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Determination of quinolones in bovine kidney using hollow-fiber supported liquid membrane extraction prior to liquid chromatography tandem mass spectrometryGaolape, Kefilwe Precious 10 1900 (has links)
Focus of this study was on the development of one of the faster, simpler, cost effective and environmentally friendly sample pre-treatment techniques which employs a supported liquid membrane, in this case a Hollow-fiber supported liquid membrane (HF-SLM) for determination of seven (7) quinolone antibiotics (enrofloxacin, ciprofloxacin, danofloxacin, difloxacin, norfloxacin, nalidixic acid and sarafloxacin) in bovine kidney samples followed by LC-MS/MS analysis. The key parameters of the method were optimized and the method was validated following the 2002/657 EC guidelines. The optimum HF-SLM conditions were therefore; NaH2PO4 as a donor phase at pH 7, 0.1% formic acid at pH 3 as acceptor phase. Triethylamine was the optimized liquid membrane and the stirring time was optimized at 1 hour. Separation of the 7 quinolones including 3 internal standards (enrofloxacin-d5, norfloxacin-d5 and difloxacin-d3) was carried out on a Phenomenex Kinetex 2.6 μm XB-C18, 100 mm x 4.6 mm, 100Å column. Validation parameters such as Correlation coefficients (r2) ranging from 0.9714-0.9975 were obtained, while limit of detection (LOD) ranged between 3-39 ug kg-1 and limit of quantification (LOQ) ranged between 10-130 ug kg-1. The obtained limits at which it can be concluded with an error probability of α = 95% that a sample is non-compliant (CCα) ranged from 28 – 422 ug kg-1 while CCβ; the smallest content of the substance that may be detected, identified or quantified in a sample with an error probability of β = 95%, ranged from 29 – 454 ug kg-1. The method was found to be reproducible with CVs ≤ 23 %. The tested samples from Botswana local abattoirs showed no presence of quinolone antibiotics when the method was applied to real bovine kidney samples. Hollow-fiber supported liquid membrane can therefore be used for extraction of biological samples since it is a “greener technique” which uses less solvent which are less harmful to the environment when disposed as compared to dispersive Solid Phase Extraction (dSPE). / Chemistry / M. Sc. (Chemistry)
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Alimentation électrique d'un site isolé à partir d'un générateur photovoltaïque associé à un tandem électrolyseur/pile à combustible (batterie H2/O2)Gailly, Frédéric 18 July 2011 (has links) (PDF)
Les systèmes à énergies renouvelables couplés à un stockage hydrogène apportent des solutions nouvelles et innovantes à l'alimentation électrique des milieux peu ou non électrifiés. Le concept de batterie H2 qui équipe ce type de système est une forme de stockage originale qui apporte l'autonomie et l'indépendance électrique pour des longues durées (typiquement stockage saisonnier). Le fonctionnement de cette batterie H2 est le suivant : un électrolyseur produit des gaz (H2 et O2) avec les surplus d'énergie de la source renouvelable ; l'hydrogène, voire l'oxygène, est ensuite stocké dans des réservoirs pour être utilisé ultérieurement grâce à une pile à combustible lorsque la source renouvelable est insuffisante. Dans cette étude, nous nous intéresserons spécifiquement au couplage entre des générateurs photovoltaïques avec une batterie H2/O2 pour l'alimentation d'un site isolé sans interruption. Ces travaux de recherche s'inscrivent dans le projet ANR PEPITE (ANR-PanH 2007-2012) et ont été menés en partenariat avec HELION Hydrogen Power, le CEA Liten et l'Université de Corse. Le projet est également labellisé par les pôles de compétitivité CAPENERGIES et TENERRDIS. Tout d'abord, une réflexion générale s'appuyant sur les propriétés d'une batterie H2/O2 démontre la nécessité d'introduire une batterie (ici au plomb) pour garantir un fonctionnement instantané et sans interruption. Puis, une étude qualitative sur les architectures électriques possibles (bus de tension DC, AC…) a été menée pour s'achever sur une étude quantitative réalisée spécifiquement pour le projet PEPITE. Parallèlement à cela, différentes stratégies de gestions énergétiques ont été proposées afin d'utiliser les deux stockages dans les meilleures conditions, de limiter leur vieillissement ainsi que les pertes. Deux bancs d'essais à échelle réduite (un premier à bus DC et un second à bus AC) ont été réalisés au sein du laboratoire LAPLACE afin de valider les études et de préparer le prototype final qui sera testé sur le site de HELION Hydrogen Power au cours de l'été 2011.
