Dissertations / Theses on the topic 'Nuclear products'

The angular anisotropy, $ omega$, of individual fission products produced from the $ sp{238} rm U( sp{12}$C, f) 119.9 MeV incident heavy-ion induced fission reaction, was modelled in terms of the angular momentum, l, conferred upon the intermediate nucleus. Evidence of incomplete momentum transfer led to a model treating fission products as being the result of two fission inducing processes: complete fusion resulting in compound nucleus formation, and an $ alpha$-transfer incomplete fusion process. The average angular anisotropies for each of the two processes were calculated to be, $ omega sb{ rm CF}$ = 2.57, and $ omega sb alpha$ = 1.71, respectively, which fit well to the experimental data. A new method was developed to estimate the total kinetic energy release of heavy-ion fission events leading to individual fission products from the above reaction. The average total $ langle$E$ sb{ rm k}{ rangle} approx 195$ MeV calculated using the new method is consistent with other experimental data, and with theories regarding heavy-ion induced fission.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
O presente trabalho descreve o isolamento e identificação dos constituintes químicos de Aristolochia melastoma Manso. O extrato acetônico de caules e raízes foi fracionado por cromatografia em coluna de sílica gel, e as frações obtidas foram submetidas a outros fracionamentos cromatográficos (CCDP, Sephadex LH-20, CC de C-18 e CLAE) e/ou lavagens com solventes orgânicos, resultando no isolamento de vinte compostos conhecidos: aristolactama AII, 9,9'-diacetato-secoisolariciresinol dimetil éter, tirosol, ácido p-hidroxibenzóico, ácido vanilínico, ácidos aristolóquicos I e II, aristolocatos de sódio IIIa e IVa, 4,5-dioxodeidroasimilobíneo, aristolocato de sódio I, sitosterol 3-O-β-D-glucopiranosídeo, glicerol, talictosídeo, uridina, talictricosídeo, icarisídeo D2, adenosina, kaempferol 3-O-β-robinobiosídeo e isorhamnetina 3-O-β-robinobiosídeo. A lignana 9,9'-diacetato-secoisolariciresinol dimetil éter e talictricosídeo são relatados pela primeira vez na família Aristolochiaceae. As identificações desses compostos foram baseadas nas análises dos seus dados espectrométricos (RMN 1D e 2D, UV e EM). Além disso, a análise dos dados obtidos a partir de literatura especializada acerca da ocorrência e biogênese de derivados nitrofeniletílicos sugere que a família Aristolochiaceae pode ter evoluído no sentido de formação de compostos nitrados
This work describes the isolation and identification of the chemical constituents of A. melastoma Manso. The acetone extract from stems and roots was fractionated by CC over silica gel and the resultant fractions were subjected to other chromatographic methods (PTLC, Sephadex LH-20, CC RP-18, and HPLC) and/or washed with organic solvents to give twenty known compounds: aristolactam AII, secoisolariciresinol dimethyl ether diacetate, tyrosol, p-hydroxybenzoic acid, vanillic acid, sodium aristolochates I, IIIa, and IVa, 4,5-dioxodehydroasimilobine, aristolochic acids I and II, sitosterol-3-O-β-D-glucopyranoside, glycerol, uridine, thalictoside, icariside D2, adenosine, thalictricoside, kaempferol 3-O-β-robinobioside, and isorhamnetin 3-O-β-robinobioside. Among these, secoisolariciresinol dimethyl ether diacetate and thalictricoside have being reported for the first time in the Aristolochiaceae family. The identifications of these compounds were based on analyses of their spectroscopic data (1D- and 2D-NMR, UV, and MS). Furthermore, an analysis of data obtained from specialized literature on the occurrence and biogenesis of nitrophenylethyl derivatives suggests that the Aristolochiaceae family may have evolved towards nitro compounds

Simultaneous measurements of the angular distribution, mass distribution and average total kinetic energy of fission fragments produced by the neutron-induced fission of 235U and 232Th have been made using a gridded ionisation chamber. The neutron energy range used was thermal to 1.9 MeV for 235U and 1.4 to 1.7 MeV for 232Th. The following topics were investigated: the interdependence of the fission fragment angular and mass distribution; the anomalous behaviour of fragment anisotropy for 235U(n,f) at neutron energies En below 150 keV; the possible existence of a third symmetric mass peak for 232Th(n,f); the mass fine structure in 235U(n,f) and 232Th(n,f); and the dependence of the fission fragment average total kinetic energy on the excitation energy of the fissioning nucleus. For this study, mono-energetic neutrons were produced by the and reactions. Four signals produced by the fission chamber were fed into a data acquisition system and processed by a specially modified comprehensive computer program. The results indicate that there is no interdependence between the angular and mass distributions of fragments for 235U(n,f) and for 232Th(n,f). The angular distribution of 235U fission fragments showed an anisotropy of less than one for En below 150 keV. For 232Th, the expected minimum in the anisotropy near En = 1.6 MeV was confirmed. No evidence for a third peak in the mass symmetry region of 232Th(n,f) was observed, within the yield sensitivity limitation of the chamber. Fine structure was observed in the mass yield distributions for 235U(n,f) and 232Th(n,f) at mass locations predicted by theory. The fission fragment average total kinetic energy for 235U(n,f) and 232Th(n,f) showed no significant dependence on the excitation energy of the fissioning nucleus. Possible reasons for some of these results are advanced.

Includes bibliographical references.
Multipulse Nuclear Magnetic Resonance (NMR) techniques were investigated via structural assignment of various natural products. The natural products chosen for investigation of 2D NMR spectroscopy as a structural tool were the opium alkaloids codeine and papaverine, the diterpenoid alkaloids delphinine and aconitine and the triterpenoid derivatives of cucurbitaceae. One dimensional NMR spectroscopy viz 1H, 13C and Distortionless Enhancement by Polarisation Transfer (DEPT) spectroscopy was initially applied to obtain a level of indication of the complexity of the structural problem solving. Various multipulse techniques were chosen depending on the sample quantity available, the sensitivity of the technique, the information provided and its applicabilty in the field of natural products. Both homonuclear scalar and dipolar correlation as well as short and long range heteronuclear correlation was investigated. The homonuclear Correlation Spectroscopy (COSY) experiment which revealed scalar 1H-1H scalar correlations was adequate for the structural assignment. The Heteronuclear Multiple Quantum Coherence (HMQC) experiment offered greater sensitivity on small sample quantities whilst the long range Heteronuclear Correlation (HETCOR) and Heteronuclear Multiple Bond Coherence (HMBC) experiments were essential for complete assignment of the quaternary groups. The stereochemical designation of some of the compounds was confirmed using the Rotating Frame Overhauser Enhancement Spectroscopy (ROESY) experiment which proved to be a more applicable pulse sequence for the natural products under investigation. The 1H and 13C assignments of these derivatives and the experimental approach used to obtain this data was compared to that present in the literature. The results indicate that apart from offering tremendous versatility depending on the special attributes of the compound, two dimensional NMR techniques are imperative for the unambiguous structural assignment of natural products.

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O perfil químico de folhas e frutos de Piper fuligineum foi analisado por cromatografia líquida de alta eficiência. A composição química de média polaridade dos dois órgãos vegetais apresentou semelhança. As análises demonstraram também que os frutos apresentavam composição química complexa, principalmente devido a presença de substâncias de maior polaridade. Essas análises permitiram selecionar as folhas de P. fuligineum para dar continuidade aos estudos químicos. Estes estudos resultaram no isolamento de cinco substâncias, sendo duas kavalactonas: (E)-6-(8-feniletil)-4-metoxi-2H-piran-2-ona e 6-(2-fenil-7,8-diidroxetil)-4-metoxi-2H-piran-2-ona; uma cromanona: (2,2-dimetil-4-oxocromano-6-carboxilato de metila) e dois derivados prenilados do acido benzoico: 4-hidroxi-3-(3-metilbutil-2-en-1-il)benzoato de metila e 4-metoxi-3-(3-metil-1-oxobut-2-en-1-il) benzoato de metila. As estruturas químicas das substâncias foram determinadas utilizando técnicas espectrométricas, incluindo RMN 1D e 2D. Todas as substâncias estão sendo descritas pela primeira vez em Piper fuligineum. A substância 4 é inédita como produto natural. O extrato etanolico das folhas e as frações obtidas de P. fuligineum foram avaliadas quanto ao potencial tripanocida frente à forma epimastigota da cepa Y de Trypanosoma cruzi, mostrando promissora atividade do extrato etanólico com IC50 de 26,67 g.mL-1 quando comparado com o controle positivo, benznidazol, com IC50 de 11,11 g.mL-1. O extrato acetato de etila, a fração clorofórmica e a substância 1 foram submetidos a testes antifúngicos frente aos fungos Candida albicans, C.krusei, C. tropicalis, C. parapsilosis e a levedura Cryptococcus neoformans. O extrato apresentou forte atividade frente ao fungo Candida tropicalis e moderada atividade frente aos fungos C. krusei, C. parapsilosis e a levedura Cryptococcus neoformans, enquanto a fração clorofórmica apresentou forte atividade frente ao...
The chemical profile of leaves and fruits of Piper fuligineum was analyzed by high performance liquid chromatography. The chemical composition of medium polarity related to leaves and fruits showed great similarity. The analysis also showed that the chemical composition of the fruits was more complex, mainly due to the presence of more polar substances. These analyzes allowed the selection of the leaves of P. fuligineum to continue the chemical studies. The chemical studies of the leaves of Piper fuligienum resulted in the isolation of six compunds, including two kavalactones (4- methoxy-6- [(E)-2-phenyl -vinyl] -2H-pyran-2-one and 6-(1,2-dihydroxy-2-phenyl- ethyl)-4-methoxy-2H- pyran-2-one), one chromanone (methyl-2,2-dimethyl-4-oxo-6- cromanacarboxylate) and two prenylated derivatives of benzoic acid (methyl-4-hydroxy-3-(3-methyl-2- buten-1-yl) benzoate and methyl-4-methoxy-3-(3-methyl -2-butenoyl) benzoate. The chemical structures of the isolated compounds were determined using spectrometric techniques, including 1D and 2D NMR. All compounds were described for the first time in Piper fuligineum, and the compound 4 is a new natural product. The ethanolic leaf extract and fractions obtained from P. fuligineum were evaluated for trypanocidal potential against epimastigote form of Trypanosoma cruzi Y strain, showing promising activity of the ethanol extract with IC50 of 26.67 g.mL-1 compared with the positive control benznidazole, with IC50 of 11.11 g.mL-1. The ethyl acetate extract, the chloroform fraction and substance 1 underwent antifungal drugs against fungi Candida albicans, C.krusei, C. tropicalis, C. parapsilosis and Cryptococcus neoformans yeast. The extract showed strong activity against the fungus Candida tropicalis and moderate activity against fungi C. krusei, C. parapsilosis and Cryptococcus neoformans yeast while the chloroform fraction showed strong activity against the fungus C. krusei, and moderate activity against...

