Purificação de C-ficocianina e sua incorporação em nanofibras

C-ficocianina (C-FC) é uma ficobiliproteína, de cor natural azul, com diversas aplicações na indústria alimentícia, farmacêutica e biomédica, dependendo do seu grau específico de pureza, que pode variar de 0,7 a 4,0, com respectivo aumento de seu valor comercial. Essa pureza é alcançada através de diversas técnicas de purificação, que podem ser aplicadas em diferentes sequências. Um destes processos de purificação de proteínas baseia-se na cromatografia de troca iônica, que utiliza trocadores que adsorvem as proteínas como resultado de interações iônicas entre a superfície da proteína e o trocador. Resinas e colunas de leito expandido podem ser utilizadas para aumentar a produtividade dessa técnica. É fundamental conhecer o perfil do processo de adsorção, para melhor aplicá-lo como ferramenta para o design e otimização de parâmetros operacionais. Outra tecnologia para o tratamento de biomoléculas é a ultrafiltração. Esta técnica é aplicável em larga escala, apresenta baixa complexidade de aplicação e pode ser realizada em condições brandas, minimizando o dano para o produto. Para aumentar a estabilidade da C-FC, e facilitar a sua aplicação, podem ser avaliadas técnicas recentes, não exploradas para este fim, como as nanofibras obtidas através do processo de electrospinning. Estas fibras possuem uma área superficial específica extremamente elevada devido a seu pequeno diâmetro. O objetivo deste trabalho foi avaliar parâmetros de adsorção e diferentes técnicas para purificação de C-ficocianina de Spirulina platensis e obter nanofibras poliméricas incorporadas de C-ficocianina. O trabalho foi dividido em quatro artigos. No primeiro artigo, foram avaliados os parâmetros e as isotermas de adsorção de C-ficocianina em resina de troca iônica para leito expandido Streamline® DEAE. Verificou-se que o maior coeficiente de partição foi obtido em pH 7,5, nas temperaturas de 15 e 25 °C. As isotermas de adsorção da Cficocianina foram bem representadas pelos modelos de Langmuir, de Freundlich e de Langmuir-Freundlich, sendo os valores estimados para Qm e Kd obtidos pela isoterma de Langmuir foram, respectivamente, 33,92 mg.mL-1 e 0,123 mg.mL-1, respectivamente. No segundo artigo foi avaliada a purificação de C-FC até grau alimentar, utilizando ultrafiltração (UF). Com a membrana de 50 kDa, identificou-se que somente a temperatura e a aplicação de diferentes ciclos de diafiltração (DF) causaram influência significativa sobre a purificação e recuperação da C-ficocianina. Foram então aplicados o aumento gradativo da quantidade de ciclos, e a diafiltração previamente à ultrafiltração (DF/UF), onde obteve-se um extrato de Cficocianina com pureza de 0,95. No terceiro artigo foram propostos processos de purificação, envolvendo a utilização das diferentes técnicas para obtenção de C-FC com diferentes purezas. Determinou-se que a partir de cromatografia de troca iônica em leito fixo seguido de DF/UF, obtém-se C-FC para uso em cosméticos e a partir de precipitação com sulfato de amônio, e DF/UF obtém-se C-FC para uso em biomarcadores. Com uma sequência de precipitação com sulfato de amônio, DF/UF e cromatografia de troca iônica em leito fixo chega-se a C-FC de grau analítico. No último artigo, C-FC foi incorporada a nanofibras de óxido de polietileno (PEO) através de processo de electrospinning. Foram determinadas a condutividade da solução de C-FC/PEO, a estrutura e comportamento termogravimétrico das nanofibras formadas. Soluções de polímeros com concentração de 6 e 8% proporcionaram a formação de nanofibras com diâmetro médio inferior a 800 nm, homogêneas, sem a presença de gotas. A análise termogravimétrica identificou aumento na resistência térmica da C-FC incorporada nas fibras.

