Fotodegradação de antibióticos de nitrofurano em condições ambientais

Ao submeter uma solução aquosa de 5-nitro-2-furaldeído (NFA) a fotólise com impulsos de luz de curta duração (produzidos por um laser de estado sólido de Nd-YAG) origina-se uma absorvância (transiente) de curta duração que é atribuída à absorção de luz pelo NFA no estado tripleto mais baixo (3NFA*). O espectro desta absorção de luz apresenta um λmax = 475 ± 5 nm, que se mostrou ser insensível à polaridade do solvente. Em solução aquosa, a absorção do 3NFA* decai para uma absorção transiente de tempo de vida mais longo e que, medida em tempos diferentes (depois do fim do impulso), revelou ser devida a um radical furiloxilo (a de λmax ≈ 375 nm) e ao anião radical NFA•‒ (a de λmax ≈ 400 nm). Estes dois radicais foram gerados independentemente um do outro, o que permitiu confirmar a atribuição daquela absorção de longo tempo de vida (obtida na fotólise de NFA em água) aos radicais furiloxilo e anião radical do NFA. O tempo de vida (τ) do 3NFA* revelou uma dependência em relação à natureza do solvente e à concentração de NFA no estado fundamental. Da propensão do 3NFA* para abstrair um átomo de hidrogénio de solventes (com átomos de H abstraíveis) concluiu-se a natureza (n, π*) do estado tripleto de menor energia do NFA. A dependência de τ em relação à concentração de NFA (no estado fundamental) forneceu evidência cinética em favor da formação de um excímero tripleto que supostamente se dissocia em iões radicais (catião e anião) como é proposto no mecanismo de auto-supressão do 3NFA* por transferência de electrão. O efeito da acididade sobre τ corrobora o mecanismo de auto-supressão por transferência de electrão. A análise cromatográfica e espectroscópica da solução fotolisada de NFA em água permitiu identificar a 5-hidroximetileno-2(5H)-furanona, o ião nitrito e uma substância desconhecida de tR 3.69 minutos como os fotoprodutos maioritários. Apresenta-se evidência conclusiva de que a 5-hidroximetileno-2(5H)-furanona provém do radical furiloxilo. Mostra-se que a substância desconhecida também pode ser obtida na foto-redução de NFA em propan-2-ol e na redução química de NFA por Fe (s) em água (em ambas, conjuntamente com produção de 5-amino-2-furaldeído). Com base na análise por espectroscopia de absorção de RMN de 1H e de 13C (com 2-D HMQC) e vibracional por FT no infravermelho médio, discute-se a possível estrutura da substância de tR 3.69 minutos obtida como um produto da foto-redução de NFA em água. Experiências de sensibilização e supressão do 3NFA* permitiram obter a energia de excitação do estado tripleto como 238 ± 2 kJ mol-1 o que, conjuntamente com o potencial de redução monoelectrónica (E71) do NFA fornece E71 (3NFA* / NFA•‒) = 2.26 V vs. SHE para o potencial de redução monoelectrónica do 3NFA* em solução aquosa neutra. Mostra-se que os aniões inorgânicos (usados como nucleófilos) são mono-oxidados pelo 3NFA* (como é indicado pela observação de NFA•‒ e do radical inorgânico) com constantes de velocidade de segunda-ordem (

Remoção de nitratos em água utilizando diferentes materiais e processos

The need to preserve the environment has led to the search for new materials for efficient disposal of chemical compounds that alter the stability of our natural resources. Among these resources, stands in first place the water, as a precious commodity and scarce, leading to the proper use and reuse. As a result, the World Health Organization has established maximum permissible values in drinking water, such as: 50 mg/L, 0, 1 mg/L and 0, 5 mg/L to at-3, at-2, NH 4, respectively. For these reasons, assesses the implementation of new materials and water treatment processes aiming at the removal of these compounds, such as alumina, in the form of powder or as a support for a catalytic system using inorganic membranes capable of supporting more severe conditions of temperature and pressure by opening new possibilities for applications of membrane reactors; and also for electrochemical treatments with doped diamond bobo electrodes (BDD) as anode and copper as cathode. For such purpose, was conducted the study of adsorption of nitrate in different times to assess the time required to achieve equilibrium by employing three commercial alumina called: acidic, basic and neutral alumina, with subsequent treatment only in the acidic alumina impregnating metals (PdCu/Al2O3) for the catalytic reaction. The materials were previously characterized by XRD, SEM techniques and ABET. Aluminas presented a considerable adsortive capacity of nitrate in the first thirty minutes, equivalent to 50% of removal reaching equilibrium in that time. After treatment, using alumina as catalyst for the reaction in batch reactor (Pd-Cu/Al2O3), the results were more favourable, totalling 64% reduction of ion NO3-at the end of three hours. On the other hand, the results for the catalytic reaction using the catalytic support Pd-Cu/TiO2 in membrane reactor proved to be low. -if, in this way, improve the conditions of catalytic system to optimize the process. Already, for the electrochemical tests using DDB1 electrodes as anode, and Cu, as cathode, there was a fairly significant nitrate reduction, approximately 80% of ion removal during three hours and cost viable applications.

