Orientador: Luiz Carlos Dias / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-03T05:30:59Z (GMT). No. of bitstreams: 1 Bau_RosanaZanetti_D.pdf: 4826979 bytes, checksum: c2d4893b0a8176373826c4d9e9e933f8 (MD5) Previous issue date: 2002 / Doutorado

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work a procedure for boron determination in samples of silicon carbide by pyrohydrolysis and detection by inductively coupled plasma optical emission spectrometry was developed. The silicon carbide samples were also decomposed by microwave assisted wet digestion in closed vessels and alkaline fusion. However, complete digestion was not observed under the conditions used for wet digestion and for fusion. Regarding the proposed pyrohydrolysis procedure important variables were initially investigated such as: oven temperature, air and water flow rate, sample mass, reaction time and use of accelerator. Spectral interference promoted by tungsten was observed during the studies and the selection of suitable emission lines for B determinations should be carried out. Sample mass of 200 mg, use of 200 mg of vanadium pentoxide (accelerator), reaction time of 15 minutes and a temperature of 1050 ° C were some of the optimized conditions wich were used for subsequent samples analysis. It was found that the spectral interference caused by W did not allowed the use of the main emission line to determine B. The absorbing solution used was distilled water and only the emission lines of 249.772, 208.889 and 182.639 nm could be used for the determination of boron. The accuracy of the proposed procedure was checked using certified reference material of silicon carbide (BAM S003) and agreement better than 96% were obtained using the three emission lines for boron. Coefficients of variation lower than 10% were obtained for the analysis (triplicate) of different samples of silicon carbide. Detection limits of 0.20, 0.90 and 2.0 mg-1 g were obtained for the emission lines of 249.772, 208.889 and 182.639 nm, respectively, using 200 mg of sample and a final volume of the absorbing solution equal to 30 mL. / Neste trabalho é proposto um procedimento para determinação de boro em amostras de carbeto de silício por piroidrólise e detecção por espectrometria de emissão óptica com plasma indutivamente acoplado. As amostras de carbeto de silício também foram decompostas utilizando decomposição por via úmida em sistema fechado com radiação micro-ondas e por fusão alcalina. Contudo, nas condições utilizadas não foi possível a completa solubilização das amostras quando tais métodos de preparo de amostra foram empregados. Com relação ao procedimento de piroidrólise proposto, inicialmente, investigaram-se algumas variáveis importantes tais como: temperatura do forno, vazão de ar e água, massa de amostra, tempo de piroidrólise e utilização de acelerador. Massas de amostra de 200 mg junto a 200 mg de pentóxido de vanádio, tempo de reação de 15 minutos e temperatura de 1050 oC foram algumas das condições otimizadas e utilizadas para as subsequentes determinações de boro nas amostras de carbeto de silício. Verificou-se que a interferência espectral causada por W não permitiu a utilização da linha de emissão de 249,676 nm para determinação de B. A solução absorvedora utilizada foi água com resistividade igual ou maior a 18,2 MΩ.cm e somente as linhas de emissão de 249,772; 208,889 e 182,639 nm puderam ser utilizadas na determinação de boro. A exatidão do procedimento proposto foi verificada mediante a análise do material de referência certificado de carbeto de silício (BAM S003) obtendo-se uma concordância superior a 96%, para todas as linhas de emissão utilizadas. Coeficientes de variação inferiores a 10% foram obtidos para as análises em triplicata das diferentes amostras de carbeto de silício. Limites de detecção de 0,20; 0,90 e 2,0 μg g-1 foram obtidos nas linhas de emissão de 249,772; 208,889 e 182,639 nm, respectivamente, utilizando-se 200 mg de amostra e volume final do extrato da solução absorvedora de 30 mL.