Orientador: Maysa Furlan
Banca: Nivaldo Boralle
Banca: Marcos Pivatto
Resumo: O perfil químico de folhas e frutos de Piper fuligineum foi analisado por cromatografia líquida de alta eficiência. A composição química de média polaridade dos dois órgãos vegetais apresentou semelhança. As análises demonstraram também que os frutos apresentavam composição química complexa, principalmente devido a presença de substâncias de maior polaridade. Essas análises permitiram selecionar as folhas de P. fuligineum para dar continuidade aos estudos químicos. Estes estudos resultaram no isolamento de cinco substâncias, sendo duas kavalactonas: (E)-6-(8-feniletil)-4-metoxi-2H-piran-2-ona e 6-(2-fenil-7,8-diidroxetil)-4-metoxi-2H-piran-2-ona; uma cromanona: (2,2-dimetil-4-oxocromano-6-carboxilato de metila) e dois derivados prenilados do acido benzoico: 4-hidroxi-3-(3-metilbutil-2-en-1-il)benzoato de metila e 4-metoxi-3-(3-metil-1-oxobut-2-en-1-il) benzoato de metila. As estruturas químicas das substâncias foram determinadas utilizando técnicas espectrométricas, incluindo RMN 1D e 2D. Todas as substâncias estão sendo descritas pela primeira vez em Piper fuligineum. A substância 4 é inédita como produto natural. O extrato etanolico das folhas e as frações obtidas de P. fuligineum foram avaliadas quanto ao potencial tripanocida frente à forma epimastigota da cepa Y de Trypanosoma cruzi, mostrando promissora atividade do extrato etanólico com IC50 de 26,67 g.mL-1 quando comparado com o controle positivo, benznidazol, com IC50 de 11,11 g.mL-1. O extrato acetato de etila, a fração clorofórmica e a substância 1 foram submetidos a testes antifúngicos frente aos fungos Candida albicans, C.krusei, C. tropicalis, C. parapsilosis e a levedura Cryptococcus neoformans. O extrato apresentou forte atividade frente ao fungo Candida tropicalis e moderada atividade frente aos fungos C. krusei, C. parapsilosis e a levedura Cryptococcus neoformans, enquanto a fração clorofórmica apresentou forte atividade frente ao...
Abstract: The chemical profile of leaves and fruits of Piper fuligineum was analyzed by high performance liquid chromatography. The chemical composition of medium polarity related to leaves and fruits showed great similarity. The analysis also showed that the chemical composition of the fruits was more complex, mainly due to the presence of more polar substances. These analyzes allowed the selection of the leaves of P. fuligineum to continue the chemical studies. The chemical studies of the leaves of Piper fuligienum resulted in the isolation of six compunds, including two kavalactones (4- methoxy-6- [(E)-2-phenyl -vinyl] -2H-pyran-2-one and 6-(1,2-dihydroxy-2-phenyl- ethyl)-4-methoxy-2H- pyran-2-one), one chromanone (methyl-2,2-dimethyl-4-oxo-6- cromanacarboxylate) and two prenylated derivatives of benzoic acid (methyl-4-hydroxy-3-(3-methyl-2- buten-1-yl) benzoate and methyl-4-methoxy-3-(3-methyl -2-butenoyl) benzoate. The chemical structures of the isolated compounds were determined using spectrometric techniques, including 1D and 2D NMR. All compounds were described for the first time in Piper fuligineum, and the compound 4 is a new natural product. The ethanolic leaf extract and fractions obtained from P. fuligineum were evaluated for trypanocidal potential against epimastigote form of Trypanosoma cruzi Y strain, showing promising activity of the ethanol extract with IC50 of 26.67 g.mL-1 compared with the positive control benznidazole, with IC50 of 11.11 g.mL-1. The ethyl acetate extract, the chloroform fraction and substance 1 underwent antifungal drugs against fungi Candida albicans, C.krusei, C. tropicalis, C. parapsilosis and Cryptococcus neoformans yeast. The extract showed strong activity against the fungus Candida tropicalis and moderate activity against fungi C. krusei, C. parapsilosis and Cryptococcus neoformans yeast while the chloroform fraction showed strong activity against the fungus C. krusei, and moderate activity against...
Mestre

Denna licentiatavhandling behandlar effekten av två inneboende egenskaper (fissions produkter och egenbestrålning) hos utbränt kärnbränsle på hastigheten för strålningsinducerad upplösning av bränslematris (UO2). I ett framtida djupförvar kommer det utbrända kärnbränslet att deponeras 500 meter ner i berggrunden i en reducerande miljö. Under dessa förhållanden är UO2-matrisen själv en av de skyddande barriärerna mot frigörande av radionuklider, på grund av dess låga löslighet. När bränslet kommer i kontakt med vatten kommer U(IV) att oxideras till U(VI) av radiolysprodukter från vattnet och lösligheten för bränslematrisen kommer därmed att öka betydligt.

De flesta tidigare studier har utförts på obestrålad UO2 som skiljer sig signifikant från utbränt kärnbränsle. I utbränt kärnbränsle är de flesta fissionsprodukterna och neutronaktivieringsprodukterna radioaktiva och bränslet kommer därför bli bestrålat av sig självt. Effekten av joniserande strålning på reaktiviteten för UO2(s) har undersökts här. UO2 (pulver och fragment av en kuts) bestrålades i en 60Co γ-källa eller framför en elektronaccelerator varpå reaktiviteten för UO2 studerades genom oxidation av UO2 med MnO4 -. Det visade sig att reaktiviteten för UO2 ökar när det blir bestrålat för första gången (<20 kGy). Effekten ökar med ökande dos tills den når ett maxvärde ~1.3 gånger reaktiviteten för obestrålad UO2 vid torrbestrålning. Vid våtbestrålning ökar en dos på 140 kGy reaktiviteten 2.5 gånger. Effekten verkar vara permanent.

Tidigare studier har visat att H2O2 är den viktigaste oxidanten för upplösning av utbränt kärnbränsle under djupförvarsförhållanden. I vätgasatmosfär, som förväntas i ett djupförvar, har det visat sig att upplösningshastigheten är långsammare. Det har delvis förklarats med reaktionen mellan H2O2 och H2, som är väldigt långsam utan katalysator. Den katalytiska effekten av UO2 på den reaktionen har undersökts och det visades att den inte katalyseras av UO2.

En annan möjlig katalysator för reaktionen är ε-partiklar (ädelmetallpartiklar bestående av Mo, Ru, Tc, Pd och Rh) som bildats av fissionsprodukterna. Pd är en välkänd katalysator för reduktion med H2. Den eventuella katalytiska effekten av Pd har undersökts här. Även en eventuell katalytisk effekt av Pd på reduktionen av U(VI) med H2 undersöktes, både i vattenfas och i UO2-kutsar innehållande olika mängder Pd (som en modell för ε-partiklar).

Vi fann att Pd har en katalytisk effekt på reaktionen mellan H2O2 och H2 och andra ordningens hastighetskonstant är bestämd till (2.1±0.1)x10-5 m s-1. Pd har också en katalytisk effekt på reduktionen av U(VI) med H2 både i vattenlösning, hastighetskonstant (1.5±0.1)x10-5 m s-1, och i den fasta fasen. Hastighetskonstanten för processen i fast fas är 4x10-7 m s-1 och 7x10-6 m s-1 för kutsar med 1 respektive 3 % Pd. Dessa värden är väldigt nära diffusionsgränsen för den här typen av system. Den katalytiska effekten i den fasta fasen visar att upplösningen för 100 år gammalt bränsle kan stoppas helt. Vid 40 bar H2 krävs 10-20 ppm ädelmetallpartiklar och med 1 % ädelmetallpartiklar räcker det med 0.1 bar H2 för att stoppa upplösningen.

This licentiate thesis deals with the influence of two inherent properties (fission products and self irradiation) of spent nuclear fuel on the rate of radiation induced fuel matrix (UO2) dissolution. In a future deep repository the spent nuclear fuel will be deposited 500 meters down in the bedrock in a reducing environment. Under these conditions the UO2-matrix itself is one of the protective barriers against release of radionuclides due to its very low solubility. When the fuel comes in contact with water, U(IV) will be oxidized to U(VI) by products from radiolysis of water and the solubility of the fuel matrix will increase significantly.

Most previous studies have been performed on unirradiated UO2 which differ significantly from spent nuclear fuel. In spent nuclear fuel most of the fission products and neutron activation products are radioactive and therefore the fuel will be irradiated by itself. The effect of ionizing radiation on the reactivity of UO2 has been investigated here. UO2 (powder and fragment of a pellet) has been exposed to irradiation in a 60Co γ-source or in an electron accelerator and then the redox reactivity was studied. The kinetics for oxidation of UO2 by MnO4 - was used as a monitoring reaction. It was shown that the reactivity of UO2 increases when being irradiated for the first time (<20kGy). The effect increases with increasing dose until reaching a maximum value ~1.3 times the reactivity of unirradiated UO2 for dry irradiation. For wet irradiation a dose of 140 kGy increases the reactivity ~2.5 times. This effect appears to be permanent.

Previous studies have shown that H2O2 is the most important oxidant for spent nuclear fuel dissolution under deep repository conditions. Under H2 atmosphere, as expected in a deep repository, it has been shown that the dissolution rate is slower. This has partly been attributed to the reaction between H2O2 and H2 which is very slow without a catalyst. The catalytic effect of UO2 on this reaction was examined showing that UO2 does not catalyze this reaction.

Another possible catalyst for this reaction is the ε-particles (noble metal particles containing Mo, Ru, Tc, Pd and Rh) formed by the fission products. Pd is a well known catalyst for reduction by H2. The possible catalytic effect of Pd on the reaction between H2O2 and H2 is examined here. The possible catalytic effect of Pd on the reduction of U(VI) by H2 is also examined, both in aqueous phase and in UO2 pellets containing different amounts of Pd (as a model for spent fuel containing ε-particles).

It was found that Pd has a catalytic effect on the reaction between H2O2 and H2, the second order rate constant is determined to (2.1±0.1)x10-5 m s-1. Pd also has a catalytic effect on the reduction of U(VI) by H2 both in aqueous solution, rate constant (1.5±0.1)x10-5 m s-1, and in the solid phase, rate constants 4x10-7 m s-1 and 7x10-6 m s-1 for pellets with 1 and 3 % Pd respectively. These values are very close to the diffusion limit for these systems. The catalytic effect in the solid phase shows that the dissolution for 100 year old fuel can be completely inhibited, at 40 bar H2 a noble metal particle content of 10-20 ppm is needed and with 1 % noble metal particle content 0.1 bar H2 is enough to stop the dissolution.

Structures were determined for 48 new natural products and several related compounds by NMR methods. One new natural product and two unnatural product structures were determined by X-ray diffraction. Molecular mechanics calculations on two indoles related to the neurotransmitter serotonin and on some synthetic cyclophanes were used to gain information about their preferred conformations. Considerable time is wasted redetermining the structures of known natural products when they are encountered in new sources. To help alleviate this problem, a database which searches on proton NMR chemical shifts was developed.

