantly upregulated by H2O2 stress for BFT shrimps while no change was observed for CW shrimps. In contrast, H2O2 caused down-regulation of superoxide dismutase and glutathione transferase transcripts and of the three AMP transcripts studied (penaeidin 2 and 3, and crustin) for CW shrimps, while no effect was observed on BFT shrimp transcript levels. These results suggested that BFT shrimps maintained antioxidant and AMP responses after stress and therefore can effectively protect their cells against oxidative stress, while CW shrimp immune competence seems to decrease after stress.

Nitrogênio mineral em um latossolo em função de sistemas de manejo do solo e de culturas de cobertura de inverno

The increasing advancement of agriculture makes providing adequate conditions for the growth and development of plants is the primary purpose of soil management systems. Much of the success of PD is attributed to cultural remains left by cover crops that do not require high nitrogen inputs and can thus be used to reduce nitrogen input in the agro- ecosystem. The nitrogen is one of the elements applied in agriculture, it is absorbed in higher quantities and limiting the yield of grain crops such as corn. Thus, there has been the influence of the no-till and conventional tillage combined with different crops of winter cover and bare soil when in succession to corn, on mineral nitrogen content. The experimental work was made at the experimental station of the Agronomic Institute of Paraná - Iapar. The implemented design was blocks at random split plot with three replications in factorial 6 x 2 x 3 x 5. The main plots were as treatment, beyond the bare soil, 5 winter species (ryegrass, vetch, vetch + oat, oat and radish), while in the subplots were used two tillage systems (No-till and conventional tillage). Three collections made were (before management, the urea before and after the urea), these being held in 5 depths (0-5, 5-10, 10-20, 20-40 and 40-60 cm). So a layer 0-5 cm and a que presents increased amount to NH4 + ion. The use of associated PD system in the presence of winter cover crops decreased as NO3 - losses in soil profile.

Aquatic weeds hotspots in the Lake Victoria basin Uganda and on Lake Kyoga: implications for their management

Proliferation of invasive aquatic weeds has developed into a major ecological and socio economic issue for many regions of the world. As a consequence, inference on where to target control and other management efforts is critical in the management of aquatic weeds (Ibáñez et al., 2009). Notwithstanding, aquatic systems in Uganda in general and in the basins of Lakes Victoria and Kyoga in particular, have fallen victims to aquatic weeds invasion and subsequent infestation. If these aquatic weeds infestations are to be minimized and their impacts mitigated, management decisions ought to be based on up-to-date data and information in relation to location of infestation hotspots. Aquatic systems in the basins of the two production systems are important sources of livelihoods especially from fish production and trade yet they are prone to infestation by aquatic weeds. Thus, the invasion and subsequent infestation of aquatic ecosystems by aquatic weeds pose a major conservation threat to various aquatic resources (Catford et al., 2011; Kayanja, 2002). This paper examines the extent to which aquatic weeds have infested aquatic ecosystems in the basins of Lakes Victoria and Kyoga. The information is expected to guide management of major aquatic weeds through rational allocation of the scarce resources by targeting hotspots.

A bistable reaction-diffusion system in a stretching flow

We examine the evolution of a bistable reaction in a one-dimensional stretching flow, as a model for chaotic advection. We derive two reduced systems of ordinary differential equations (ODEs) for the dynamics of the governing advection-reaction-diffusion partial differential equations (PDE), for pulse-like and for plateau-like solutions, based on a non-perturbative approach. This reduction allows us to study the dynamics in two cases: first, close to a saddle-node bifurcation at which a pair of nontrivial steady states are born as the dimensionless reaction rate (Damkoehler number) is increased, and, second, for large Damkoehler number, far away from the bifurcation. The main aim is to investigate the initial-value problem and to determine when an initial condition subject to chaotic stirring will decay to zero and when it will give rise to a nonzero final state. Comparisons with full PDE simulations show that the reduced pulse model accurately predicts the threshold amplitude for a pulse initial condition to give rise to a nontrivial final steady state, and that the reduced plateau model gives an accurate picture of the dynamics of the system at large Damkoehler number. Published in Physica D (2006)