Ordenação por translocação de genomas sem sinal utilizando algoritmos genéticos

Dissertação (mestrado)—Universidade de Brasília, Instituto de Ciências Exatas, Departamento de Ciência da Computação, Programa de Pós-Graducação em Informática, 2016.

Fenóis voláteis em vinhos tintos

As leveduras Dekkera/Brettanomyces são responsáveis pela formação de fenóis voláteis em vinhos tintos, tornando-se numa grande preocupação para a produção enológica a nível mundial, devido à dificuldade em controlá-las. Os fenóis voláteis são responsáveis por aromas desagradáveis nos vinhos tintos, diminuindo a sua qualidade e resultando em grandes perdas económicas. Este trabalho teve como principal objectivo estudar um método de preparação de amostra e um método cromatográfico para analisar e quantificar os principais fenóis voláteis (4-etilfenol, 4-etilguaiacol, 4-etilcatecol, 4-vinilfenol e o 4-vinilguaiacol), em meio sintético e em vinhos tintos comerciais. A preparação de amostras foi efectuada através do método de extracção líquido-líquido e a separação dos compostos foi efectuada por cromatografia gasosa com detector de ionização de chama (GC-FID). Os resultados obtidos permitem concluir que é possível detectar e quantificar os fenóis voláteis com este método, incluindo o 4-etilcatecol. O 4-etilfenol foi o composto mais abundante nos vinhos tintos comerciais estudados. ABSTRACT: The yeasts Dekkera I Brettanomyces are responsible for the formation of volatile phenols in red wine, becoming a major concern for the enological production worldwide because of the difficulty in controlling them. The volatile phenols are responsible for unpleasant aromas in red wines, reducing its quality and resulting in great economic lasses. The main objective of this work was to study a sample preparation and a chromatographic method to analyze main volatile phenols (4-ethylphenol, 4-ethylguaiacol, 4-ethylcatechol, 4-vinylphenol and 4-vinylguaiacol) in synthetic wine and red wines. Sample preparation was done by liquid-liquid extraction and compounds separation was achieved by gas chromatography with flame ionization detector (GC­ FID) Results showed that it is possible to detect and quantified volatile phenols with the methodology proposed, including 4-ethylcatechol. 4-ethylphenol was the main compound found in commercial red wines.

New Catalysts for the Renewable Production of Monomers for Bioplastics

Terephthalic acid (PTA) is one of the monomers used for the synthesis of the polyester, polyethylene terephthalate (PET), that is used for the large-scale manufacture of synthetic fibers and plastic bottles. PTA is largely produced from the liquid-phase oxidation of petroleum-derived p-xylene (PX). However, there are now ongoing worldwide efforts exploring alternative routes for producing PTA from renewable, biomass resources.

In this thesis, I present a new route to PTA starting from the biomass-derived platform chemical, 5-hydroxymethylfurfural (HMF). This route utilizes new, selective Diels-Alder-dehydration reactions involving ethylene and is advantageous over the previously proposed Diels-Alder-dehydration route to PTA from HMF via 2,5-dimethylfuran (DMF) since the H₂ reduction of HMF to DMF is avoided. Specifically, oxidized derivatives of HMF are reacted as is, or after etherification-esterification with methanol, with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids in order to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA) is reacted with high pressure ethylene over a pure-silica molecular sieve catalyst containing framework tin (Sn-Beta) to produce the Diels-Alder-dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with ~30% selectivity at ~20% yield. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with >70% selectivity at >20% yield. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder-dehydration product is observed.

An investigation to elucidate the reaction network and side products in the conversion of MMFC to MMBC was performed, and the main side products are found to be methyl 4-formylcyclohexa-1,3-diene-1-carboxylate and the ethylene Diels-Alder adduct of this cyclohexadiene. These products presumably form by a different dehydration pathway of the MMFC/ethylene Diels-Alder adduct and should be included when determining the overall selectivity to PTA or DMT since, like MMBC, these compounds are precursors to PTA or DMT.