The reliability of electronic products is fast becoming of major importance with the demand for increased safety, especially in the automotive industry. Tracks, pads and vias on printed circuit boards can suffer a variety of problems if circuits are contaminated with electrical-conducting substances. Electrochemical migration, especially dendrite growth, has long been a concern in safety critical and durable systems, and current preventative methods tend to focus on various styles of printed circuit board protective coatings. These measures have a number of disadvantages, mainly process and material costs with extreme scepticism on their overall efficacy. Any design related developments that can minimise the impact of dendrite growth on reliability can lead to a more economic, durable and safer product. The work in this thesis provides a thorough literature search of the field of electrochemical migration on printed circuit boards. This study then develops a novel circuit-designorientated model, based on a multilevel full-factorial design, to study the effects of temperature, voltage and electrode gap on dendritic growth under saturated conditions. Preparation of several DC-biased copper-comb patterned printed circuit boards placed in temperature-controlled water-filled cuvettes enables the specific monitoring of dendrite activity, and detects a sharp current increase that accompanies a dendritic short circuit condition. A high R2 polynomial correlation-model is derived and it is noted that increased voltage and temperature and reduced track spacing increases the impact of dendritic growth on reliability. At voltages between 3 and 4V, gas bubble formation at the electrodes has the effect of increasing reliability by destroying the dendrite fuses. It is shown that dendrites may not grow below 1.25V, which coincides with the theoretical onset voltage for the decomposition of water. It was also demonstrated that electrically biased, watercontaminated printed circuit boards form extreme acid and alkaline regions close to the anode and cathode terminations, respectively, which can cause corrosion. The thesis proposes a novel approach, termed ‘design contingency’, for preventing dendritic growth through design optimisation.

Orientador: Lucia Maria Xavier Lopes
Banca: André Luiz Meleiro Porto
Banca: Lidilhone Hamerski Carbonezi
Resumo: O presente trabalho descreve o isolamento e identificação dos constituintes químicos de Aristolochia melastoma Manso. O extrato acetônico de caules e raízes foi fracionado por cromatografia em coluna de sílica gel, e as frações obtidas foram submetidas a outros fracionamentos cromatográficos (CCDP, Sephadex LH-20, CC de C-18 e CLAE) e/ou lavagens com solventes orgânicos, resultando no isolamento de vinte compostos conhecidos: aristolactama AII, 9,9'-diacetato-secoisolariciresinol dimetil éter, tirosol, ácido p-hidroxibenzóico, ácido vanilínico, ácidos aristolóquicos I e II, aristolocatos de sódio IIIa e IVa, 4,5-dioxodeidroasimilobíneo, aristolocato de sódio I, sitosterol 3-O-β-D-glucopiranosídeo, glicerol, talictosídeo, uridina, talictricosídeo, icarisídeo D2, adenosina, kaempferol 3-O-β-robinobiosídeo e isorhamnetina 3-O-β-robinobiosídeo. A lignana 9,9'-diacetato-secoisolariciresinol dimetil éter e talictricosídeo são relatados pela primeira vez na família Aristolochiaceae. As identificações desses compostos foram baseadas nas análises dos seus dados espectrométricos (RMN 1D e 2D, UV e EM). Além disso, a análise dos dados obtidos a partir de literatura especializada acerca da ocorrência e biogênese de derivados nitrofeniletílicos sugere que a família Aristolochiaceae pode ter evoluído no sentido de formação de compostos nitrados
Abstract: This work describes the isolation and identification of the chemical constituents of A. melastoma Manso. The acetone extract from stems and roots was fractionated by CC over silica gel and the resultant fractions were subjected to other chromatographic methods (PTLC, Sephadex LH-20, CC RP-18, and HPLC) and/or washed with organic solvents to give twenty known compounds: aristolactam AII, secoisolariciresinol dimethyl ether diacetate, tyrosol, p-hydroxybenzoic acid, vanillic acid, sodium aristolochates I, IIIa, and IVa, 4,5-dioxodehydroasimilobine, aristolochic acids I and II, sitosterol-3-O-β-D-glucopyranoside, glycerol, uridine, thalictoside, icariside D2, adenosine, thalictricoside, kaempferol 3-O-β-robinobioside, and isorhamnetin 3-O-β-robinobioside. Among these, secoisolariciresinol dimethyl ether diacetate and thalictricoside have being reported for the first time in the Aristolochiaceae family. The identifications of these compounds were based on analyses of their spectroscopic data (1D- and 2D-NMR, UV, and MS). Furthermore, an analysis of data obtained from specialized literature on the occurrence and biogenesis of nitrophenylethyl derivatives suggests that the Aristolochiaceae family may have evolved towards nitro compounds
Mestre

Infections of insect cells by baculoviruses are characterized by distinct early and late temporal phases with a transition demarcated by the beginning of viral DNA replication. Three processes characteristic of baculovirus infection occur during the late phase: (1) the production of two phenotypically distinct types of virions, (2) the occlusion of one of these virion types in large proteinaceous structures, and (3) the appearance of a novel DNA-directed RNA polymerase activity that is responsible for baculovirus late gene expression. Many of the polypeptide components of the late phase processes remain to be elucidated. The identification and characterization of two baculovirus late proteins are described in this thesis. The first, gp37 or SLP, is a glycoprotein that represents the major component of spindle-shaped crystal structures which are often observed at the nuclear membrane of infected cells. Purified spindle bodies are associated with an alkaline protease activity. The second late protein, p78/83, is a phosphoprotein associated with an end-structure of the nucleocapsids. It forms complexes with other infected-cell proteins and copurifies with the virus-induced RNA polymerase activity through a number of chromatographic steps.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
No Brasil, 31 espécies vegetais de Paepalanthus foram registradas no Estado de Minas Gerais, no topo da Serra do Espinhaço, o principal centro de diversidade de Eriocaulaceae do Brasil e mais de 400 espécies de Paepalanthus e estão distribuídas geograficamente do estado do Amazonas a São Paulo. Apesar do grande número de espécies existentes em Eriocaulaceae, a sua peculiar composição química, aliadas às importantes atividades biológicas das substâncias isoladas, existem ainda muitas espécies que não possuem estudos, como no caso de Paepalanthus geniculatus. Portanto, neste trabalho, o extrato metanólico dos capítulos de Paepalanthus geniculatus (Bong.) Kunth foi estudado, utilizando HPLC-ESIMSn. As substâncias foram posteriormente isoladas do extrato metanólico e identificadas por RMN mono e bi-dimensionais. Com estas técnicas analíticas, foi possível identificar a presença de dezenove substâncias fenólicas, destas onze inéditas, sendo quinze flavonóides e quatro naftopiranonas que auxiliará na taxonomia da família. Um flavonol glicosilado ciclodimérico ligado a uma unidade truxilato, também inédito foi isolado e identificado por métodos espectroscópicos e espectrométricos. Alguns flavonóides exibiram forte atividade antioxidante e nenhuma das substâncias apresentou efeito citotóxico significativo em células humanas cancerosas de próstata
In Brazil, 31 plant species of Paepalathus were registered in the State of Minas Gerais, at the top of the Espinhaço, the main center of diversity of Eriocaulaceae in Brazil and over 400 Paepalanthus are distributed geographically from the state of Amazonas to São Paulo. Despite the large number of species existing in Eriocaulaceae, its peculiar chemical composition, which has greatly aided in the taxonomy of the family, combined with the biological activities of isolated substances, there are still many species that have no studies, as in the case of Paepalanthus geniculatus. Therefore, in this work the methanol extract of the capitulae from Paepalanthus geniculatus (Bong.) Kunth were studied. An analytical approach based on HPLC-ESI-MSn was applied to obtain the metabolite profile of this extract and led to the rapid identification of nineteen polyphenolic compounds, eleven unpublished, comprising fifteen flavonoids and four naphthopyranones. The substances were then isolated and identified by NMR mono and bidimensional. A glycosylated cyclodimeric flavonol bonded to a truxilate unit, also unpublished, was isolated and identified by spectroscopic and spectrometric methods. Some flavonoids showed strong antioxidant activity and none of the substances showed significant citotoxic effect in human prostate cancer cells

Orientador: Wagner Vilegas
Banca: Nivaldo Boralle
Banca: Miriam Sannomiya
Banca: Mônica Tallarico Pupo
Banca: Adriana Mendes Aleixo
Resumo: No Brasil, 31 espécies vegetais de Paepalanthus foram registradas no Estado de Minas Gerais, no topo da Serra do Espinhaço, o principal centro de diversidade de Eriocaulaceae do Brasil e mais de 400 espécies de Paepalanthus e estão distribuídas geograficamente do estado do Amazonas a São Paulo. Apesar do grande número de espécies existentes em Eriocaulaceae, a sua peculiar composição química, aliadas às importantes atividades biológicas das substâncias isoladas, existem ainda muitas espécies que não possuem estudos, como no caso de Paepalanthus geniculatus. Portanto, neste trabalho, o extrato metanólico dos capítulos de Paepalanthus geniculatus (Bong.) Kunth foi estudado, utilizando HPLC-ESIMSn. As substâncias foram posteriormente isoladas do extrato metanólico e identificadas por RMN mono e bi-dimensionais. Com estas técnicas analíticas, foi possível identificar a presença de dezenove substâncias fenólicas, destas onze inéditas, sendo quinze flavonóides e quatro naftopiranonas que auxiliará na taxonomia da família. Um flavonol glicosilado ciclodimérico ligado a uma unidade truxilato, também inédito foi isolado e identificado por métodos espectroscópicos e espectrométricos. Alguns flavonóides exibiram forte atividade antioxidante e nenhuma das substâncias apresentou efeito citotóxico significativo em células humanas cancerosas de próstata
Abstract: In Brazil, 31 plant species of Paepalathus were registered in the State of Minas Gerais, at the top of the Espinhaço, the main center of diversity of Eriocaulaceae in Brazil and over 400 Paepalanthus are distributed geographically from the state of Amazonas to São Paulo. Despite the large number of species existing in Eriocaulaceae, its peculiar chemical composition, which has greatly aided in the taxonomy of the family, combined with the biological activities of isolated substances, there are still many species that have no studies, as in the case of Paepalanthus geniculatus. Therefore, in this work the methanol extract of the capitulae from Paepalanthus geniculatus (Bong.) Kunth were studied. An analytical approach based on HPLC-ESI-MSn was applied to obtain the metabolite profile of this extract and led to the rapid identification of nineteen polyphenolic compounds, eleven unpublished, comprising fifteen flavonoids and four naphthopyranones. The substances were then isolated and identified by NMR mono and bidimensional. A glycosylated cyclodimeric flavonol bonded to a truxilate unit, also unpublished, was isolated and identified by spectroscopic and spectrometric methods. Some flavonoids showed strong antioxidant activity and none of the substances showed significant citotoxic effect in human prostate cancer cells
Doutor