En este trabajo de Tesis Doctoral se presentan los resultados obtenidos durante el estudio de la síntesis de derivados orgánicos bis-metalados, conteniendo estaño y silicio, a partir de tres dioles primarios cuyas estructuras poseen simetría C2: (4S,5S)-1,3-dioxolano- 2,2-dimetil-4,5-dimetanol; (11R,12R)–9,10–dihidro–9,10–etanoantraceno–11,12–dimetanol y (S)-2,2’-bis(hidroximetil)-1,1’-binaftaleno, con la finalidad de estudiar sus propiedades físicas y químicas así como también sus posibles aplicaciones como inductores asimétricos en síntesis orgánica y sus posibles aplicaciones biológicas. En todos los casos se evaluaron las mejores condiciones de reacción, tanto para sintetizar los dioles como todos los intermediarios necesarios, a fin de lograr la obtención de los derivados bis-metalados asimétricos. Los productos sililados no se obtuvieron o se consiguieron en muy baja cantidad y no pudieron ser purificados. Con respecto a los compuestos estannilados, se lograron obtener los productos bis-trifenilestannilados a partir de los derivados tosilados o halogenados de estos dioles, por reacción con trifenilestannillitio, aunque la purificación no pudo lograrse en todos los casos. A partir del compuesto bis-trifenilestannilado derivado del diol (4S,5S)-1,3-dioxolano-2,2- dimetil-4,5-dimetanol se obtuvo el correspondiente derivado bis-halodifenilestannilado y, a partir de éste, el bis-hidruro órgano-diestánnico. Este último se evaluó en cuanto a su actividad en síntesis orgánica asimétrica. Es importante destacar que, hasta donde sabemos, no existen reportes en la literatura de compuestos con simetría C2 que tengan dos unidades hidrogenodialquilestannilo en la molécula. La inducción asimétrica observada durante los estudios de aplicación de este bis-hidruro organoestánnico en reacciones de reducción de cetonas proquirales y de α-bromoésteres no fue significativa. Sin embargo, fue posible aplicarlo en cantidades catalíticas a un proceso de reducción de α-bromoésteres. Los estudios de actividad antiproliferativa de dos de los derivados organoestánnicos obtenidos sobre células provenientes de tumores sólidos humanos dieron muy buenos resultados, en particular con el (4R,5R)-1,3-dioxolano-2,2-dimetil-4,5-dimetilen-bisiododifenilestannano, que mostró ser muy activo. Por otro lado, dadas las muchas aplicaciones que presentan los ésteres borónicos, se estudió la síntesis de nuevos ésteres derivados de ácidos borónicos y diborónicos y se probó su capacidad para actuar como inductores enantioselectivos. Aplicados a la reducción de acetofenona, utilizando como agentes reductores NaBH4 o LiBH4, los ee obtenidos tampoco fueron significativos en este caso. Sin embargo, su aplicación como inductores asimétricos en reacciones multicomponente de formación de 4-tiazolidinonas, dieron resultados alentadores. Además, como parte de las tareas realizadas en la Universidad de Colonia, Alemania bajo la dirección del Prof. Dr. Hans-Günther Schmalz, se evaluó la síntesis de los dioles con simetría C2: (S)-2,2’-bis(hidroximetil)-1,1’-binaftaleno, (4R,5R)-2,2-dimetil-1,3-dioxolano-4,5- bis(3,5-difenil-fenil)metanol y (4R,5R)-2,2-dimetil-1,3-dioxolano-4,5-bis-[di(3,5-dietilfenil)- metanol]. Éstos se utilizaron en el estudio de la síntesis de ligandos modulares fosfinafosfito. Si bien, durante el período de la estancia, no se tuvo éxito en la formación de los nuevos ligandos, los dioles sintetizados seguirán siendo objeto de estudio del grupo de investigación del Prof. Schmalz para lograr la síntesis de ligandos bisfosfina y su posterior aplicación en catálisis asimétrica mediada por metales de transición. / This Doctoral Thesis presents the results obtained during the study of the synthesis of bis-metalated (bis-stannyl and bis-silyl) derivatives from three diols with C2 symmetry: (4S, 5S) -1,3 dioxolane-2,2-dimethyl-4,5-dimethanol; (11R, 12R) -9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol and (S) -2,2'-bis (hydroxymethyl) -1,1'-binaphthalene; in order to study their physical and chemical properties as well as their possible applications in organic synthesis as asymmetric inductors and their potential biological activities. It was studied the best way to obtain the three diols and the necessary derivatives to reach the synthesis of the asymmetric bis-metalated compounds. Silicon derivatives were not obtained or were obtained in low yields and could not been isolated. Organotin compounds were achieved when tosylated or halogenated derivatives were treated with triphenyltinlithium, but the purification of the organotincompounds was difficult. The bis-stannyl derivative from (4S, 5S) -1,3 dioxolane-2,2-dimethyl-4,5-dimethanol was converted into a bis-organotinhydride and its activity in asymmetric organic synthesis was evaluated. To the best of our knowledge there are no reports in the literature of C2 chiral compounds with two hydrodialkylstannyl units in the molecule. The asymmetric induction observed in reductions of prochiral ketones and in the reduction of alphabromo esters, was not significant. However, in the reduction of alphabromo esters it was possible to use catalytic amounts of the organotin hydride. Studies of antiproliferative activity of two organotin compounds on cells derived from human solid tumors were particularly good for the organotin halide (((4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(iododiphenylstannane) which proved to be very active. On the other hand, it was studied the synthesis of new boronic esters given the numerous applications that these compounds have shown in asymmetric organic