Características bioativas, funcionais e efeito protetor do resíduo desidratado de camu-camu (Myrciaria dubia H.B.K. (McVaugh)) sobre doenças degenerativas utilizando modelos in vivo C. elegans

Camu-camu (Myrciaria dubia H.B.K. (McVaugh)) is a native Amazon fruit, recognized worldwide as one of the main natural sources of ascorbic acid. Due to its great acidity, this fruit is generally consumed after processing into juice or as ingredient in food preparations. As a co-product of the camu-camu processing, a significant amount of agroindustrial residue is generated. Despite the studies showing the bioactive value and biological potential of the fruit, few studies have approached the possible processing techniques, transformation and preservation of camu-camu fruits and its agroindustrial pomace. Therefore, the present work has the objective of evaluating two different drying processes applied to camu-camu pomace (peel and seeds with residual pulp), freeze drying and hot air drying, in order to obtain a functional fruit product. This thesis was divided into three stages: the first one shows the studies related to the freeze drying and hot air drying, where we demonstrated the impact of the selected drying techniques on the bioactive components of camu-camu, taking the fresh pomace as the control group. Among the investigated conditions, the groups obtained at 50ºC and 4 m/s (SC50) and 80ºC and 6 m/s (SC80) were selected as for further studies, based on their ascorbic acid final content and Folin-Ciocalteau reducing capacity. In addition to SC50 and SC80, the fresh pomace (RF) and freeze dried (RL) samples were also evaluated in these further stages of the research. Overall, the results show higher bioactive concentration in the RF samples, followed by RL, SC50 and SC80. On the second step of the research, the antioxidant, antimicrobial and antienzymatic activities were evaluated and the same tendency was observed. It was also reported, for the first time in the literature, the presence of syringic acid in dried camu-camu pomace. In the third and final stage of the research, it was investigated the effect of dried camu-camu on aging and neuroprotective disorders, using the in vivo model C.elegans. It was observed that camu-camu extracts were able to modulate important signaling genes relevant to thermal and oxidative stresses (p < 0.05). The polar acid, polar basic and polar neutral fractions obtained from the low molecular extracts of SC50 were able to extend the lifespan of wild type N2 C. elegans in 20% and 13% (p < 0.001). Results also showed that the paralysis induced by the β1-42 amyloid was significantly (p < 0.0001) retarded in CL4176 worms. Similarly, the camu-camu extracts attenuated the dopaminergic induction associated to Parkinson’s disease. Finally, a global analysis of the data presented here reveal that the camu-camu pomace, a co-product obtained from the industrial processing of a native Brazilian fruit, is a relevant natural source of health relevant compounds. This thesis, shows for the first time, the multifunctionality of camu-camu pomace, a natural resource still underexploited for scientific, commercial and technological purposes.

A predominância do filtro ambiental local na montagem de uma floresta tropical de ambiente estressante

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Novos protocolos teóricos utilizados nos estudos das ligações hidrogênio-hidrogênio, na estabilidade do tetraedrano, seus derivados e das reações de diels-alder e na quantificação da afinidade de fármacos