O objetivo dessa dissertação foi analisar a influência de possíveis reações de fusão nuclear quando elementos leves, definidos como alvos são adicionados ao combustível nuclear. A energia cinética dos produtos de fissão, na concepção desse estudo, é utilizada para vencer a repulsão elétrica entre os núcleos. Para esse trabalho foram considerados a adição de hidrogênio, deutério, lítio e berílio em fração mássica de 0,30. A escolha desses elementos foi realizada através da análise da energia de ligação, do número atômico e das seções de choque experimentais de fusão. A avaliação da fusão nuclear foi realizada via principio da incerteza, pois não há um modelo que pudesse cobrir um grande número de reações possíveis. A probabilidade de reação foi aproximada como uma função da probabilidade de um produto de fissão encontrar determinado elemento leve. Adicionalmente foram calculados os tempos de freamento eletrônico para os produtos de fissão com isso verificou-se que a escala de freamento não representa limitação para a fusão. A principal alteração, devido à adição dos alvos, foi na distribuição dos tempos de meia vida dos produtos de fissão, na direção de maiores tempos. A alteração nessa grandeza indica que é possível reduzir a atividade média do rejeito nuclear, em especial o de alto nível de radioatividade, tornando sua manipulação mais segura. Os alvos de hidrogênio e lítio apresentaram os melhores resultados para o aumento do tempo de meia vida médio dos produtos de fissão, conseguindo altera-la em média duas ordens de grandeza. Outras alterações, que não foram alvo desse estudo, são esperadas devido à inserção desses alvos, como por exemplo, na cinética.
The objective of this dissertation was to analyze the influence of possible nuclear fusion reactions when light elements, defined as targets are added to the nuclear fuel. The kinetic energy of the fission products, in the conception of this study, is used to overcome the electrical repulsion between the nuclei. For this work were considered the addition of hydrogen, deuterium, lithium and beryllium in mass fraction of 0.30. The choice of these elements was performed by analyzing the binding energy, the atomic number and experimental fusion cross sections. The assessment of fusion was performed via the uncertainty principle, since there is no model that could cover a large number of possible reactions. The probability of reaction was approximated as a function of the probability of fission product find a particular light element. Additionally times were calculated for the electronic stopping fission products where was found that scale of stopping does not impose limits on fusion. The main change due to the addition of the targets was the distribution of halflives of the fission products, towards longer times. The change in this magnitude indicates that it is possible to reduce the average activity of the nuclear waste, in particular the high level of radioactivity, making handling safer. The targets of hydrogen and lithium showed the best results for increasing the half-life of the average fission products, managing change a on the average of two orders of magnitude. Other modifications, which were not discussed in this study, are expected due to the insertion of these targets, e.g. kinetics.

O trabalho apresentado nesta tese pretendeu desenvolver e aplicar métodos espectroscópicos, em especial espectroscopia de ressonância magnética nuclear e técnicas acopladas, e também espectroscopia de infravermelho, para estudar a composição e a bioquímica de frutos e bebidas. No Capítulo I, apresenta-se o estado do conhecimento sobre a composição e bioquímica dos alimentos em análise neste trabalho, evidenciando-se os aspectos que justificam o seu estudo mais aprofundado e completo, para o qual a presente tese pretende contribuir. O Capítulo II descreve, de forma resumida, os fundamentos das técnicas analíticas utilizadas, focando nomeadamente a espectroscopia de RMN de estado líquido e de estado sólido, o acoplamento da RMN com cromatografia líquida e espectrometria de massa (HPLCRMN/ MS) e a espectroscopia de infravermelho. Os métodos de análise multivariada usados encontram-se também sumariamente descritos neste Capítulo. No Capítulo III, descreve-se a aplicação de técnicas de RMN de alta resolução para caracterizar a composição de sumo e polpa de manga. O espectro de RMN-1H do sumo (600 MHz) apresenta elevada complexidade e contém informação sobre uma vasta gama de compostos. Recorrendo a espectros bidimensionais, conseguem identificar-se cerca de 50 compostos, incluindo vários açúcares, ácidos orgânicos e aminoácidos. O fruto intacto (polpa) é estudado directamente e de forma não-invasiva por RMN de estado sólido (400 e 500 MHz), utilizando a técnica de rotação segundo o ângulo mágico (MAS) e uma sonda de alta resolução (HR-MAS). A técnica de HRMAS permite obter espectros com uma resolução seis vezes maior do que a obtida com MAS, sendo possível registar espectros 2D e caracterizar detalhadamente a composição da polpa. Comparando os espectros da polpa e do sumo respectivo, encontram-se algumas diferenças na composição em lípidos e pectinas, que se encontram em maior abundância no fruto intacto, demonstrando que a usual extrapolação da composição do sumo como composição global do fruto pode não ser totalmente aplicável. No Capítulo IV apresenta-se um estudo sistemático do processo de amadurecimento da manga (cv. Tommy Atkins), levado a cabo através de medições físico-químicas e de espectroscopia de RMN-1H de alta resolução aplicada a sumos e polpas. A quantificação de alguns componentes do sumo é efectuada por integração dos sinais de RMN, usando uma referência interna (TSP). As principais alterações de composição com o amadurecimento consistem no aumento dos teores de sacarose, alguns aminoácidos (ex. valina, alanina, ácido ?-aminobutírico), constituintes pécticos e polifenóis e na diminuição dos teores de glucose, ácido cítrico, ácido xiquímico, arginina, tirosina e fenilalanina. Uma segunda variedade estudada (cv. Haden) apresenta diferenças no processo de amadurecimento sobretudo ao nível da variação de alguns aminoácidos e compostos aromáticos. Ainda neste capítulo, um estudo preliminar sobre o efeito da refrigeração mostra que a maior parte das alterações indicadas acima são retardadas ou não ocorrem a baixa temperatura, daí resultando frutos com baixa qualidade organoléptica. O Capítulo V descreve a quantificação dos três principais açúcares do sumo de manga em função do amadurecimento, usando regressão parcial dos mínimos quadrados (PLS) aplicada a espectros de infravermelho (FTIR-ATR) e de RMN-1H. A calibração é efectuada com base em soluções padrão de glucose, frutose e sacarose, seguindo um desenho experimental triangular, com seis níveis de concentração para cada açúcar. O método de PLS-FTIR permite prever a concentração dos três açúcares com elevada exactidão, excepto no caso da glucose quando, nos últimos estágios de amadurecimento, esta atinge teores abaixo da gama de concentrações usada na calibração. Por outro lado, a aplicação de PLS aos espectros de RMN das soluções padrão e dos sumos de manga apresenta erros elevados, cuja magnitude parece depender do alinhamento dos espectros, necessitando este método de optimização. No Capítulo VI, a espectroscopia de RMN-1H de alta resolução é usada para monitorizar e identificar alterações de composição em sumos de manga sujeitos a degradação natural, aquecimento e contaminação microbiológica. Permitindo identificar muitos dos compostos que se alteram em função destes efeitos, de forma rápida e simultânea, e seguir a sua variação ao longo do tempo, a técnica de RMN revela-se promissora para a detecção de indicadores de degradação/contaminação do sumo, sendo potencialmente útil para fins de controlo de qualidade. No Capítulo VII, alguns componentes minoritários de sumo de manga, sumo de uva e vinho são investigados através do acoplamento das técnicas de RMN, cromatografia líquida e espectrometria de massa (HPLC-RMN/MS). Em particular, o sumo de manga é analisado com vista ao estudo dos hidratos de carbono menos abundantes, tendo-se alcançado uma melhor caracterização da fracção péctica. A análise de sumo de uva e vinho (extracto fenólico) destina-se a caracterizar os constituintes aromáticos destas amostras, tendose conseguido identificar vários compostos fenólicos de difícil atribuição só com base na análise directa por RMN. Os compostos identificados na uva incluem o ácido gálico e vários ácidos cinâmicos (ex. p-cumárico, transcutárico e trans-caftárico), enquanto que no vinho se detectam catequina e epicatequina, trans-resveratrol, tirosol e ácido cafeico. O Capítulo VIII centra-se na caracterização da composição química da cerveja através das técnicas de RMN e de HPLC-RMN/MS. A análise directa por RMN uni- e bidemsional (500 MHz) permite a identificação de cerca de 30 compostos, entre os quais vários ácidos orgânicos, aminoácidos e álcoois. Os oligossacarídeos de maltose (dextrinas) dão origem aos sinais mais largos e intensos do espectro, mas o elevado grau de sobreposição impede a sua caracterização estrutural. A identificação de dextrinas de diferentes tamanhos é conseguida através da análise da cerveja por HPLC-RMN/MS, que requer apenas a desgaseificação da amostra. A análise por HPLC-RMN/MS permite também confirmar a presença de vários compostos aromáticos e revelar outros não identificados só com base na análise por RMN, tais como os álcoois aromáticos 2-feniletanol, tirosol e triptofol. Finalmente, no Capítulo IX, descreve-se a análise de componentes principais (PCA) dos espectros de RMN-1H e de FTIR-ATR de um conjunto de 50 cervejas de diferentes marcas, tipos e países de origem. Por PCA dos espectros de RM N as cervejas são separadas de acordo com a sua composição em hidratos de carbono, embora alguns componentes minoritários (em particular compostos aromáticos) também contribuam para a distinção das amostras, nomeadamente em termos dos dois tipos principais ‘ale’ e ‘lager’. A aplicação de PCA aos espectros de FTIR origina a distinção das cervejas com base no seu teor alcoólico e na sua composição em hidratos de carbono. A análise canónica de correlação (CCA) entre os espectros de RMN e de FTIR mostra uma correlação elevada entre os dois domínios, permitindo identificar os sinais que variam no mesmo sentido.
The work reported in this thesis aimed at developing and applying spectroscopic methods, principally nuclear magnetic resonance (NMR) spectroscopy and hyphenated techniques (HPLC-NMR and HPLC-NMR/MS), along with infrared spectroscopy, for studying the complex composition and biochemistry of different fruit products and beverages. Chapter I summarises some of the present knowledge about the food systems studied, giving particular emphasis to the aspects that frame the problems investigated in this thesis. The fundamentals of the analytical methods employed are shortly presented in Chapter II, focusing on the principles underlying the experiments that have been carried out in this work, namely solution and solid state high resolution 1H NMR spectroscopy, HPLC-NMR/(MS) and Fourier-transform infrared spectroscopy. The multivariate analysis methods that have been applied to the spectroscopic data are also briefly presented. In Chapter III, the application of high resolution NMR to characterise the composition of mango juice and intact pulp is described. The high field (600 MHz) 1H spectra of juices show a high degree of complexity, revealing the potential of the technique for the simultaneous detection of a wide range of components. Spectral assignment is carried out with basis on 1D and 2D spectra, resulting in the identification of about 50 components, including several sugars, organic acids and amino acids. Mango pulps are studied directly and non-invasively by techniques derived from solid state NMR, namely 1H HR-MAS NMR (400 and 500 MHz), which results in a six-fold resolution improvement compared to standard 1H MAS. HR-MAS enables 2D experiments to be carried out, thus allowing for the pulp composition to be thoroughly characterised. The pulp is found to have a richer composition in lipids and pectins than the corresponding juice, showing that the composition of the liquid phase is not fully representative of the composition of the whole fruit as usually assumed. Chapter IV presents a systematic study of the ripening process of mango (cv. Tommy Atkins), monitored by physicochemical parameters and by high resolution 1H NMR of both juices and pulps. Some juice components are quantified by integration of NMR signals, using an internal reference (TSP). Mango ripening is found to be characterised by increases in the contents of sucrose, some amino acids (e.g. valine, alanine, GABA), pectic constituents and polyphenols, and by decreases in the contents of glucose, citric acid, shikimic acid, arginine, tyrosine and phenylalanine, reflecting the complex biochemistry of ripening. The other cultivar studied (cv. Haden) is found to differ mainly in the variation patterns of some amino acids and aromatic compounds. Furthermore, a preliminary study of the effect of refrigeration on ripening shows that most changes indicated above do not occur under low temperature, resulting in fruits with poor edible quality. In Chapter V, partial least squares (PLS1) regression is applied to FTIRATR and to 1H NMR data in order to quantify the three main sugars in mango juices as a function of ripening. Calibration is based on standard solutions of glucose, fructose and sucrose, following a triangular experimental design with six concentration levels for each sugar. The PLS -FTIR method shows good predictive ability, although the accuracy of glucose determination decreases at later ripening stages, when concentrations fall below the lower limit of the concentration range used for calibration. The PLS -NMR method shows much higher prediction errors, which seem to depend on spectral alignment, and needs further optimisation. In Chapter VI, the application of high resolution NMR to monitor the complex compositional changes of mango juices subject to natural degradation, heat treatment and microbial contamination is described. Enabling the identification of many compounds undergoing changes upon these effects, in a rapid and simultaneous manner, and their variations to be followed throughout time, the NMR technique may be regarded as a sensitive and powerful tool for detecting indicators of spoilage/contamination, being potentially useful for quality control purposes. Chapter VII describes the application of hyphenated NMR methods (HPLC-NMR and HPLC-NMR/MS) to investigate minor components in mango juice, grape juice and wine. In particular, the carbohydrate composition of mango juice is investigated and further advances in the characterisation of the pectic fraction achieved. The analysis of grape juice and wine (phenolic extract) aims at characterising their complex aromatic composition and results in the identification of several phenolic compounds, overcoming the difficulties found when using standard NMR. Gallic acid and several cinnamic acids (e.g. pcoumaric, trans-coutaric and trans-caftaric) are identified in grape juice, whereas catechin, epicatechin, trans -resveratrol, tyrosol and caffeic acid are found in the wine phenolic extract. Chapter VIII is focused on the characterisation of beer chemical composition by high resolution NMR and HPLC-NMR/MS. Direct analysis of beer by 1D and 2D NMR (500 MHz) is shown to enable the identification of about 30 components, such as several organic acids, amino acids and alcohols. Malto-oligosaccharides (dextrins) give rise to the broadest and most intense signals in the spectrum, but the strong spectral overlap hinders their structural characterisation. The identification of dextrins of different sizes is achieved by HPLC-NMR/MS of beer, preceded only by degassing of the sample. In addition, HPLC-NMR/MS is shown to be useful for confirming the identity of some aromatic compounds previously assigned by NMR alone, and for revealing new ones, such as the aromatic alcohols 2-phenylethanol, tyrosol and tryptophol. Finally, in Chapter IX, principal component analysis (PCA) is applied to the 1H NMR spectra and to the FTIR-ATR spectra of a set of 50 beers differing in label, type and country of origin. PCA of NMR data results in the separation of beers mainly according to their carbohydrate composition, although minor components (aromatic compounds in particular) are also found to contribute for the distinction of beers, namely in terms of the two main types ale and lager. PCA of FTIR data separates beers with basis on differences in their alcoholic content and carbohydrate composition. Canonical correlation analysis of NMR and FTIR spectra shows a high correlation between the two domains, enabling the identification of the spectral features varying in the same direction.