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Alimentation électrique d'un site isolé à partir d'un générateur photovoltaïque associé à un tandem électrolyseur/pile à combustible (batterie H2/O2)Gailly, Frédéric 18 July 2011 (has links) (PDF)
Les systèmes à énergies renouvelables couplés à un stockage hydrogène apportent des solutions nouvelles et innovantes à l'alimentation électrique des milieux peu ou non électrifiés. Le concept de batterie H2 qui équipe ce type de système est une forme de stockage originale qui apporte l'autonomie et l'indépendance électrique pour des longues durées (typiquement stockage saisonnier). Le fonctionnement de cette batterie H2 est le suivant : un électrolyseur produit des gaz (H2 et O2) avec les surplus d'énergie de la source renouvelable ; l'hydrogène, voire l'oxygène, est ensuite stocké dans des réservoirs pour être utilisé ultérieurement grâce à une pile à combustible lorsque la source renouvelable est insuffisante. Dans cette étude, nous nous intéresserons spécifiquement au couplage entre des générateurs photovoltaïques avec une batterie H2/O2 pour l'alimentation d'un site isolé sans interruption. Ces travaux de recherche s'inscrivent dans le projet ANR PEPITE (ANR-PanH 2007-2012) et ont été menés en partenariat avec HELION Hydrogen Power, le CEA Liten et l'Université de Corse. Le projet est également labellisé par les pôles de compétitivité CAPENERGIES et TENERRDIS. Tout d'abord, une réflexion générale s'appuyant sur les propriétés d'une batterie H2/O2 démontre la nécessité d'introduire une batterie (ici au plomb) pour garantir un fonctionnement instantané et sans interruption. Puis, une étude qualitative sur les architectures électriques possibles (bus de tension DC, AC…) a été menée pour s'achever sur une étude quantitative réalisée spécifiquement pour le projet PEPITE. Parallèlement à cela, différentes stratégies de gestions énergétiques ont été proposées afin d'utiliser les deux stockages dans les meilleures conditions, de limiter leur vieillissement ainsi que les pertes. Deux bancs d'essais à échelle réduite (un premier à bus DC et un second à bus AC) ont été réalisés au sein du laboratoire LAPLACE afin de valider les études et de préparer le prototype final qui sera testé sur le site de HELION Hydrogen Power au cours de l'été 2011.
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Caracterização de serina peptidases e identificação do perfil proteico em intestino de Culex quinquefasciatus, Anopheles albitarsis s.s e Aedes aegypti (Diptera: Culicidae)Veloso, André Borges January 2015 (has links)
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Previous issue date: 2015 / Fundação Oswaldo Cruz. Instituto Oswaldo Cruz. Rio de Janeiro, RJ, Brasil / Os dípteros Aedes aegypti, Anopheles albitarsis e Culex quinquefasciatus pertencem à família Culicidae e são considerados um problema de saúde pública quando atuam como vetores de parasitos e/ou arboviroses. O regime de alimentação de fêmeas dos mosquitos anautógenos influencia os processos que ocorrem no intestino e regula os genes envolvidos na reprodução. Além disso, apesar dos ciclos de vida dos parasitos veiculados por essas espécies de vetores serem distintos, todos eles são ingeridos durante a hematofagia e expostos ao ambiente do intestino médio (estômago) para em seguida atravessar o epitélio intestinal e chegarem ao tecido apropriado para seu desenvolvimento e/ou transmissão para um novo hospedeiro vertebrado. Neste trabalho, utilizamos uma abordagem proteômica para a identificação de proteínas totais, bem como ensaios em solução e enzimografia em gel copolimerizado com substrato para identificação de peptidases ativas presentes no intestino de fêmeas de Cx. quinquefasciatus e An. albitarsis s.s sob regime de alimentação com açúcar. As técnicas de enzimografia também foram utilizadas aqui para a caracterização de peptidases ativas de intestinos de fêmeas de Ae. aegypti alimentadas com açúcar ou sangue. Foi observado que o intestino de fêmeas das três espécies alimentadas com açúcar apresenta um complexo perfil de peptidases ativas, do tipo tripsina, composto por bandas migrando nas regiões entre ~ 24 a 40 kDa e em regiões de alto peso molecular