Fundamental physical and chemical information on the ethylene Diels-Alder-dehydration reactions catalyzed by the Lewis acid-containing molecular sieves was obtained. Madon-Boudart experiments using Zr-Beta as catalyst show that the reaction rates are limited by chemical kinetics only (physical transport limitations are not present), all the Zr⁴⁺ centers are incorporated into the framework of the molecular sieve, and the whole molecular sieve crystal is accessible for catalysis. Apparent activation energies using Zr-Beta are low, suggesting that the overall activation energy of the system may be determined by a collection of terms and is not the true activation energy of a single chemical step.

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline

UNDERSTANDING CHASSIS INPUTS FROM THE REAR SUSPENSION OF A SNOWMOBILE

Today’s snowmobile industry faces great challenges in the field of noise & vibration. The area of main concern is the pass-by noise restriction defined by the Society of Automotive Engineers (SAE) test standard J192, with a maximum sound pressure level of 78 dB(A) being required by many states and national parks. To continue meet or beat this requirement without effecting machine performance, a deeper understanding of the sound transfer paths is required. This thesis examines the transfer paths created by the tunnel, rear suspension, drive shaft, and rubber composite track, with the primary source being suspension input through the ground. Using a combination of field experiments and analytical modeling, perspective was gained on which suspension and drive elements create the primary transfer paths. With further understanding of these paths, industry can tailor and fine-tune the approaches taken in to control overall noise output.

Edge centrality via the Holevo quantity

In the study of complex networks, vertex centrality measures are used to identify the most important vertices within a graph. A related problem is that of measuring the centrality of an edge. In this paper, we propose a novel edge centrality index rooted in quantum information. More specifically, we measure the importance of an edge in terms of the contribution that it gives to the Von Neumann entropy of the graph. We show that this can be computed in terms of the Holevo quantity, a well known quantum information theoretical measure. While computing the Von Neumann entropy and hence the Holevo quantity requires computing the spectrum of the graph Laplacian, we show how to obtain a simplified measure through a quadratic approximation of the Shannon entropy. This in turns shows that the proposed centrality measure is strongly correlated with the negative degree centrality on the line graph. We evaluate our centrality measure through an extensive set of experiments on real-world as well as synthetic networks, and we compare it against commonly used alternative measures.

Entre riscos e rabiscos: da leitura à representação (gráfica) de provérbios

De tradição oral e de origem remota, os provérbios circunscrevem a realidade cultural dos seus criadores e utilizadores. A sua riqueza reside, por um lado, na mensagem sintética e por isso, também, pragmática, ao ser utilizada como âncora em contextos específicos; reside, por outro lado, na construção de metáforas conceptuais, tradutoras de verdades e generalizações sedimentadas na observação empírica. É nestas que a língua portuguesa (LP) germina a dimensão cultural e permite a exploração de mundividências partilhadas, transparentes, translúcidas ou opacas. O trabalho que propomos apresentar descreve um conjunto de atividades realizadas com alunos do 5.o ao 8.o ano de escolaridade, no âmbito de um programa desenvolvido por um agrupamento de escolas da região de Viseu e uma instituição de ensino superior durante o ano letivo de 2013-2014. As atividades que propusemos implicaram considerar a LP a partir de diferentes prismas, perspetivando-a não só como código verbal, como herança cultural, mas também como espaço de criação e criatividade. Assim, a sedimentação de significados que foram construindo a LP é apresentada aos alunos como enigma a desvelar. Neste sentido, propomos a) analisar a representação gráfica de provérbios feita por alunos do ensino básico; b) refletir sobre a influência da LP na formação de provérbios em países de expressão portuguesa. A sua interpretação é padronizada, mas permeável a ambiguidades. Neste caso, e a partir da comparação de um exercício de equivalência entre provérbios representados pela variedade do português, revelamos a seleção dos alunos.

Investigating the Role of PDE4D1/2 in Vascular Smooth Muscle Cell Desensitization

Thesis (Master, Biochemistry) -- Queen's University, 2016-10-14 02:44:01.604

Anotação sintética, numa perspectiva de Direito Público-penal e Direito Privado-civil, ao Acórdão do Supremo Tribunal de Justiça Português, de 19 de Abril de 2012 - A poluição sonora e o direito humano ao descanso e à saúde, sem descurar a necessidade duma adequada política tributária.