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A espécie Casearia sylvestris Sw. (Salicaceae) é um importante representante do gênero Casearia Jacq. destacando-se nos pontos de vista químico, farmacológico, econômico, biotecnológico e ecológico. Por possuir alta capacidade adaptativa, encontra-se amplamente disseminada nas Américas Central e do Sul, sendo que, no Brasil, ocorre em praticamente todos os biomas. Os dados morfo-anatômicos, químicos e genéticos disponíveis sobre C. sylvestris, indicam relação próxima entre variedade lingua e bioma Cerrado e entre variedade sylvestris e Mata Atlântica, havendo também dados descrevendo diferenças genéticas significativas entre estas duas variedades. Em ecótonos Cerrado/Mata Atlântica, estas duas variedades co-existem, havendo principalmente nessas regiões indivíduos com características intermediárias, tanto do ponto de vista morfo-anatômico quanto genético. Há também indícios de que em C. sylvestris var. lingua/Cerrado ocorram predominantemente compostos fenólicos, enquando em C. sylvestris var. sylvestris/Mata Atlântica predominam os diterpenos clerodânicos. Assim, este trabalho tem como objetivo principal avaliar e confirmar indícios de que a composição química, no que concerne a metabólitos secundários, está relacionada e/ou condicionada pelos biomas, e principalmente associada aos respectivos morfotipos predominantes e, portanto, sob forte controle genético. Para tanto, desenvolveu-se e validou-se um método analítico por UHPLC-DAD para a análise simultânea de compostos fenólicos e diterpenos clerodânicos produzidos pelas duas variedades de C. sylvestris. Através do estudo metabolômico destas duas variedades utilizando foram identificados 15 diterpenos clerodânicos em C. sylvestris var. sylvestris e 14 flavonoides glicosilados e uma catequina em C. sylvestris var. lingua. O estudo dos ciclos circadiano e sazonal de ambas as variedades evidenciou um...
The species Casearia sylvestris Sw (Salicaceae) is an important representative of the Casearia Jacq. genus, due to its chemical, pharmacological, economic, environmental and biotechnological aspects. Because of its high adaptive capacity, this species is widespread in Central and South America and, in Brazil, it occurs in practically all biomes. The morpho-anatomical, chemical and genetic data available on C. sylvestris, indicate close relationship between the variety lingua and the Cerrado biome, and between the variety sylvestris and Atlantic Forest. Also, there are data describing significant genetic differences between these two varieties. In ecotones Cerrado/Atlantic Forest, it can be found these two varieties, including individuals with intermediate characteristics, considering both morpho-anatomical and genetic ones. There is evidence that in C. sylvestris var. lingua/Cerrado occur predominantly the phenolic compounds, while in C. sylvestris var. sylvestris/Atlantic Forest the clerodane diterpenes predominate. So, the main objective of this work is to evaluate if the chemical composition, considering the secondary metabolites, is related to and/or conditioned by biomes, and mainly associated to their predominant morphotypes and, therefore, under strong genetic control. To evaluate this, an analytical method using UHPLC-DAD was developed and validated for the simultaneous analysis of phenolic compounds and clerodane-type diterpenes produced by the two C. sylvestris varieties. The metabolomic study allowed the identification of 15 clerodane-type diterpenes in C. sylvestris var. sylvestris and 14 glycosylated flavonoids and one catechin in C. sylvestris var. lingua. The study of the circadian rhythm and seasonal cycle of both varieties showed a decrease in the production of the two secondary metabolites classes in the reproductive period. In the infraspecific chemical...

Orientador: Alberto José Cavalheiro
Banca: Maysa Furlan
Banca: Leonardo Gobbo Neto
Banca: Marina Franco Maggi Tavares
Banca: Marcelo Mattos Cavallari
Resumo: A espécie Casearia sylvestris Sw. (Salicaceae) é um importante representante do gênero Casearia Jacq. destacando-se nos pontos de vista químico, farmacológico, econômico, biotecnológico e ecológico. Por possuir alta capacidade adaptativa, encontra-se amplamente disseminada nas Américas Central e do Sul, sendo que, no Brasil, ocorre em praticamente todos os biomas. Os dados morfo-anatômicos, químicos e genéticos disponíveis sobre C. sylvestris, indicam relação próxima entre variedade lingua e bioma Cerrado e entre variedade sylvestris e Mata Atlântica, havendo também dados descrevendo diferenças genéticas significativas entre estas duas variedades. Em ecótonos Cerrado/Mata Atlântica, estas duas variedades co-existem, havendo principalmente nessas regiões indivíduos com características intermediárias, tanto do ponto de vista morfo-anatômico quanto genético. Há também indícios de que em C. sylvestris var. lingua/Cerrado ocorram predominantemente compostos fenólicos, enquando em C. sylvestris var. sylvestris/Mata Atlântica predominam os diterpenos clerodânicos. Assim, este trabalho tem como objetivo principal avaliar e confirmar indícios de que a composição química, no que concerne a metabólitos secundários, está relacionada e/ou condicionada pelos biomas, e principalmente associada aos respectivos morfotipos predominantes e, portanto, sob forte controle genético. Para tanto, desenvolveu-se e validou-se um método analítico por UHPLC-DAD para a análise simultânea de compostos fenólicos e diterpenos clerodânicos produzidos pelas duas variedades de C. sylvestris. Através do estudo metabolômico destas duas variedades utilizando foram identificados 15 diterpenos clerodânicos em C. sylvestris var. sylvestris e 14 flavonoides glicosilados e uma catequina em C. sylvestris var. lingua. O estudo dos ciclos circadiano e sazonal de ambas as variedades evidenciou um...
Abstract: The species Casearia sylvestris Sw (Salicaceae) is an important representative of the Casearia Jacq. genus, due to its chemical, pharmacological, economic, environmental and biotechnological aspects. Because of its high adaptive capacity, this species is widespread in Central and South America and, in Brazil, it occurs in practically all biomes. The morpho-anatomical, chemical and genetic data available on C. sylvestris, indicate close relationship between the variety "lingua" and the Cerrado biome, and between the variety "sylvestris" and Atlantic Forest. Also, there are data describing significant genetic differences between these two varieties. In ecotones Cerrado/Atlantic Forest, it can be found these two varieties, including individuals with intermediate characteristics, considering both morpho-anatomical and genetic ones. There is evidence that in C. sylvestris var. "lingua"/Cerrado occur predominantly the phenolic compounds, while in C. sylvestris var. "sylvestris"/Atlantic Forest the clerodane diterpenes predominate. So, the main objective of this work is to evaluate if the chemical composition, considering the secondary metabolites, is related to and/or conditioned by biomes, and mainly associated to their predominant morphotypes and, therefore, under strong genetic control. To evaluate this, an analytical method using UHPLC-DAD was developed and validated for the simultaneous analysis of phenolic compounds and clerodane-type diterpenes produced by the two C. sylvestris varieties. The metabolomic study allowed the identification of 15 clerodane-type diterpenes in C. sylvestris var. sylvestris and 14 glycosylated flavonoids and one catechin in C. sylvestris var. lingua. The study of the circadian rhythm and seasonal cycle of both varieties showed a decrease in the production of the two secondary metabolites classes in the reproductive period. In the infraspecific chemical...
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The shortage in water resources have been observed all over the world. However, the safety of drinking water has been given much attention by scientists because the disinfection will react with organic matters in drinking water to generate disinfection by-products (DBPs) which are considered as the cancerigenic matters. Although much research has been carried out on the water quality control problem in DWDS, the water quality model considered is linear with only chlorine dynamics. Compared to the linear water quality model, the nonlinear water quality model considers the interaction between chlorine and DBPs dynamics. The thesis proposes a nonlinear model predictive controller which utilises the newly derived nonlinear water quality model as a control alternative for controlling water quality. EPANET and EPANET-MSN are simulators utilised for modelling in the developed nonlinear MPC controller. Uncertainty is not considered in these simulators. This thesis proposes the bounded PPM in a form of multi-input multi-output to robustly bound parameters of chlorine and DBPs jointly and to robustly predict water quality control outputs for quality control purpose. The methodologies and algorithms developed in this thesis are verified by applying extended case studies to the example DWDS. The simulation results are presented and critically analysed.