Atividades proteolíticas foram detectadas entre pH 3,5 \2013 10, revelando diferenças quantitativas e qualitativas entre os perfis proteolíticos das três espécies. Em fêmeas de Ae. aegypti, o regime de alimentação com açúcar ou sangue alterou o perfil de SPtrip ativas do intestino de forma qualitativa e quantitativa. Um total de oito tripsinas em Cx. quinquefasciatus e dez tripsinas em An. albitarsis, foram identificadas por SDS-PAGE acoplado a LC-MS/MS. Apesar dessas SPtrip identificadas apresentarem características comuns às tripsinas digestivas de invertebrados, foram observadas diferenças nas sequências de aminoácidos, como por exemplo, em regiões de especificidade ao substrato e de ativação do zimogênio. Foi observado que os genes codificadores para SPtrip possuem diferentes tamanhos e organização, tais como, diferenças no número de éxons/introns. Com relação à composição de proteínas totais solúveis do intestino de fêmeas de Cx. quinquefasciatus e An. albitarsis, análise por LC-MS/MS e bioinformática revelou a presença de proteínas envolvidas em processos fisiológicos importantes, como exopeptidaes, glicosidades, enzimas detoxificantes e proteínas relacionadas com a interação parasito/vetor
Em Cx. quinquefasciatus, foram identificadas 1397 proteínas, distribuídas em 1090 grupos, representando um total de ~ 7,5% das proteínas codificadas pelo genoma dessa espécie. Em An. albitarsis foram identificadas 916 proteínas distribuídas em 748 grupos. As centenas de proteínas presentes no intestino de fêmeas alimentadas com açúcar, de ambas as espécies, foram classificadas segundo sua ontologia gênica e o papel de algumas famílias de proteínas historicamente importante em mosquitos foram discutidas. Finalmente, foi demonstrado que abordagem proteômica combinada à enzimografia e bioinformática é uma ferramenta que pode auxiliar na anotação funcional dos genes de tripsinas expressos no intestino de fêmeas alimentadas com açúcar, bem como auxilia no mapeamento do repertório de proteínas totais presentes no intestino de Cx. quinquefasciatus e An. albitarsis / Culex quinquefasciatus, Anopheles albitarsis and Aedes aegypti are hematophagous insect from the Culicidae family that feeds on the blood of humans, dogs, birds and livestock. These species transmit a wide variety of pathogens between humans and animals. The midgut environment is the first location of pathogen-vector interaction for blood-feeding mosquitoes and the expression of specific peptidases in the early stages of feeding could influence the outcome of the infection. Trypsin-like serine peptidases belong to a multi-gene family that can be expressed in different isoforms under distinct physiological conditions. However, the confident assignment of the trypsin genes that are expressed under each condition is still a challenge due to the large number of trypsin-coding genes in the Culicidae family and most likely because they are low abundance proteins. We used zymography for the biochemical characterization of the peptidase profile of the midgut from Cx. quinquefasciatus, An. albitarsis, and Ae. aegypti females fed on sugar. We also caracterized the peptidses profile of the midgut from Ae. aegypti fed on blood, during different moments after fedding. Protein samples were also submitted to SDS-PAGE followed by liquid chromatography–tandem mass spectrometry (LC–MS/MS) analysis for peptidase identification. The peptidases sequences were analyzed by bioinformatics tools to assess their distinct features. Zymography revealed that trypsin-like serine peptidases were responsible for the proteolytic activity in the midgut of females fed on sugar or blood diet. In addition, we observed that the profile is influenced by the blood ingestion. After fractionation in SDS-PAGE, eight and ten trypsin-like serine peptidases were identified by LC-MS/MS in Cx. quinquefasciatus and An. albitarsis, respectively. Peptidases from Cx. quinquefasciatus were also analysed with bioinformatic tools revealing that they have structural features typical of invertebrate digestive trypsin peptidases but exhibited singularities at the protein sequence level such as: the presence of different amino acids at the autocatalytic motif and substrate binding regions as well as different number of disulfide bounds. Data mining revealed a group of trypsin-like serine peptidases that are specific to C. quinquefasciatus when compared to the culicids genomes sequenced so far. We demonstrated that proteomics approaches combined with bioinformatics tools and zymographic analysis can lead to the functional annotation of trypsin-like serine peptidases coding genes and aid in the understanding of the complexity of peptidase expression in mosquitoes. / 2016-10-11