Resumo: 1 – Sumário do Acórdão do Supremo Tribunal de Justiça, de 19 de Abril de 2012; 2 – Texto completo do Acórdão do Supremo Tribunal de Justiça, de 19 de Abril de 2012: cfr. http://www.dgsi.pt/jstj.nsf/954f0ce6ad9dd8b980256b5f003fa814/fc664c231f3e73cf802579ea003d91d2?OpenDocument&Highlight=0,polui%C3%A7%C3%A3o , 2 de Junho de 2012; 3 – Anotação sintética; 3.1 – Introdução à anotação sintética e suas características neste caso concreto; 4 – Algumas referências constitucionais centrais em relação a Direitos humanos e, nomeadamente, a um Direito humano a um meio-ambiente sadio, saudável em todas as suas vertentes e sentidos – o exemplo central do artigo 9.º da CRP; 4.1 – Algumas referências constitucionais centrais em relação a Direitos humanos e, nomeadamente, a um Direito humano a um meio-ambiente sadio, saudável em todas as suas vertentes e sentidos – o exemplo central do artigo 66.º da CRP e o Regime Geral do Ruído; 5 – O direito humano ao descanso e à saúde, rectius o direito ao ambiente sadio vs o direito ao lazer e/ou exploração económica de indústrias de diversão, rectius o direito à liberdade de iniciativa económica privada; 6 – A violação do direito humano, de personalidade, ao descanso e à saúde, rectius o direito a um ambiente sadio, numa perspectiva de Direito privado e Direito civil; 7 – A criminalização da poluição, designadamente a criminalização da poluição sonora – uma perspectiva de Direito público e Direito penal; 8 - A necessidade duma adequada política tributária que compatibilize desenvolvimento sustentado com a protecção dum meio ambiente sadio e com qualidade de vida; 9 – Conclusões. Palavras-chave: Direitos Humanos; Direito constitucional; Direito público; Direito penal; Direito privado; Direito civil; Direito ambiental; meio ambiente sadio; Direito ao descanso; Direito à saúde; Direito ao lazer e/ou exploração económica de indústrias de diversão; direito à liberdade de iniciativa económica privada; Direito tributário; Direito fiscal; Direito aduaneiro. Abstract: 1 - Summary of the Judgment of the Supreme Court of April 19, 2012, 2 - Complete text of the Judgment of the Supreme Court of April 19, 2012: cf. http://www.dgsi.pt/jstj.nsf/954f0ce6ad9dd8b980256b5f003fa814/fc664c231f3e73cf802579ea003d91d2?OpenDocument&Highlight=0,polui%C3%A7%C3%A3o , June 2, 2012, 3 - Synthetic Note: 3.1 - Introduction to synthetic annotation and its characteristics in this case 4 - Some references constitutional power over human rights and in particular to a human right to a healthy environment, healthy in all its forms and meanings - the central example of Article 9. of CRP; 4.1 - Some references constitutional power over human rights and in particular to a human right to a healthy environment, healthy in all its forms and meanings - the central example of Article 66. No of CRP and the General Noise; 5 - the human right to rest and health, rectius the right to healthy environment vs. the right to leisure and / or economic exploitation of industries fun, rectius the right to freedom of private economic initiative; 6 - the violation of human personality, to rest and health, rectius the right to a healthy environment, a perspective of private law and civil law; 7 - criminalization of pollution, including the criminalization of noise - a perspective of public law and criminal law; 8 - the need for appropriate tax policy that reconciles sustainable development with the protection of a healthy environment and quality of life; 9 - Conclusions.