synthesis. These boronic esters were tested as chiral inductors in the reduction of acetophenone using NaBH4 or LiBH4 as reducing agents but the product was obtained with poor ee. Nevertheless, in the synthesis of 4-thiazolidinones through a multicomponent reaction the ed obtained are promising. Furthermore it was evaluated the synthesis of modular phosphine-phosphite ligands based on the diols with C2 symmetry (S) -2,2'-bis (hydroxymethyl) -1,1'-binaphthalene, (4R, 5R) -2,2 dimethyl-1,3-dioxolane-4,5-bis (3,5-diphenyl-phenyl) methanol and (4R, 5R) - 2,2-dimethyl-1,3-dioxolane-4,5-bis-[di-(3,5-diethylphenyl) methanol] as part of the tasks performed at the University of Cologne, Germany under the direction of Prof. Dr. Hans-Günther Schmalz. Although the synthesis of the new ligands was unsuccessful, the three diols synthetized in this period of the present thesis will be evaluated by the group of Prof. Schmalz in the synthesis of bisphosphines ligands and their subsequent application in asymmetric catalysis mediated by transition metals.

Submitted by Aelson Maciera (aelsoncm@terra.com.br) on 2017-08-16T18:44:54Z No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-30T17:35:55Z (GMT) No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-30T17:36:40Z (GMT) No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Made available in DSpace on 2018-01-30T17:44:12Z (GMT). No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) Previous issue date: 2017-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Sintering additives (AS) have great potential to be applied in refractory castables as they reduce the densification temperature of these products. Additionally, these components may induce the generation of a transient liquid phase in the microstructure at high temperatures, which can react with the other materials of the composition to give rise novel solid refractory phases. Considering these aspects, the present work evaluated the role of five different AS (boron oxide, boric acid, sodium borosilicate, magnesium borate and boron carbide) when added to alumina-based castable compositions containing hydratable alumina as binder. Based on the thermomechanical characterization, XRD analysis and the in situ elastic modulus measurement, boron carbide (B4C) have been selected as a promising AS because this material sped up the sintering process at lower temperatures and induced the aluminum borates formation due to the reaction between the liquid phase and the fine alumina contained in the castable matrix. Afterwards, the effects of B4C was evaluated in ultra-low calcium oxide castables bonded with: colloidal alumina (AC), hydratable alumina (AB) and/ or SioxX®-Zero (SZ). SZ-bonded materials (4 wt.%) had good performance at temperatures around 1100°C due to the mullite generation. On the another hand, castables containing AC as binder (4 wt.% of solids) and 0.5 wt.% of B4C are promising options to be used in working conditions between 600-815°C, whereas the same mixture without B4C could only be densified above 1100°C. Similar effect was observed when 1.0 wt.% B4C was added to SZ-containing castables as the aluminum borates generation allows these compositions to be used in working conditions around 815°C. Therefore, an appropriate AS selection for high-alumina castables with ultra-low CAC content has the potential to favour the earlier sintering of the refractory and improve its thermomechanical properties, which can fulfill the requirements of the petrochemical industry. / Os aditivos sinterizantes (AS) possuem potencial para serem aplicados em concretos refratários, pois diminuem a temperatura de densificação destes produtos. Adicionalmente, tais componentes podem atuar favorecendo a formação de líquidos transientes na microestrutura em altas temperaturas, os quais têm a capacidade de reagir com os outros constituintes da composição para formar novas fases refratárias. Diante desta possibilidade, neste trabalho foram avaliados os efeitos da adição de cinco fontes de boro como AS (óxido de boro, ácido bórico, borosilicato de sódio, borato de magnésio e carbeto de boro) em concretos de alta alumina contendo alumina hidratável como ligante. Baseado na caracterização das propriedades termomecânicas destes refratários, assim como nas análises de DRX e da avaliação do módulo elástico in situ, foi selecionado o carbeto de boro (B4C) como o AS promissor, pois este promoveu o início da sinterização dos concretos em temperaturas inferiores e induziu a formação de boratos de alumínio a partir da reação do líquido com a alumina da matriz dos concretos refratários. Posteriormente, avaliou-se o efeito da adição do B4C em concretos com ultra-baixo teor de óxido de cálcio e ligados com: alumina coloidal (AC), alumina hidratável (AB) e/ou SioxX®-Zero (SZ). Materiais ligados com SZ (4%-p) são promissores em temperaturas próximas a 1100°C devido à formação de mulita. Por outro lado, concretos contendo AC (4%-p de sólidos) e 0,5%-p B4C são indicados para condições de serviço entre 600-815°C, pois sem a fonte de boro densificaram apenas acima de 1100°C. Efeito similar foi observado quando adicionado 1,0%-p B4C no concreto contendo SZ, visto que também foram formados boratos de alumínio possibilitando sua utilização em condições de serviço próximas aos 815°C. Desta forma, realizando-se a correta seleção do AS adicionado em concretos de alta alumina com ultra-baixo teor de CAC, tem o potencial de aumentar a sinterabilidade do material e melhorar suas propriedades termomecânicas, podendo assim atender os requisitos da indústria petroquímica.