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Análise da influência dos parâmetros de soldagem sobre a geometria do cordão de solda depositado pelo processo de soldagem TIG - MAG em tandemTeixeira, Gustavo Simões January 2011 (has links)
O objetivo deste trabalho é analisar a influência dos parâmetros de um sistema mecanizado de soldagem, composto por uma tocha TIG e outra MAG em tandem, sobre a geometria do cordão de solda resultante. Os resultados obtidos foram comparados com soldas realizadas pelos processos TIG e MAG operando isoladamente. Os testes foram executados por meio de simples deposição de cordões sobre chapas de aço ao carbono AISI 1010 com espessura de 6,3 mm. Os parâmetros analisados foram: corrente de soldagem e distância da ponta do eletrodo até a peça no processo TIG, velocidade de alimentação de arame e tensão do arco no processo MAG, além de velocidade de soldagem e distância entre as tochas. Os cordões de solda foram executados em um dispositivo de soldagem mecanizado, que permite a variação da velocidade de soldagem, distância da ponta do eletrodo TIG e a distância entre as tochas. Os ajustes de corrente e tensão de soldagem foram feitos em duas fontes de potência separadas, ambas do tipo transformador-retificador, uma para cada tocha, devido às diferentes curvas características de cada processo. Através do projeto de experimento fatorial fracionado, foram avaliados os efeitos de dois níveis, um mínimo e outro máximo, mais quatro réplicas dos seus níveis intermediários, resultando em 20 experimentos para cada processo de soldagem. Os valores dos resultados finais indicam uma diferença ao utilizar uma tocha TIG para pré-aquecer o material base, porém, estatisticamente, essa diferença não é significativa entre os processos TIG e MAG em tandem e MAG convencional para a faixa de parâmetros de soldagem adotada. / This study aims to investigate the influence of process parameters of a mechanized welding system, comprising a GTAW torch and a GMAW torch in tandem configuration, on the geometry of the resulting weld bead, performed using GTAW and GMAW welding processes in tandem. The results were compared with weld beads performed by conventional GTAW and GMAW welding processes. The tests were conducted performing bead-on-plate deposits over AISI 1010 6,3 mm thick carbon steel plates. GTAW current, GMAW wire feed speed, GTAW arc length, GMAW voltage, welding speed and the distance between GTAW and GMAW torches were the analyzed parameters. The weld beads were performed in a mechanized welding bench, which allows the variation of speed, distance between torches and arc length of the GTAW torch. Current and voltage adjustments were made in two separate transformer-rectifier power sources, one for each welding torch, due to their different characteristic curves of each process. Through the fractional factorial design of experiment, the effects of two different levels for each parameter were analyzed, plus four replicates of the average values of these levels, resulting in 20 experiments for each welding process. The results show a difference on the weld bead geometry using a GTAW torch to preheat the base metal, however, this difference is not statistically significant between GTAW and GMAW welding process in tandem and GMAW welding process for the adopted range of welding parameters.
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Construction of Complex Polycyclic Systems using Gold Catalyzed Intramolecular Diyne/Enyne/ Hydroalkoxylation ReactionsNagaraju, CH January 2015 (has links) (PDF)
First section of chapter 1 deals with gold catalyzed synthesis of ring fused furo[3,2,b]pyrans and furo[3,2,b]furans. Furo[3,2,b]pyrans and furo[3,2,b]furans are ubiquitous structural segments found in a number of natural products including polyether containing marine toxins. Synthesis of furo[3,2,b]pyrans 2a was accomplished from the bis-propargyl ethers 1a, while the synthesis of furo[3,2,b]furans 2b was accomplished from the prenyl propargyl ethers 1b.