The wicking properties of multi-ply paper samples with dissimilar plies were investigated. These materials exhibit wicking performance in excess of either of their individual plies. Samples were produced from a ply of softwood pulp and a ply of hardwood pulp of equal caliper and basis weight. The softwood sample possessed a larger average pore size, a fact verified via porometry. Samples of a single ply were also produced for comparison. The samples were tested using both upward and downward gravimetric wicking tests. There was no saturation gradient observed, however there was a variation in the degree of bulk expansion during wicking. Capillary pressure and permeability for the various sample types were determined from the results of these tests and compared. It is shown that the wicking performance of the two ply sample is comparable to that of a theoretical material with the capillary pressure of the hardwood ply but the permeability of the softwood ply. Wicking in two-ply samples was also observed in an NMR apparatus. This was used to determine that the hardwood ply leads during wicking, and observe the rate of saturation as well as bulk expansion. A third type of experiment tracked the transport of dyed water from one ply to the other, establishing the direction of fluid transport during wicking to be from the softwood ply to the hardwood ply. The theory is proposed, based on these results, that wicking in this type of material consists of a smaller pored leading ply that draws water from a more permeable larger pored material that acts as a moving reservoir.

The general fission process is well known and is applied in nuclear power plants all over the world. However many properties of fission fragments are still not well understood. The angular momentum distribution of fission fragments is an important property to gain a better understanding of the fission process, and that can be derived indirectly from isomeric yield ratios. The goal of this project has been to develop a script in Python that runs the nuclear reaction code TALYS with the Total Monte Carlo method to calculate the isomeric yield ratio. The script generates a matrix consisting of excitation energies and angular momenta that is provided to TALYS. One matrix corresponds to one calculation of the isomeric ratio. Thus, the dependency of the isomeric yield ratio on these matrices can be observed. After looking into the matrices, the dependencies of the isomeric yield ratios on the excitation energies and the angular momentum distribution are observed. In this project, the calculated isomeric yield ratios are compared with the experimental value obtained from an experiment conducted in August of 2019 at the IGISOL-JYFLTRAP facility in Jyväskylä, Finland. It is worth mentioning that, fission system is of Uranium-238 which was induced by a proton beam at an energy of 25 MeV. The dependency of the isomeric yield ratio (IYR) on the angular momentum and the excitation energy has been investigated. However, it has proved more difficult than expected, to deduce an estimation for the angular momentum distribution. Another finding of this project is that the two codes used, GEF and TALYS sometimes produce inconstant results.

Pour augmenter les performances des barres de combustible nucléaire, les mécanismes de relâchement des produits de fission (H2, He, Kr, Xe) doivent être étudiés. Ainsi, le département d’étude du combustible du CEA Cadarache a décidé d’améliorer son dispositif expérimental consacré au recuit thermique des combustibles irradiés (MERARG II). La première partie de ce mémoire s'adresse à la mesure du relâchement de gaz de fission de combustibles irradiés et soumis à des transitoire thermiques. Le choix de l'appareil s'est porté sur un analyseur de type filtre quadripolaire du fait des performances requises par le cahier des charges, une identification isotopique du Kr et Xe et des masses 4 et 2 u à la ppm. C'est un spectromètre commercial de type Residual Gaz Analyser, monté dans une enceinte à vide de très faible volume qui a nécessité des adaptations à la ligne de l'expérience MERARG II. Les performances (résolution, sensibilité, vitesse de balayage) du spectromètre ont été évaluées. Le spectromètre calibré est en cours d’installation sur une réplique en zone « froide » de MERARG II.La seconde partie de la thèse concerne des travaux de recherche sur l’adaptation à l’analyse des faibles masses d’un mode opératoire appliqué à un piège à ions RF 3D utilisant un mode par Transformé de Fourier. Nous étudions plus précisément un dispositif d’injection des ions et son mode opératoire afin d’obtenir les distributions en positions et vitesses des ions confinables. La connaissance de ces conditions initiales et de leur dispersion est importante car elles conditionnent la dynamique du signal détecté (la hauteur de la raie) et sa fluctuation, respectivement
In order to increase fuel rod performances, the basic mechanisms that promote gas (i.e. He, H2, Kr and Xe) release from irradiated nuclear fuels must be studied. In this context, the CEA fuel study department at Cadarache decided to improve its experimental facility devoted to fuel behaviour under thermal transient by modifying the existing annealing device, called MERARG-II.The first part of this dissertation adresses the fuel gas release monitoring from irradiated fuel during thermal transient. The device choice leads to a quadrupole mass filter as mass analyser according to the specification requirement, i.e. isotopic identification of Xe, Kr and masses at 4 and 2 u. It is commercialized Residual Gas Analyser, mounted in a small-volume vacuum chamber requiring adaptations to be connected to the MERARG II line. The resolution and sensitivity of the mass spectrometer have been evaluated. The calibrated device is being installed in MERARG II replica.The second part of this dissertation relates adaptation to low-mass analysis of an RF 3D ion trap operated a Fourier Transform mode. Theoretically, using this operating mode, the lower the mass, the higher the resolution. More particularly, an ion injection device and its operating mode are studied in order to gain position and velocity distributions of confinable ions. The knowledge of these initial conditions is of a great concern as they fix the signal dynamic (peak height) and the signal fluctuation, respectively. This feasibility study, using simulation, allows us to obtain the optimal values of trap operating condition for 1-6 u mass injection and confinement with high resolution

L’identification des mécanismes de relâchement des Produits de Fission (PF) hors de combustible nucléaire irradié lors d’un accident grave est primordiale pour le développement de codes capables d’estimer précisément le terme source (nature et quantité des radionucléides émis dans l’environnement). Parmi les différents PF, les Ba, Cs, Mo et le Ru sont particulièrement intéressants, car ils peuvent interagir entre eux ou avec d’autres éléments et donc affecter leur relâchement. Dans le cadre de cette thèse, deux axes de travail ont été mis en place avec l’objectif d’identifier les phases chimiques présentes avant l’accident et leur évolution au cours de l’accident lui-même. L’approche expérimentale a consisté à reproduire les conditions d’un accident nucléaire à l’échelle du laboratoire, en utilisant des échantillons de combustibles irradiés et des matériaux modèles (UO₂ vierge dopés en 12 PF). Le principal avantage de ces derniers est l’utilisation de méthodes de spéciation chimique comme la Spectroscopie d’Absorption des rayons X, qui n’est pas aujourd’hui encore disponible pour les combustibles irradiés. Trois échantillons de combustible irradié ont été étudies, représentatifs de l’état initial (i.e. avant l’accident), d’une étape intermédiaire en température (1773K) et d’un état avancé d’accident nucléaire (2873K). Pour les matériaux modèles, plusieurs séquences accidentelles (de 573K à 1973K) ont été réalisés. Les résultats expérimentaux ont permis d’établir un nouveau mécanisme de relâchement des PF en en fonction des conditions oxydantes et réductrices du scénario accidentel. Ces résultats ont démontré aussi l’importance des matériaux modèles pour l’étude des accidents nucléaires graves, en complémentarité aux combustibles irradiés
The identification of Fission Products (FP) release mechanism from irradiated nuclear fuels during a severe accident is of main importance for the development of codes for the estimation of the source-term (nature and quantity of radionuclides released into the environment). Among the many FP Ba, Cs, Mo and Ru present a particular interest, since they may interact with each other or other elements and thus affect their release. In the framework of this thesis, two work axes have been set up in order to identify, firstly, the chemical phases initially present before the accident and, secondly, their evolution during the accident itself. The experimental approach consisted in reproducing nuclear severe accidents conditions at laboratory scale using both irradiated fuels and model materials (natural UO₂ doped with 12 FP). The advantage of these latter is the possibility of using characterization methods such as X-ray Absorption Spectroscopy which are not available for irradiated fuels. Three irradiated fuel samples have been studied, representative to an initial state (before the accident), to an intermediate stage (1773K) and to an advanced stage (2873K) of a nuclear severe accident. Regarding to model materials, many accident sequences have been carried out, from 573 to 1973K. Experimental results have allowed to establish a new release mechanism, considering both reducing and oxidizing conditions during an accident. These results have also demonstrated the importance of model materials as a complement to irradiated nuclear fuels in the study of nuclear severe accidents

The structural identification of organic substances has always been a challenge for chemistry, since its emergence as a science. Initially, the techniques employed induced error, because it used destructive techniques to generate derivatives that had nothing to do with the starting material. From the mid-twentieth century there was an evolution of spectroscopy and spectrometry, along with new methods of isolation and purification, increasing the reliability of the results. Nuclear Magnetic Resonance spectroscopy (NMR) is a technique widely used to study the structure and dynamic of organic compounds in solution. The NMR technique is not only used in structural determination, but also to track the performance of a synthetic reaction. The present study aimed the identification of organic compounds in the Chemistry of Natural Products by uni- and bi-dimensional NMR. We studied metabolites from Melloa quadrivalvis, a plant of the Bignoniaceae family, known as vine basket, through the structural elucidation of a compound, one flavonoid glycoside. The study was conducted in two fractions isolated from Serjania lethalis St. Hil, and it was possible to identify and quantify by NMR, a mixture of sitosterol and stigmasterol glycoside, in one of the fractions. The analysis of the NMR spectra of a compound isolated from the other fraction of Serjania gave evidence for a saponin structure. Additionally, a study was made on secondary metabolites from Curvularia eragrostidis (Henn.) Meyer, a fungus that is responsible for burning the yam leaf and can cause total loss of production.
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A identificação estrutural de substâncias orgânicas sempre foi um desafio para a química, desde o seu surgimento como ciência. Inicialmente as técnicas empregadas induziam a erro, pois empregavam técnicas destrutivas que geravam derivados que nada tinham a ver com a substância de partida. A partir da metade do século XX houve uma evolução da espectroscopia e da espectrometria, juntamente com novas metodologias de isolamento e de purificação, aumentando a confiabilidade dos resultados obtidos. A espectroscopia por ressonância magnética nuclear (RMN) é uma técnica muito usada no estudo estrutural e na dinâmica de compostos orgânicos em solução. A RMN além de ser uma técnica empregada na determinação estrutural, pode também ser aplicada no acompanhamento de reações de síntese. Este trabalho teve como objetivo a identificação de compostos orgânicos na Química de Produtos Naturais por técnicas de RMN uni e bidimensionais. Foram estudados metabólitos da casca do tronco de Melloa quadrivalvis, uma planta da família das Bignoniaceae conhecida como cipó de cesto, onde foi feita elucidação estrutural de um composto, um flavonoide glicosilado. Foram ainda estudadas duas frações isoladas de Serjania lethalis St. Hil, sendo identificados e quantificados por RMN, uma mistura de sitosterol glicosilado e estigmasterol, em uma das frações, e na outra fração, a estrutura de uma saponina foi elucidada. Adicionalmente, foi feito estudo de metabólitos secundários de Curvularia eragrostidis (Henn.) Meyer, um fungo que é um dos responsáveis pela queima da folha do inhame e pode causar a perda total de uma produção.