This thesis was performed in four chapters, at the theoretical level, focused mainly on electronic density. In the first chapter, we have applied an undergraduate minicourse of Diels-Alder reaction in Federal University of Rio Grande do Norte. By using computational chemistry tools students could build the knowledge by themselves and they could associate important aspects of physical-chemistry with Organic Chemistry. In the second chapter, we studied a new type of chemical bond between a pair of identical or similar hydrogen atoms that are close to electrical neutrality, known as hydrogen-hydrogen (H-H) bond. In this study performed with complexed alkanes, provides new and important information about their stability involving this type of interaction. We show that the H-H bond playing a secondary role in the stability of branched alkanes in comparison with linear or less branched isomers. In the third chapter, we study the electronic structure and the stability of tetrahedrane, substituted tetrahedranes and silicon and germanium parents, it was evaluated the substituent effect on the carbon cage in the tetrahedrane derivatives and the results indicate that stronger electron withdrawing groups (EWG) makes the tetrahedrane cage slightly unstable while slight EWG causes a greater instability in the tetrahedrane cage. We showed that the sigma aromaticity EWG and electron donating groups (EDG) results in decrease and increase, respectively, of NICS and D3BIA aromaticity indices. In addition, another factor can be utilized to explain the stability of tetra-tert-butyltetrahedrane as well as HH bond. GVB and ADMP were also used to explain the stability effect of the substituents bonded to the carbon of the tetrahedrane cage. In the fourth chapter, we performed a theoretical investigation of the inhibitory effect of the drug abiraterone (ABE), used in the prostate cancer treatment as CYP17 inhibitor, comparing the interaction energies and electron density of the ABE with the natural substrate, pregnenolone (PREG). Molecular dynamics and docking were used to obtain the CYP1ABE and CYP17-PREG complexes. From molecular dynamics was obtained that the ABE has higher diffusion trend water CYP17 binding site compared to the PREG. With the ONIOM (B3LYP:AMBER) method, we find that the interaction electronic energy of ABE is 21.38 kcal mol-1 more stable than PREG. The results obtained by QTAIM indicate that such stability is due a higher electronic density of interactions between ABE and CYP17

Entspannte Moderne

Die Dissertation ist eine grundlegende Untersuchung des modernen westdeutschen Bungalows - eines prägenden Einfamilienhaustypus' der Nachkriegszeit, der bis dato in der Literatur nur anhand von Einzelbeispielen diskutiert wurde. Einleitend wird der Forschungsstand zur globalen Bungalowhistorie referiert und die Historie des Einfamilienhauses und der politisierten Architekturmoderne in Deutschland vor 1945 sowie die soziologischen Rahmenbedingungen des Bungalowbooms in Nachkriegsbundesrepublik werden überblicksartig dargelegt. Im Zentrum der Arbeit stehen die Forschungsergebnisse einer Analyse von 64 exemplarischen westdeutschen Bungalows 1952-1969. Diese wurden auf Basis einer systematischen Literaturrecherche ausgewählt und klassifiziert (vgl. Katalogteil). Es wird zunächst die spezifisch westdeutsche Begrifflichkeit des Nachkriegsterminus Bungalow herausgearbeitet und der westdeutsche Bungalowboom wird in drei überlappende Phasen periodisiert. Die Ergebnisse zu den untersuchten Bungalowprojekten werden ihrer Ikonografie, Materialität und Konstruktion sowie ihrer Typologie und ihres Naturbezugs erläutert. Es wird gezeigt, dass es sich bei der ikonografischen Darstellung des Bungalows als verglastem Pavillon um eine mediale Konstruktion handelt, die hier als die Pavillonisierung des Bungalows bezeichnet wird. Diese unterschlägt die Doppelgesichtigkeit des Bungalowtypus: neben der verglasten Gartenseite ist eine deutlich geschlossenere Straßenfassade ebenso charakteristisch für diesen Typus. Trotz der jeweils unterschiedlich ausgebildeten räumlichen Bezüge zum privaten Garten weisen alle drei identifizierten Bungalowtypen (Winkelbungalow, Rechteckbungalow, Wohnhofbungalow) diese Dualität auf. Hinsichtlich der historischen Konnotationen werden zwei unterschiedliche Rezeptionsweisen identifiziert: In der Architekturgeschichte wurde der Bungalow durch Motive rezipiert, die ihm im Kontext der Moderne Relevanz verliehen, z. B. das Motiv des allseitig verglasten Pavillons oder des fließenden Raums. Die sozialhistorische Betrachtung der Beispiele verdeutlicht jedoch, dass es der moderne Wohnhauscharakter war, der den skalierbaren Bungalowtypus zu einem idealen Wohnhaustypus für eine breite Bevölkerungsschicht machte. In seiner Modellhaftigkeit leicht zu identifizieren und hinsichtlich der Größe schwer einzuschätzen, wurde der flache Bungalow in der Nachkriegsbundesrepublik zum Symbol einer nivellierten Mittelschichtsgesellschaft.