Scheme 1: Synthesis of furo[3,2,b]pyrans and furo[3,2,b]furans
Second section of chapter 1 describes an unusual ring-contraction rearrangement route to functionalized 2,8-oxymethano-bridged di and triquinane. During the course of investigations concerning the total synthesis of 6-oxabicyclo[3.2.1]octane framework containing natural products, an unusual ring-contraction rearrangement sequence was observed in the reaction of 5-substituted 1-methyl-4-isopropenyl-6-oxabicyclo[3.2.1]octan-8-ones 4 to the 2,8-oxymethano-bridged diquinanes 5. The reaction was further demonstrated in the synthesis of triquinane 7 framework.
Scheme 2: Synthesis of functionalized di and triquinane
In third section of chapter 1 gold catalyzed synthesis of isochromanones and isoquinolones from suitable substituted allyl propargyl ethers was discussed. Synthesis of isochromanones and isoquinolones comprising a quaternary center with high diastereoselectivity was realized via AuCl3 catalyzed tandem intramolecular exo-dig heterocyclization/enol isomerization/Claisen rearrangement sequence in excellent yields. The reaction was general and amenable for the synthesis of structurally diverse analogues.
Scheme 3: Synthesis of isochromanones and isoquinolones
Forth section of chapter 1 consists of gold catalyzed intramolecular hydroalkoxylation assisted ring opening of furans to the corresponding saturated -keto esters. During the course investigations concerning gold catalyzed intramolecular enyne cyclization reactions, an interesting ring opening of furans in furyl propargyl alcohols to the corresponding tetrahydrofuran appended saturated -keto esters exclusively driven by intramolecular hydroalkoxylation of the alkyne was observed. Reaction of furyl propargyl alcohols without free hydroxyl group, under similar conditions afforded the conjugated enynes involving dehydration/ketalization.
Scheme 4: Synthesis of saturated -keto esters and enynes
Chapter 2 delineates the enantiospecific synthesis of bicyclo[4.2.2]decadienes 15 via gold catalyzed tandem enyne cyclization, semipinacol rearrangement reaction. Bicyclodecadienes are key structural units of natural products nakafuran-8 and pallescensin B.
Scheme 5: Synthesis of bicyclo[4.2.2]decadienes
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Estudo de frequências alélicas de 15 STRs autossômicos na população paraibanaCastro, Sarah Gurgel de 26 February 2014 (has links)
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Previous issue date: 2014-02-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Human identification is based on analyzing DNA through present throughout the genome molecular markers. These markers are transmitted from parents to offspring by heredity. STR markers are currently the most commonly used genetic markers in Forensic Genetics due to their high polymorphism, high reproducibility, possibility of being amplified by PCR in multiple copies in a single reaction, and minute quantities of DNA (1ng). The DNA test that allows individualization of the people is essential tool to the solution of forensic human identification cases, sex crimes, crime scenes (including or excluding suspects), mass disasters, and its result is presented in statistical calculations that consider allele frequency of markers used. So it is important to know the allele frequencies presented in the regional population so that the results are the most reliable possible. In this study , 15 autossomal markers (loci) STR or microsatellite (CSF1PO, D13S317, D16S539, D18S51, D19S433, D21S11, D2S1338, D3S1358, D5S818, D7S820, D8S1179, FGA, TH01, and VWA TPOX) were studied in 766 unrelated individuals paraibanos, demonstrating a tri population - hybrid formed Africans (25.86 %), Amerindian (6.81 %) and Europeans (67.33 %). The most informative were D21S11 and FGA, and were less informative TPOX, D7S820 and D13S317. The results are important for a database with allele frequencies found in Paraiba population can serve as a useful basis for calculating forensic practice in the State of Paraíba. / A identificação humana está baseada na análise do DNA através de marcadores moleculares presente em todo o genoma. Estes marcadores são transmitidos de pais para filhos por hereditariedade. Atualmente os marcadores STR são os marcadores genéticos mais utilizados em Genética Forense devido ao seu elevado polimorfismo, alta reprodutibilidade, possibilidade de serem amplificados por PCR em inúmeras cópias numa só reação e em mínimas quantidades de DNA (1ng). O exame de DNA que permite a individualização das pessoas é ferramenta indispensável à solução de casos forenses de identificação humana, crimes sexuais, locais de crime (incluindo ou excluindo suspeitos), desastres em massa, e tem seu resultado apresentado em cálculos estatísticos que consideram a frequência alélica dos marcadores usados. Por isso é importante o conhecimento das frequências alélicas apresentadas na população regional de forma que os resultados sejam os mais fidedignos possíveis. Neste trabalho, 15 marcadores autossômicos (loci) STR ou microssatélites (CSF1PO, D13S317, D16S539, D18S51, D19S433, D21S11, D2S1338, D3S1358, D5S818, D7S820, D8S1179, FGA, TH01, TPOX e vWA) foram estudados em 766 indivíduos paraibanos não aparentados, demonstrando uma população tri - hibrida, formada de africanos (25,86%), ameríndios (6,81%) e europeus (67,33%). Os mais informativos foram D21S11 e FGA, e os menos informativos foram TPOX, D7S820 e D13S317. Os resultados são importantes para que um banco de dados com as frequências alélicas encontradas na população paraibana possa servir de base de cálculo útil para prática forense no Estado da Paraíba.