As the battle against ever-increasing drug resistence bacteria rages on, novel and sometimes more complex natural products can be used to combat this. In this study, two-dimensional NMR techniques were utilized to collect a complete spectral data set for two natural products. The first structure, a synthesized Pyrrolobenzodiazepine alkaloid natural product was confirmed through these methods. The second, a strain of Rhodococcus, MTM3W5.2, produces a novel antibacterial molecule in broth cultures and the active compound was fractionated using a Sephedex LH-20 column. Chromatographic purification yielded a pure sample at 58.90 minutes, RT.58. HRMS data deduced an exact mass of 911.5490 Da, equivalent to a molecular formula of C52H78O13. Several major spin systems were constructed from the 2D-NMR spectra. However, due to limited sample quantity in compound with a large molecular weight and product instability, the long range HMBC signals needed to connect these fragments have not yet been obtained.

Due to the nuclear testing, reentry and disintegration of nuclear powered satellites, nuclear reactor accidents, uranium nuclear fuel cycle and nuclear weapons production, actinides have been introduced into the environment. Proposed disposal of high-level radioactive waste in mined repositories in geologic formation as well as the storage and disposal of uranium and plutonium from weapons dismantlement are further possible sources for actinide releases to the environment. The mobilization of radionuclides in the environment has been studied for many years with the prime objective of tracing the routes by which they accumulate in the food chain and become available for human consumption. Therefore, it is necessary to have available accurate, reliable and precise analytical methods to determine actinides and fission products in environmental samples as well as their isotopic ratio. These procedures should also be as fast as possible in order to give results in radiological emergency cases to take decision for radiation protection of the environment and human beings.

In this Ph.D. thesis, different kinds of phases for liquid chromatography have been tested to achieve the separation of the interfering elements and isotopes before the mass spectrometry and -spectrometry measurements. UTEVA and TEVA extraction resin (Eichrom Industries, USA) have been packed in chromatographic column as stationary phases and used for the separation of tri, tetra and hexavalent actinides and for the separation of trivalent lanthanides (La-Eu) and actinides, respectively. IonPac CS5A and CS10 (Dionex, Sunnyvale, USA) ion chromatography column were used for the simultaneous separation of actinide and lanthanides elements and for the actinides separation. The columns were coupled on-line to an Inductively Coupled Plasma Mass Spectrometer (ICP-MS) to solve isobaric interferences between actinide and lanthanide elements and off-line to a -spectrometer to solve the energy interferences between the analytes. Moreover, an investigation on the use of the UTEVA resin and IonPac Trace Cation Concentrator II column (TCC-II from Dionex, Sunnyvale, USA) as preconcentrator columns for actinide and lanthanide elements has been carried-out.

The analytical measurements have been made by mass spectrometric as well as by radiometric techniques. ICP-MS has been used for the characterization of spent nuclear fuels in terms of actinides and lanthanides content and burn-up calculation as well as for the determination of the long-lived actinides and lanthanides in environmental samples. - and -spectrometry have been used for 241Am determination in sediments and soils samples. -spectrometry and Liquid Scintillation Counting (LSC) have been used to analyze the eluted fractions from on-batch experiments.

The results obtained with the analytical procedures developed, for spent nuclear fuel solutions as well as for environmental samples, were always compared to those obtained by other independent techniques and good agreements have been always achieved.

Comprendre les mécanismes de spéciation des Produits de Fission (PF) dans le combustible nucléaire est un enjeu majeur pour pouvoir estimer précisément le terme source d’un accident grave. Parmi les nombreux PF créés, certains sont très réactifs et peuvent avoir un impact radiologique important en cas de relâchement dans l’atmosphère. C’est notamment le cas du césium (Cs), du molybdène (Mo) et du baryum (Ba). C’est dans ce contexte que s’inscrit le travail de thèse qui propose d’apporter des données expérimentales sur l’effet du potentiel oxygène sur la spéciation du Cs, du Mo et du Ba dans des combustibles nucléaires, à différents stades d’un accident grave.Une approche thermodynamique a été utilisée en support à l’interprétation des données expérimentales obtenues dans le cadre de ce travail. Deux types d’échantillons ont été étudiés: des combustibles MOX irradiés et des matériaux simulant un combustible UO2 à fort taux de combustion, obtenus par frittage à haute température (SIMFuel). Les échantillons ont été traités thermiquement dans des conditions représentatives d’un accident grave survenant dans un Réacteur à Eau Pressurisée (REP). Les conditions expérimentales ont couvert une gamme de température allant de 400°C à 2530°C et des potentiels oxygène situés entre -470 kJ.mol(O2)-1 et -100 kJ.mol(O2)-1. Les échantillons ont été caractérisés finement avant et après chaque traitement à l’aide de techniques complémentaires comme la microscopie optique et électronique, la microsonde et le SIMS dans le cas de l’irradié. Des mesures de XANES sur synchrotron ont été réalisées sur SIMFuel et ont conduit à des résultats importants en termes de spéciation des PF. Enfin, la technique de Spark Plasma Sintering (SPS) a été explorée avec succès pour la fabrication de SIMFuel contenant du Cs, du Mo et du Ba sous des formes chimiques représentatives d’un combustible REP en fonctionnement nominal.Ce travail a permis de mettre en évidence l’effet de la température en conditions oxydantes sur le comportement du combustible et des PF. Une oxydation du Mo, initialement présent sous forme métallique dans les inclusions blanches du combustible, en MoO2 a été observée dès 1000°C en conditions oxydantes. Une interaction entre le MoO2 formé et le Ba contenu dans la phase oxyde a eu lieu dans les mêmes conditions, menant à la formation de BaMoO4. Le potentiel oxygène joue aussi un rôle important dans le phénomène d’interaction pastille-gaine, en favorisant la diffusion des espèces en conditions oxydantes, diminuant ainsi la température de fusion du combustible
In the nuclear community, it is a top priority to gain in-depth understanding of fission product (FP) speciation mechanisms occurring in nuclear fuel in order to precisely estimate the source term of a severe accident. Among the FP produced, some are highly reactive and may have a strong radiological impact if released into the environment. This is particularly the case of cesium (Cs), molybdenum (Mo) and barium (Ba). In this context, the objective of this study is to provide experimental data on the effect of the oxygen potential on Cs, Mo and Ba speciation in nuclear fuels at different stages of a severe accident.A thermodynamic approach was coupled with the experimental work to support the interpretation of experimental data. Two types of samples were studied in detail: irradiated MOX fuels and simulated high burn-up UO2 fuels produced through sintering at high temperature (SIMFuel). The samples were submitted to thermal treatments in conditions representative of a pressurised water reactor (PWR) severe accident. This approach made it possible to cover a temperature range from 400°C up to 2530°C and oxygen potentials from -470 kJ.mol(O2)-1 to -100 kJ.mol(O2)-1. The samples were characterized before and after each test using complementary techniques like OM, SEM, EPMA and SIMS in the case of irradiated fuels. XANES measurements using synchrotron radiation facilities were performed on SIMFuels and provided valuable results on FP speciation. Moreover, spark plasma sintering (SPS) was successfully investigated for the production of SIMFuel samples containing Cs, Mo and Ba in a chemical state representative of PWR fuel in normal operating conditions.This work highlighted the effect of oxidizing severe accident conditions on the fuel and FP behavior. Oxidation of Mo initially contained in the fuel’s metallic inclusions into MoO2 was observed to take place around 1000°C in oxidizing conditions. An interaction between MoO2 and the oxide phase containing Ba took place in the same conditions, leading to the formation of BaMoO4. The oxygen potential also plays an important role in fuel-cladding interactions, enhancing the diffusion of species in oxidizing conditions and lowering the temperature at which fuel melting occurs

Orientador: Anita Jocelyne Marsaioli
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: Opiliões são aracnídeos encontrados em todos os continentes, com mais de 6000 espécies descritas, e secretam uma mistura de compostos voláteis que atuam principalmente como defesa contra predadores naturais. A família Gonyleptidae, pertence à subordem Laniatores, é a mais diversa química e morfologicamente e está presente em todo o território brasileiro. Assim, o estudo da identidade e da origem biossintética dos compostos presentes no exudato de espécimes desta família fornece informações filogenéticas, além de ser uma fonte de novos produtos naturais. Neste trabalho foram caracterizados os exudatos de cinco espécies de opiliões de diferentes subfamílias. As espécies Cobania picea, Roeweria virescens e Serracutisoma proximum secretam uma mistura benzoquinonas. Por outro lado, Iporangaia pustulosa e Neosadocus maximus produzem 1-hepten-3-ona e 1-(6-butil-3,4-diidro-2H-piran-2-il)-pentan-1-ona. Este último foi descrito pela primeira vez na literatura, revelando uma nova classe de compostos com esqueleto piranil em opiliões, originados da reação de hetero-Diels-Alder in vivo de duas moléculas de vinil cetona. Também foi determinada a configuração absoluta da (R)-4-metil-1-hexen-3-ona produzida por Acanthogonyleptes pulcher e Gonyleptes saprophilus. Outras 4-metil-3-cetonas de insetos possuem configuração (S). Adicionalmente foi realizado o primeiro estudo biossintético com opiliões através da incorporação de precursores marcados com C e espectroscopia de RMN de C. Foram estudados I. pustulosa, que produz vinil cetona, e Magnispina neptunus, que produz benzoquinona, revelando que ambas as classes químicas são formadas através de unidades acetato e propionato pela via policetídica
Abstract: Harvestmen are arachnids widespread in all continents, with more than 6,000 described species. They secrete a mixture of volatiles compounds with the main function of defense against natural predators. The family Gonyleptidae belongs to the suborder Laniatores, is the most diverse in chemistry and morphology and is predominant in Brazil. Therefore, studying the identity and biosynthetic origin of this family exudate components gives phylogenetic information and is a source of new natural products. In this work five species exudate from different subfamilies were characterized. The species Cobania picea, Roeweria virescens and Serracutisoma proximum secrete a mixture of benzoquinones, while Iporangaia pustulosa and Neosadocus maximus produce 1-hepten-3-one and 1-(6-butil-3,4-dihydro-2H-piran-2-yl)-pentan-1-one. The latter was described for the first time, and belongs to a new class of harvestman metabolites with piranyl moiety in harvestmen, which were rationalized as the hetero-Diels-Alder adduct of two vinyl ketone molecules. Additionally the absolute configuration of (R)-4-methyl-1-hexen-3-one from Acanthogonyleptes pulcher and Gonyleptes saprophilus was determined. Analogous 4-methyl-3-cetones from insects have S configuration. It was also performed the first biosynthetic investigation with harvestmen by C labeled precursors incorporation and C NMR. The studied species were /.pustulosa and Magnispina neptunus, which produce vinyl ketones and benzoquinones, respectively. The results revealed that these chemical classes are biosynthesized with acetate and propionate units via polyketide pathway
Doutorado
Quimica Organica
Doutora em Ciências