Recent Developments in Wine Tartaric Stabilization

Tartrate precipitation is still a relevant subject in Enology, being one of the most common problems of wine physical-chemical instability. Potassium bitartrate and calcium tartrate precipitations are undesirable phenomena which can occur in bottled wines, especially when these are stored at low temperatures. The occurrence of tartrate salt crystals (potassium hydrogen tartrate – KHT and calcium tartrate – CaT) in bottles has severe consequences in the final aspect of the wine and therefore on the consumer’s acceptance, making tartrate wine stabilization virtually mandatory before bottling. Currently, several solutions to prevent this haze are available: subtractive methods including the conventional cold treatments that promote the cristalization of KHT, removal of potassium and calcium ions either by electrodialysis or ion exchange resins; and additive methods such as the addition of carboxymethylcellulose, mannoproteins or metatartaric acid. For monitoring the KHT stability, several analytical methods have been developed based on conductivity evaluation, namely the mini-contact test and the saturation temperature measurements (TS). These methods will also be revisited, aiming to raise awareness of their utility as tools in quality control of wines. This review addresses tartrate precipitation subject and the most recent preventive solutions available, pointing out the advantages and drawbacks of each one, and its impact on the final characteristics of the wine.

Flow of Complex Fluids in Geological Fractures

In this study, the lubrication theory is used to model flow in geological fractures and analyse the compound effect of medium heterogeneity and complex fluid rheology. Such studies are warranted as the Newtonian rheology is adopted in most numerical models because of its ease of use, despite non-Newtonian fluids being ubiquitous in subsurface applications. Past studies on Newtonian and non-Newtonian flow in single rock fractures are summarized in Chapter 1. Chapter 2 presents analytical and semi-analytical conceptual models for flow of a shear-thinning fluid in rock fractures having a simplified geometry, providing a first insight on their permeability. in Chapter 3, a lubrication-based 2-D numerical model is first implemented to solve flow of an Ellis fluid in rough fractures; the finite-volumes model developed is more computationally effective than conducting full 3-D simulations, and introduces an acceptable approximation as long as the flow is laminar and the fracture walls relatively smooth. The compound effect of shear-thinning fluid nature and fracture heterogeneity promotes flow localization, which in turn affects the performance of industrial activities and remediation techniques. In Chapter 4, a Monte Carlo framework is adopted to produce multiple realizations of synthetic fractures, and analyze their ensemble statistics pertaining flow for a variety of real non-Newtonian fluids; the Newtonian case is used as a benchmark. In Chapter 5 and Chapter 6, a conceptual model of the hydro-mechanical aspects of backflow occurring in the last phase of hydraulic fracturing is proposed and experimentally validated, quantifying the effects of the relaxation induced by the flow.

A study on tackling visual odometry by a transformer architecture

This dissertation describes a deepening study about Visual Odometry problem tackled with transformer architectures. The existing VO algorithms are based on heavily hand-crafted features and are not able to generalize well to new environments. To train them, we need carefully fine-tune the hyper-parameters and the network architecture. We propose to tackle the VO problem with transformer because it is a general-purpose architecture and because it was designed to transformer sequences of data from a domain to another one, which is the case of the VO problem. Our first goal is to create synthetic dataset using BlenderProc2 framework to mitigate the problem of the dataset scarcity. The second goal is to tackle the VO problem by using different versions of the transformer architecture, which will be pre-trained on the synthetic dataset and fine-tuned on the real dataset, KITTI dataset. Our approach is defined as follows: we use a feature-extractor to extract features embeddings from a sequence of images, then we feed this sequence of embeddings to the transformer architecture, finally, an MLP is used to predict the sequence of camera poses.

End of life treatment options for bioplastics; a composting efficency case study

The constant increase in plastic production creates many problems, from its oil-based production all the way to end-of-life treatment, as the same proprieties that make plastic useful make conventional plastic into long-lasting waste that’s quickly piling up. One alternative is a different kind of plastic, bioplastic, a polymeric compound that is both functionally like synthetic plastics and largely environmentally sustainable. It is not necessarily enough to solve the plastic waste issue there's a need for effective strategies to manage bioplastic products at their end of life, to avoid undoing the reduction of environmental impact. One such treatment, unique to biodegradable bioplastics, is composting. This prompts a closer study of how efficient this process is in degrading bioplastics.