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Espectrometria de massas aplicada aos estudos de biossíntese de alcalóides de Senna spectabilis /Pivatto, Marcos. January 2010 (has links)
Resumo: O presente trabalho teve como objetivo o estudo das vias biossintéticas dos alcalóides piperidínicos presentes em Senna spectabilis, motivado pela potente atividade anticolinesterásica e baixa toxicidade observada no derivado (-)-3-O-acetil-espectalina (15), eleito como composto líder para o desenvolvimento de fármacos anti-Alzheimer que estão em fase de estudos pré-clínicos. Por outro lado, o interesse acadêmico no conhecimento das vias metabólicas, pode levar a estudos futuros de engenharia genética para potencializar a produção desses metabólitos uma vez que a síntese é extremamente complexa em função da presença de três centros estereogênicos. Tendo isso em vista, foram selecionadas seis espécies de Senna e Cassia para avaliar a presença dos alcalóides e selecionar aquela que os produz em maior quantidade. Foram estudadas as flores de S. spectabilis, S. multijuga, S. macranthera, S. velutina, C. fistula, C. leptophylla, sendo que só foram detectados alcalóides piperidínicos e piridínicos em S. spectabilis e S. multijuga, respectivamente, utilizando a espectrometria de massas tandem. Embora sejam de classes diferentes, esses metabólitos têm padrão de substituição similar, porém, apresentaram atividade anticolinesterásica diferenciada. De S. spectabilis foram isolados os alcalóides piperidínicos: (-)-cassina (1), (-)-espectalina (9), (-)-3-O-acetil-espectalina (15), (-)-3-O-acetil-cassina (16) e identificados 7-hidroxi-carnavalina (71), 7-hidroxi-cassina (18) e/ou espicigerina (42) utilizando a EM. De S. multijuga foram isolados os alcalóides piridínicos: 7'-multijuguinona (67) e 12'-hidroxi-7'-multijuguinona (69) e identificados 7'-multijuguinol (68) e 12'-hidroxi-7'- multijuguinol (70). Para os estudos biossintéticos dos alcalóides piperidínicos foi inicialmente proposta a biogênese onde lisina e acetato foram eleitos potenciais... (resumo completo, clicar acesso eletrônico abaixo) / Abstract: The following work encompass as main goal the study of biosynthetic pathways to produce piperidine alkaloids using Senna spectabilis as natural matrix. Such research was instigated due to the high acetylcholinesterase activity and low toxicity showed by the derivative (-)-3-O-acetyl-spectaline (15), selected as a lead compound against Alzheimer's disease and currently under pre-clinical trials. Still yet, the academic interest on researching metabolic pathways that may lead to further genetic engineering studies to enhance the production of these metabolites is of extremely importance, due to the inability of producing any commercially viable synthetic strategy for their stereogenic centers. We selected six Senna and Cassia species to evaluate the presence of these metabolites aiming to select which matrix will produce them the most. We studied flowers from S. spectabilis, S. multijuga, S. macranthera, S. velutina, C. fistula and C. leptophylla. From those, we were able to detect piperidine and pyridine alkaloids only in S. spectabilis and S. multijuga, respectively, using tandem mass spectrometry. Regardless of the different structural nature towards 15, those metabolites have similar substitution patterns and showed differential acetylcholinesterase activity. From S. spectabilis were isolated the piperidine alkaloids: (-)-cassine (1), (-)-spectaline (9), (-)-3-O-acetyl-spectaline (15), (-)-3-O-acetyl-cassine (16), and identified 7-hidroxy- carnavaline (71), 7-hidroxy-cassine (18) and/or spicigerine (42) by tandem mass spectrometry and from S. multijuga were isolated the pyridine alkaloids: 7'-multijuguinone (67), 12'-hydroxy-7'-multijuguinone (69) and, identified by MS: 7'-multijuguinol (68) and 12'-hydroxy-7'-multijuguinol (70). We initially proposed the incorporation of lysine and acetate as main precursors of the piperidine alkaloids biosynthetic pathway and thus... (Complete abstract click electronic access below) / Orientador: Vanderlan da Silva Bolzani / Coorientador: Maysa Furlan / Banca: Ian Castro-Gamboa / Banca: Frederico Guaré Cruz / Banca: Márcia Nasser Lopes / Banca: Maria Claudia Marx Young / Doutor