Orientador: Eduardo Melani Rocha
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Ciencias Medicas
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Resumo: Este estudo avaliou as possíveis vias comuns na fisiopatogênese da síndrome do olho seco no Diabetes Mellitus (DM) e no envelhecimento, envolvendo o acúmulo dos produtos de glicosilação ("Advanced Glycation End-products" - AGEs), seu receptor RAGE e a ativação do Fator Nuclear-?B (NF-?B) na glândula lacrimal (GL) e alterações do filme lacrimal nessas condições. Modelos animais de DM induzido com estreptozotocina e animais senis (24 meses de vida) foram comparados a animais controle tratados com tampão citrato e adultos jovens (2 meses de vida). Foram avaliadas vias de sinalização, envolvendo AGEs, RAGE e a ativação do NF-?B na GL e alterações no filme lacrimal em ratos Wistar de todos os grupos. A análise do filme lacrimal foi realizada através de medidas de volume de secreção basal e dosagem de citocinas como a Interleucina-1 ß (IL-1 ß) e Fator de Necrose Tumoral - a (TNF- a). A capacidade secretória da GL foi avaliada através de medidas da atividade de peroxidase. Técnicas de "western blot" foram utilizadas para avaliar a expressão e ativação do NF-?B na GL. A expressão de AGE, RAGE e NF-?B na GL e córnea nos grupos estudados, foi avaliada através de microscopia confocal com imunofluorescência. O volume lacrimal foi significativamente menor nos animais diabéticos e senis (P=0,02 e 0,016, respectivamente). Concentrações de IL-1ß e TNF-a na lágrima foram mais altas nos ratos diabéticos e senis do que nos controles e adultos jovens (P=0,007 e 0,02 nos diabéticos e P= 0,007 e P= 0,05 nos senis). A atividade de peroxidase foi significativamente mais baixa no grupo senil (P=0,016), mas não nos experimentos, comparando animais diabéticos e controles (P=0,34). A expressão de AGE, RAGE e NF-?B na GL foi aumentada nos animais diabéticos e senis. O DM e a senilidade induzem alterações estruturais e secretórias significativas na GL e nos tecidos da superfície ocular e associa-se a maior incidência de olho seco. A expressão aumentada de AGE, RAGE e NF-?B na GL sugere a participação desses fatores nas vias de sinalização e subseqüentes alterações inflamatórias relacionadas ao olho seco nessas condições.
Abstract: The present study evaluates the dry eye syndrome related to diabetes and aging through the involvement of the Advanced Glycation End-product (AGEs), the Advanced Glycation End-product Receptor (RAGE) axis and Nuclear Factor-?B (NF-?B) activation in lacrimal gland (LG) and tear film dysfunction in these conditions. To evaluate whether AGE, RAGE and NF-?B signaling in LG are altered in diabetes and aging, streptozotocin-induced diabetic, normoglicaemic, aging (24 month-old) and young adults (2 month-old) male Wistar rats were compared. Tear film alterations and the expression of AGE, RAGE and NF-?B in ocular tissues were evaluated in all considered groups. Tear secretion parameters as basal tear secretion volume, Interleukin-1 ß (IL-1 ß) and Tumor Necrosis Factor- a (TNF- a) levels and LG and peroxidase activity in LG tissue were measured. NF-?B expression and activation was evaluated in LG by western blot. Immunohistochemistry with confocal microscopy was used to assess AGE, RAGE and NF-?B expression in LG of all groups. Tear volume was significantly lower in diabetic and aging rats (P=0.02 and 0.016, respectively). IL-1ß and TNF-a concentrations in tears were higher in diabetic and aging than in control and young rats (P=0.007 and 0.02 in diabetic and P= 0.007 and P= 0.05 in aging). Peroxidase activity was significantly lower in the aging group (P=0.016) but not the assays with diabetic rats (P=0.34). AGE, RAGE and NF-?B expressions were increased in LG of diabetic and aging rats. Diabetes and aging induce significant alterations in rat LG structure and secretion. The higher expression of AGE, RAGE and NF-?B in LG may suggest that these factors are involved in signalling and in subsequent inflammatory alterations related to dry eye related to these conditions.
Doutorado
Clinica Medica
Doutor em Clínica Médica

In the event of a nuclear power plant accident, fission products could be released into the atmosphere potentially affecting the health of local citizens. In order to triage the possibly large number of people impacted, a detection device is needed that can acquire data quickly and that is sensitive to internal contamination. The portal monitor TPM-903B was investigated for use in the event of a fission product release. A list of fission products released from a Pressurized Water Reactor (PWR) was generated and separated into two groups--Group 1 (gamma- and beta-emitting fission products) and Group 2 (strictly beta-emitting fission products.) Group one fission products were used in the previously validated Monte Carlo N-Particle Transport Code (MCNP) model of the portal monitor. Two MIRD anthropomorphic phantom types were implemented in the MCNP model--the Adipose Male and Child phantoms. Dose and Risk Calculation software (DCAL) provided inhalation biokinetic data that were applied to the output of the MCNP modeling to determine the radionuclide concentrations in each organ as a function of time. For each phantom type, these data were used to determine the total body counts associated with each individual gamma-emitting fission product. Corresponding adult and child dose coefficients were implemented to determine the total body counts per 250 mSv. A weighted sum of all of the isotopes involved was performed. The ratio of dose associated with gamma-emitting fission products to the total of all fission products was determined based on corresponding dose coefficients and relative abundance. This ratio was used to project the total body counts corresponding to 250mSv for the entire fission product release inhalation--including all types of radiation. The developed procedure sheets will be used by first response personnel in the event of a fission product release.

The objective of the present work is to better understand chemical evolution of both solid and gaseous phases during torrefaction of various biomasses. Torrefaction experiments were carried out with a dynamic profile of temperatures between 200 and 300°C, under inert atmosphere, for pine, ash-wood, miscanthus and wheat straw. Mass loss and formation of condensable species were analyzed by TGA-GC-MS, and chemical evolution of solid phase was characterized by 13C CP/MAS solid-state NMR. Thirty condensable species could be detected; a half of these species were formed during the whole temperature range, and a third were formed by all biomass types. The main phenomena that occurred in solid phase were found to be decrystallization of cellulose, severe degradation of hemicellulose, devolatilization of acetyl groups, conservation of methoxyl groups and charring. It was also found that mass loss and chemical evolution of solid were not directly correlated for different biomasses. Based on the experimental results, a conceptual model was developed to describe biomass degradation duringtorrefaction. Thirty reactions were determined for the three major macromolecular constituents, namely cellulose, hemicellulose – represented by C5 and C6 sugars – and lignin – represented by H, G and S units. The main innovations of this model are in thedetailed approach of hemicellulose and lignin compositions, as well as in the prediction of sixteen condensable and five permanent species, and six forms of solid char, through chemically meaningful and stoichiometrically valid reactions.

The role of antioxidants in the prevention of neurodegenerative diseases has been well documented. The use of synthetic antioxidants has decreased due to the ssociation of these compounds with certain cancers. Thus, the search for novel natural antioxidants has gained much focus in research. Most common methods of determining antioxidant capacity are the radical generated assays and biological assays such as lipid peroxidation and the nitroblue tetrazolium assay. Electrochemical methods have been proposed for the determination of bio-active compounds such as antioxidants. The electrochemical methods of cyclic voltammetry and square wave voltammetry were evaluated for the determination of antioxidant capacity initially examining known antioxidants and then using plant extracts of Sutherlandia frutescens as a case study. The antioxidant properties determined by electrochemical methods were validated utilising the non-biological methods of the DPPH, TEAC, ferrozine and FC assay and biological pharmacological methods. The results indicated that Sutherlandia frutescens contains potent antioxidant compounds that are able to reduce lipid peroxidation. The electrochemical techniques of square wave voltammetry and cyclic voltammetry were applied for the screening of a large number of extracts of various algae for the detection of antioxidant compounds. The results indicated that electrochemistry can be used as a preliminary method for the rapid screening of a large number of crude samples for antioxidant compounds. Electrochemical methods were also evaluated as a method for guiding the isolation and purification of antioxidant metabolites in Sargassum elegans. Solvent partitioning and fractionation of the marine alga allowed for the purification of antioxidant compounds. At each step of purification electrochemical methods were utilized to determine which fractions contained the more potent antioxidant compounds and thus guide further purification. The purified antioxidant compounds were elucidated using NMR to determine the structure of the antioxidant compounds.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
FAPESP:06/54851-8

O sistema especialista SISTEMAT tem por objetivo auxiliar pesquisadores da área de produtos naturais no processo de determinação estrutural de substâncias. Para tanto, utilizando dados provenientes de várias técnicas espectrométricas e espectroscópicas, principalmente RMN 13C, inúmeros programas foram desenvolvidos com a finalidade de propor o provável esqueleto de uma substância. Essa informação, juntamente com as substruturas apresentadas a partir de um conjunto de dados, é utilizada por geradores estruturais como grandes restrições, a fim de impedir a explosão combinatória e a geração de propostas estruturais incompatíveis com produtos naturais, além de reduzir o elevado tempo computacional gasto durante uma análise. Esse trabalho descreve o desenvolvimento e utilização dos módulos de reconhecimento de esqueletos, determinação e geração estrutural e simulação de dados de RMN 13C de esteróides. Assim, foi elaborada uma base de dados com 1436 substâncias distribuídas entre 119 tipos de esqueletos provenientes das mais diversas fontes naturais. Vários testes foram realizados e bons percentuais de acerto foram obtidos para o reconhecimento de esqueletos e geração de propostas estruturais através da sobreposição dos tipos de anéis encontrados em esqueletos de esteróides. Para validar as propostas estruturais apresentadas pelo gerador, bem como para prever os dados de deslocamentos químicos de novos esteróides, o simulador de dados de RMN 13C foi usado e, quando comparado a um programa comercial de mesma finalidade, apresentou maior exatidão na previsão dos dados.
The aim of the expert system SISTEMAT is to aid natural product researchers in the process of structural determination of organic substances. For that, using data from various spectrometric and spectroscopic techniques, mainly 13C NMR, countless programs were developed to propose the most probable skeleton of a substance. This information together with the substructures shown from the data set are utilized by structural generators as important constraints in order to avoid the combinatorial explosion problem and the generation of incompatible structural proposals for natural products, besides reducing the computational time spent during the analysis. This work describes the development and use of the modules of skeleton identification, structural determination and generation, and the 13C NMR data prediction of steroids. Thus, was built a database containing 1436 steroids distributed in 119 different skeletons originated from the most varied natural sources. Several tests were performed, wherein good hit percentuals were obtained for the skeleton identification and structural generation through the overlapping of the types of rings found in the steroid skeletons. For validation of the structural proposals shown by the generator as well as for prediction of the chemical shift data of new substances, the simulator of 13C NMR data was used and next compared with a commercial program of the same purpose, and exhibited higher accuracy in the data prediction.

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

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