Development and characterization of Poly(L-lactic acid) (PLLA) platforms for bone tissue engineering

The development of scaffolds based on biomaterials is a promising strategy for Tissue Engineering and cellular regeneration. This work focuses on Bone Tissue Engineering, the aim is to develop electrically tailored biomaterials with different crystalline and electric features, and study their impacts onto cell biological behavior, so as to predict the materials output in the enhancement of bone tissue regeneration. It is accepted that bone exhibits piezoelectricity, a property that has been proved to be involved in bone growth/repair mechanism regulation. In addition electrical stimulations have been proved to influence bone growth and repair. Piezoelectric materials are therefore widely investigated for a potential use in bone tissue engineering. The main goal is the development of novel strategies to produce and employ piezoelectric biomaterials, with detailed knowledge of mechanisms involved in cell-material interaction. In the current work, poly (L-lactic) acid (PLLA), a synthetic semi-crystalline polymer, exhibiting biodegradibility, biocompatibility and piezoelectricity is studied and proposed as a promoter of enhanced tissue regeneration. PLLA has already been approved for implantation in human body by the Food and Drug Administration (FDA), and at the moment it is being used in several clinical strategies. The present study consists of first preparing films with different degrees of crystallinity and characterizing these PLLA films, in terms of surface and structural properties, and subsequently assessing the behavior of cells in terms of viability, proliferation, morphology and mineralization for each PLLA configuration. PLLA films were prepared using the solvent cast technique and submitted to different thermal treatments in order to obtain different degrees of crystallinity. Those platforms were then electrically poled, positively and negatively, by corona discharge in order to tailor their electrical properties. The cellular assays were conducted by using two different osteoblast cell lines grown directly onto the PLLA films:Human osteoblast Hob, a primary cell culture and Human osteosarcoma MG-63 cell line. This thesis gives also a comprehensive introduction to the area of Bone Tissue Engineering and provides a review of the work done in this field in the past until today, in that same field, including the one related with bone’s piezoelectricity. Then the experimental part deals with the effects of the crystallinity degrees and of the polarization in terms of surface properties and cellular bio assays. Three different degrees of crystallinity, and three different polarization conditions were prepared; which results in 9 different configurations under investigation.

Inteligência coopetitiva setorial: uma proposta de modelo

The business environment context points at the necessity of new forms of management for the sustainable competitiveness of organizations through time. Coopetition is characterized as an alternative in the interaction of different actors, which compete and cooperate simultaneously, in the pursuit of common goals. This dual relation, within a gain-increasing perspective, converts competitors into partners and fosters competitiveness, especially that of organizations within a specific sector. The field of competitive intelligence has, in its turn, assisted organizations, individually, in the systematization of information valuable to decision-making processes, which benefits competitiveness. It follows that it is possible to combine coopetition and competitive intelligence in a systematized process of sectorial intelligence for coopetitive relations. The general aim of this study is, therefore, to put forth a model of sectorial coopetitive intelligence. The methodological outlining of the study is characterized as a mixed approach (quantitative and qualitative methods), of an applied nature, of exploratory and descriptive aims. The Coordination of the Strategic Roadmapping Project for the Future of Paraná's Industry is the selected object of investigation. Protocols have been designed to collect primary and secondary data. In the collection of the primary ata, online questionary were sent to the sectors selected for examination. A total of 149 answers to the online questionary were obtained, and interviews were performed with all embers of the technical team of the Coordination, in a total of five interviewees. After the collection, all the data were tabulated, analyzed and validated by means of focal groups with the same five members of the Coordination technical team, and interviews were performed with a representative of each of the four sectors selected, in a total of nine participants in the validation. The results allowed the systematization of a sectorial coopetitive intelligence model called ICoops. This model is characterized by five stages, namely, planning, collection, nalysis, project development, dissemination and evaluation. Each stage is detailed in inputs, activities and outputs. The results suggest that sectorial coopetition is motivated mainly by knowledge sharing, technological development, investment in R&D, innovation, chain integration and resource complementation. The importance of a neutral institution has been recognized as a facilitator and incentive to the approximation of organizations. Among the main difficulties are the financing of the projects, the adhesion of new members, the lack of tools for the analysis of information and the dissemination of the actions.

Mobilidade elétrica

No último século, a utilização de combustíveis fosseis permitiram uma acelerada industrialização intimamente associada a consumos crescentes de energia. Mas a sua utilização não é neutra do ponto de vista ambiental, pois liberta gases de efeito de estufa (GEE), que estão a alterar o equilíbrio da nossa atmosfera que existia no período préindustrial. Apoiado em estudos científicos cada vez mais credibilizados pela comunidade científica, o poder político está consciente das suas consequências climáticas, e por isso empenhado em mudar a matriz energética com vista a uma redução progressiva dos GEE.

Memória autobiográfica em jovens adultos com comportamentos suicidários

2008 Dissertação de Mestrado apresentada no Instituto Superior de Psicologia Aplicada para a obtenção de grau de Mestre na especialidade de Psicologia Clínica

Aportes críticos para a cooperação internacional em saúde : uma perspectiva bioética

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ciências da Saúde, Programa de Pós-Graduação em Bioética, 2015.