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New ways to take advantage from solar energy and produce hydrogen / Nuevas formas de aprovechar la energía solar y producir hidrógenoRey de Castro, Ana 25 September 2017 (has links)
Un grupo de investigadores del Instituto Tecnológico de Israel ha observado que el uso de foto ánodos de Fe2O3 produce una mejora importante en el rendimiento de las celdas fotoelectroquímicas. Las mejoras están basadas en el uso de láminas muy delgadas de Fe2O3 que mejoran la eficiencia en el transporte de carga. La elección de Fe2O3 está basada en su estabilidad en agua, su alta eficiencia de absorción de luz, su no toxicidad y su bajo coste. Las celdas fotoelectroquímicas son importantes para la electrólisis del agua y la producción de hidrógeno. / A research group at the Israel Institute of Technology has outlined the use of Fe2O3 photoanodes to enhance the efficiency of photoelectrochemical cells. The improvement is based on the design of extremely thinsheets of Fe2O3, which allow for a more efficient transport of charge carriers, reducing the amount of them that are lost due to recombination. Fe2O3 was chosen as a photoanode material due to its high stability in water, its high light absorption efficiency, the fact that it is non toxic and its low cost. Photoelectrochemical cells are extremely important in order to electrolyse water, hence producing hydrogen,a green fuel.
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Experimental and Computational Studies on the Design of Dyes for Water-splitting Dye-sensitized Photoelectrochemical Tandem CellsJanuary 2014 (has links)
abstract: Solar energy is a promising alternative for addressing the world's current and future energy requirements in a sustainable way. Because solar irradiation is intermittent, it is necessary to store this energy in the form of a fuel so it can be used when required. The light-driven splitting of water into oxygen and hydrogen (a useful chemical fuel) is a fascinating theoretical and experimental challenge that is worth pursuing because the advance of the knowledge that it implies and the availability of water and sunlight. Inspired by natural photosynthesis and building on previous work from our laboratory, this dissertation focuses on the development of water-splitting dye-sensitized photoelectrochemical tandem cells (WSDSPETCs). The design, synthesis, and characterization of high-potential porphyrins and metal-free phthalocyanines with phosphonic anchoring groups are reported. Photocurrents measured for WSDSPETCs made with some of these dyes co-adsorbed with molecular or colloidal catalysts on TiO2 electrodes are reported as well. To guide in the design of new molecules we have used computational quantum chemistry extensively. Linear correlations between calculated frontier molecular orbital energies and redox potentials were built and tested at multiple levels of theory (from semi-empirical methods to density functional theory). Strong correlations (with r2 values > 0.99) with very good predictive abilities (rmsd < 50 mV) were found when using density functional theory (DFT) combined with a continuum solvent model. DFT was also used to aid in the elucidation of the mechanism of the thermal relaxation observed for the charge-separated state of a molecular triad that mimics the photo-induced proton coupled electron transfer of the tyrosine-histidine redox relay in the reaction center of Photosystem II. It was found that the inclusion of explicit solvent molecules, hydrogen bonded to specific sites within the molecular triad, was essential to explain the observed thermal relaxation. These results are relevant for both advancing the knowledge about natural photosynthesis and for the future design of new molecules for WSDSPETCs. / Dissertation/Thesis / Ph.D. Chemistry 2014
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