Avaliação da ecotoxicidade de percolados em áreas de disposição de resíduos na região metropolitana de Natal/RN

Leachates are effluent produced by decomposition of solid waste, they have complex composition and can be highly toxic. Therefore such percolated liquid should be collected and treated properly to avoid environmental contamination of soil and of water bodies. The objective of this study was to evaluate the toxicity through ecotoxicological tests with Ceriodaphnia dubia (Cladocera - Crustacea) of percolated liquids generated in two different systems of municipal solid waste (MSW) disposal in the city of Natal/ RN: A Sanitary Landfill in the Metropolitan Region of Natal/ RN, and in a dump off area. Furthermore, it was evaluated the possible contamination of the underground water of the dump off area. Two monthly samples were taken at four points between the months of May/2009 and January/2010. The Point "A" corresponds to the end of the pond leachate treatment in ASRMN; The Point "B" corresponds to a containment pond at the dump. The Point "C" is an area near one of the cells of the dump off area where the leachate outcrops; The Point "D" stands for an underground water well at the area. The last point, called "E" was sampled only once and corresponds to the slurry produced by temporary accumulation of solid waste in the open area of the dump. The ecotoxicological tests, acute and chronic, followed the ABNT 13373/2005 rules, with some modifications. The samples were characterized by measuring the pH number, the dissolved oxygen (DO), the salinity, BOD5, COD, Cd, Cu, Pb, Cr, Fe, Mg, Ni, and Zn. At Point A, the average number of EC50-48h ranged between 1.0% and 2.77% (v/v), showing a high toxicity of the leachate to C.dubia in all months. To this point, positive correlations were found between the EC50- 48 with precipitation. Negative correlations were found between the EC50- 48h with salinity. At point B there was no response of the acute exposure of organisms to the test samples. At point C the EC50-48h ranged from 17.68% to 35.36% in just two months of the five ones analyzed, not correlated meaning. Point D, the EC50-48h level ranged between 12.31% and 71.27%, showed a negative correlation with, only, precipitation. Although it was observed toxicity of underground water in the Landfill Area, there was no evidence of water contamination by leachate, however, due to the toxic character of this water, additional tests should be conducted to confirm the quality of water that is used for human supply. At point E there was no acute toxicity. These results support the dangers of inappropriate disposal of MSW to water bodies due to the high toxicity of the leachate produced highlighting the necessity of places of safe confinement and a treatment system more effective to it

Performance Energética no contexto do sistema LEED

Com o aumento constante de procura de recursos naturais por parte dos vários setores da sociedade é urgente encontrar soluções para reduzir o seu consumo sem se travar a expansão demográfica que se tem vindo a sentir nos grandes centros urbanos. É através da implementação de medidas de sustentabilidade e pelo aumento da eficiência de utilização desses recursos que se tem vindo a combater esta tendência cada vez maior de consumismo global, sendo isto apenas possível com a implementação de ferramentas tecnológicas avançadas que permitem estabelecer limites ao considerado eficiente e premiando, em termos financeiros e de imagem de marketing, as entidades que o alcancem. O LEED é um sistema de certificação de sustentabilidade voluntário de edifícios residenciais e comerciais que estabelece métricas de comparação de parâmetros indicadores de consumos energéticos, hídricos e de materiais em todo o ciclo de vida do edifício e que tem vindo a ganhar destaque em crescendo a nível mundial. Esta dissertação teve como objetivo comparar a performance de consumo energético no âmbito do sistema LEED com a do sistema de certificação energética de edifícios nacional (SCE) de um grande edifício de serviços, estabelecendo um paralelismo de semelhanças e diferenças entre os dois e de avaliar os efeitos de potenciais medidas de eficiência energética e seus efeitos nas classificações de mérito obtidas em cada sistema. Os resultados obtidos na simulação que permitiu avaliar a performance foi muito satisfatório, tendo sido aproveitado pela empresa para efeitos de certificação LEED do edifício em estudo.