Avaliação probabilística do risco de giberela do trigo considerando a influencia do ENOS.

A giberela é uma importante doença na cultura do trigo cujas epidemias ocorrem sob a influência marcante de condições ambientais específicas durante o florescimento. Neste trabalho, a influência do fenômeno El Nino/Oscilação Sul (ENOS) sobre o risco de epidemias da giberela do trigo, em Passo Fundo, RS, estimado com modelos de simulação, foi avaliada via abordagem de anos análogos. Foi utilizada uma série local histórica (1957 a 2006) de dados meteorológicos para estimar um índice de risco de giberela (IRG) para diferentes datas de plantio (1 a 30/06) nos 50 anos da série. Para quantificar a influência do ENOS, foram comparadas medianas e funções probabilidade de excedância (FPE) do IRG (Prob(IRG>y)para três fases do ENOS (quente, fria e neutra) nos anos da série, utilizando métodos não paramétricos. Foi observado um efeito pronunciado do ENOS, principalmente para a fase fria, onde o risco estimado de epidemias moderadas ou severas foi nulo para todas as datas de plantio. Nas demais fases, o referido risco variou de 0,10 a 0,25.

A não cumulatividade do IPI na exportação de mercadorias nacionais sob a perspectiva da análise jurídica da política econômica : neutralidade da incidência tributária e efetiviade do creditamento

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Direito, Programa de Pós-Graduação Stricto Sensu em Direito, 2016.

Conocimientos, actitudes y prácticas en pacientes con diabetes mellitus tipo 2 que acuden al centro de atención ambulatoria 302 del IESS en el periodo de mayo a julio, Cuenca Ecuador, 2015

Objetivo Determinar el nivel de conocimientos, actitudes y prácticas en pacientes con Diabetes mellitus tipo 2 que acudieron al centro de Atención Ambulatorio 302 del Instituto Ecuatoriano de Seguridad Social, de la ciudad de Cuenca, durante mayo a julio de 2015. Material y métodos Se realizó un estudio descriptivo, en una muestra no probabilística de 289 pacientes durante el periodo de mayo a julio de 2015. Los datos de conocimientos, actitudes y prácticas se obtuvieron por entrevista directa mediante la aplicación de cuestionarios validados y fueron analizados con el software SPSS versión 2015. Resultados La edad osciló entre 40 y 94 años, con una mediana de 69. El 61,6% fueron mujeres. El 91% residía en el área urbana. La mediana del tiempo de evolución de la diabetes fue 12 años. El nivel de conocimientos adecuados en diabetes fue 1,4%; intermedio de 61% e inadecuado de 77,5%. Actitudes positivas se detectó en el 88,2%, neutra 6,6% y negativas 5,2%. Muy buenas prácticas se determinaron en 5.5%, buenas prácticas en 67.1%, y malas prácticas en 27.3%. Conclusión La aplicación de los cuestionarios nos permitió determinar cuáles son las falencias de los diabéticos; para que tanto médicos como personal de salubridad, diseñen y apliquen estrategias, métodos de aprendizaje y comunicación para aumentar el nivel de conocimientos y prácticas, en pro de disminuir las tasas de morbimortalidad a causa de esta patología.

Recepción y traducción en alemán de Mamita Yunai, de Carlos Luis Fallas

Se plantea la doble tipología entre una literatura marcada (la nacional) y una neutra (universalista) y sus posibles aplicaciones desde el punto de vista traductológico. Se exploran las dificultades y potencialidad de la traducción de las letras costarricenses, a partir del caso de una novela paradigmática costarricense (Mamita Yunai, de C. L. Fallas), su traducción y recepción en alemán. Mediante un análisis detenido de oportunos ejemplos, se explican aspectos esenciales del proceso traductológico. El rasgo central de este análisis es mostrar el binomio entre la neutralización (en su traducción) del discurso literario y el rescate de sus rasgos discursivos distintivos (del texto original).A double typology is posed between marked (national) and neutral (universal) Iiterature, and its possible applications from a translation standpoint. The difficulties and potential are explored for the translation of Costa Rican literature, starting with the case of a paradigmatic novel (Mamita Yunai, by C. L. Fallas), its translation and its reception in German. Through a detailed analysis of illustrative examples, essential aspects of the translation process are explained. The main objective of this analysis is to illustrate the issue of neutralization (in the translation) of literary discourse or conservation of distinctive discursive features (from the original text).