Trapping phosphorus (III) into polyoxometalates: synthesis, characterisation and electronic behaviour study

The introduction of electronically-active heteroanions into polyoxometalates (POMs) is one of the emerging topics in this field. The novel clusters have shown unprecedented intramolecular electron-transfer features that can be directly mediated by the incorporated heteroanions. In this thesis, we will focus on the study of phosphite (HPO32-) as new non-traditional heteroanions, discover HPO32- templated nanostructures, investigate their electronic behaviours as well as understand the self-assembly process of HPO32--templated species. The thesis starts with incorporating HPO32- into POM cages. The feasibility of this work was illustrated by the successful trapping of HPO32- into a “Trojan Horse” type {W18O56} nanocage. The reactivity of embedded {HPO3} was fully studied, showing the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerise to form a weakly interacting (O3PH···HPO3) moiety. In the crystalline state a temperature-dependent intramolecular redox reaction and structural rearrangement occurs. This rearrangement appears to proceed via an intermediate containing two different templates, a pyramidal {HPO3} and a tetrahedral {PO4} moiety. {HPO3} templated POM cages were then vigorously expanded and led to the isolation of five either fully oxidised or mixed-valence clusters trapped with mono-, di-, or tri- {HPO3}. Interestingly, an intriguing 3D honeycomb-like host-guest structure was also synthesised. The porous framework was self-aggregated by a tri-phopshite anion templated {W21} cluster with a {VO4} templated Wells-Dawson type {W18} acting as a guest species within the hexagonal channels. Based on this work, we further extended the templating anions to two different redox-active heteroanions, and discovered a unique mixed-heteroatom templated system built by pairing redox-active {HPIIIO3} with {TeO3}, {SeO3} or {AsO3}. Two molecular systems were developed, ie. “Trojan Horse” type [W18O56(HPO3)0.8(SeO3)1.2(H2O)2]8- and cross-shaped [H4P4X4W64O224]32-/36-, where X=TeIV, SeIV, AsIII. In the case of {W18(HPO3)0.8(SeO3)1.2}, the compound is found to be a mixture of heteroleptic {W18(HPO3)(SeO3)} and homoleptic {W18(SeO3)2} and {W18(HPO3)2}, identified by single crystal x-ray diffraction, NMR as well as high resolution mass spectrometry. The cluster exhibited similar temperature-dependent electronic features to “Trojan Horse” type {W18(HPO3)2O56}. However, due to the intrinsic reactivity difference between {HPO3} and {SeO3}, the thermal treatment leads to the formation of an unusual species [W18O55(PO4)(SeO3)]5-, in which {HPO3} was fully oxidised to {PO4} within the cage, whereas and lone-pair-containing {SeO3} heteroanions were kept intact inside the shell. This finding is extremely interesting, as it demonstrated that multiple and independent intramolecular electronic performance can be achieved by the coexistence of distinct heteroatoms within a single molecule. On the other hand, the cross-shaped [H4P4X4W64O224]32-/36- were constructed by four {W15(HPO3)(XO3)} building units linked by four {WO6} octahedra. Each building unit traps two different heteroatoms. It is interesting to note that the mixed heteroatom species show self-sorting, with a highly selective positional preference. Smaller ionic sized {HPO3} are self-organised into the uncapped side of {W15} cavity, whereas closed side are occupied by larger heteroatoms, which is surprisingly opposed to steric hindrance. Density functional theory (DFT) calculations are currently underway to have a full understanding of the preference of heteroatom substitutions. This series of clusters is of great interest in terms of achieving single molecule-based heteroatom-dependent multiple levels of electron transfer. It has opened a new way to design and synthesise POMs with higher diversity of electrical states, which may lead to a new type of Q-bits for quantum computing. The third chapter is focused on developing polyoxotungstate building blocks templated by {HPO3}. A series of building blocks, {W15O48(HPO3)2}, {W9O30(HPO3)} {W12O40(HPO3)2} and hexagonal {W6O18(HPO3)} have been obtained. The first four building blocks have been reported with {SeO3} and/or {TeO3} heteroanions. This result demonstrates {HPO3} has a similar reactivity as {SeO3} and {TeO3}, therefore studying the self-assembly of {HPO3}-based building blocks would be helpful to have a general understanding of pyramidal heteroatom-based molecular systems. The hexagonal {W6O18(HPO3)} is observed for the first time in polyoxotungstates, showing some of reactivity difference between {HPO3} and {SeO3} and {TeO3}. Furthermore, inorganic salts and pH values have some directing influence on the formation and transformation of various building blocks, resulting in the discovery of a family of {HPO3}-based clusters with nuclearity ranging from {W29} to {W106}. High resolution mass spectrometry was also carried out to investigate the cluster solution behaviour and also gain information of building block speciation. It is found that some clusters experienced decomposition, which gives rise to potential building blocks accountable for the self-assembly.

Les contrats et les droits fondamentaux : perspective franco-québécoise

Réalisé en cotutelle

Excitonic behaviour in polymeric semiconductors : the effect of morphology and composition in heterostructures

La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus.

Coordenação entre as respostas da catalase e da ascorbato peroxidade em folhas de feijão caupi submetidas a diferentes fontes de peróxido de hidrogênio

The plants are often exposed to variations in environmental conditions that may trigger metabolic disturbances leading to a consequent loss in productivity of crops. These stressful conditions usually induce an accumulation of reactive oxygen species (ROS) in the cell, a condition known how oxidative stress. Among these species, hydrogen peroxide (H2O2) is an important molecule involved in numerous signaling mechanisms. The present study aimed to understand the relationship between the different enzymatic mechanisms of elimination of H2O2 by catalase (CAT) and ascorbate peroxidase (APX) in leaf tissues of seedlings of the species Vigna unguiculata L. Walp, under conditions of oxidative stress induced by application of CAT inhibitor, 3-amino-1,2,4-triazole (3-AT), and H2O2 itself on the roots. Three experiments were conducted. The first experiment was performed applying the compound 3-AT (5 mM) during the time (hours). In the second experiment, seedlings were exposed to different concentrations of H2O2 (2.5, 5.0, 7.5, 10 mM) for 48 h. The third strategy included the pre-treatment with H2O2 (2.5 mM) for 24 h, followed by subsequent treatment with the inhibitor 3-AT and recovery control condition. Treatment with 3-AT causes a strong inhibition of CAT activity in leaf tissues accompanied by an increase of activity of APX. However a decrease in oxidative damage to lipids is not observed as indicated by TBARS. It was observed that activity of APX is directly linked to the content of peroxide. Inductions in the activities of CAT and APX were observed mainly in the seedlings treated with 2.5 mM H2O2. This can be associated with a decrease in oxidative damage to lipids. In contrast, one same tendency was not observed in treatments with higher concentrations of this ROS. These results suggest that the concentration of 2.5 mM H2O2 can induce responses antioxidants later in seedling cowpea. This concentration when applied as pre-treatment for 24 h promoted an induction systems removers CAT and APX, both in activity and in terms of gene expression. However this increment was not observed in the recovered plants and the plants subsequently subjected to 3-AT. Additionally, the pretreatment was not sufficient to attenuate the inhibition of CAT activity and oxidative damage to lipids caused by the subsequent application of this inhibitor. The results showed that the application of 3-AT and H2O2 in the root systems of seedlings of cowpea promote changes in the parameters analyzed in leaf tissues that indicate a direct response to the presence of these factors or systemic signaling mecanisms. H2O2 appears to activate the responses of two antioxidant systems in this study thar does not promote greater protection in case of additional treatment with 3-AT. This demonstrates the importance of the CAT system. In this work, complete results indicate that there is a difference between the signaling and the effects caused by exposure to H2O2 and by treatment with 3-AT