Orientadores: Sandro Guedes de Oliveira, Jörg Kobarg / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-09-02T02:16:09Z (GMT). No. of bitstreams: 1 Smilgys_Barbara_D.pdf: 17430152 bytes, checksum: 82ba0350f1128e5f264b9ee314a4fef6 (MD5) Previous issue date: 2017 / Resumo: BNCT (do inglês, Boron Neutron Capture Therapy) é uma terapia para tratamento de cânceres que tem se mostrado efetiva em casos de metástases e tumores inoperáveis. Sua base física é a reação de captura de nêutrons pelo boro resultando na produção de uma partícula 'alfa' e de um íon de recuo de lítio: 10B(n,'alfa')7Li. O objetivo principal deste trabalho foi verificar a viabilidade de monitoração de taxa de reações de interesse em BNCT e estimar, a partir das taxas de reações medidas, quantidades probabilísticas que descrevam o campo de irradiação, utilizando-se filmes finos de boro e detectores plásticos de traços nucleares (PADC). Além disto, pretendia-se realizar estudos biológicos de sobrevivência celular, para então, com a descrição detalhada do campo de irradiação e medidas de efeitos radiobiológicos, avaliar possíveis correlações entre os efeitos de heterogeneidade de deposição de energia (quantidades probabilísticas) e as frações de sobrevivência celular. Assim, o trabalho foi dividido em três partes experimentais fundamentais: a calibração do conjunto de filmes finos de boro acoplados a detectores PADC, cuja importância é a quantificação de átomos de 10B presentes nos filmes finos utilizados para a medida da taxa da reação 10B(n,'alfa')7Li, a realização de experimentos in vitro com irradiações com partículas 'alfa' que visavam o desenvolvimento da metodologia de quantificação de sobrevivência celular, que seriam utilizadas posteriormente, quando realizados os experimentos in vitro com nêutrons, os quais unem os resultados obtidos das calibrações dos filmes finos de boro e os métodos aplicados nas análises de resposta biológica de irradiações de células com partículas 'alfa'. A partir das fluências de partículas 'alfa' e das taxas da reação 10B(n,'alfa')7Li, calculou-se as médias da distribuição de eventos poissonianos em uma célula de área A e com estas médias foram feitas simulações de distribuição de eventos em uma matriz de células, para quantificação da formação de clusters de células (primeiras vizinhas) atingidas. Por se tratar de um problema de muitas variáveis (sobrevivência celular, média de eventos, eventos por célula, células por cluster e total de clusters), escolheu-se fazer uma análise de componentes principais, na tentativa de se determinar quais destas variáveis introduzem as maiores variabilidades no problema. Mostrou-se que a formação de clusters de células vizinhas influencia a inativação das células, embora não tenha sido possível estabelecer modelos quantitativos. Portanto, com este trabalho, foi possível estabelecer uma metodologia segura para a quantificação da taxa de reação de interesse na BNCT, e a partir desta, calcular descritores que levam em conta a heterogeneidade da distribuição de energia durante as irradiações. A partir de dados de experimentos in vitro, tanto de irradiações com partículas 'alfa' quanto com nêutrons térmicos, foi possível encontrar correlações com estes descritores de heterogeneidade e conclui-se, então, que eles podem ser usados como descritores de efeitos biológicos / Abstract: BNCT (Boron Neutron Capture Therapy) is a therapy for the treatment of cancers that has been proven to be effective in cases of metastases and inoperable tumors. Its physical basis is the boron neutron capture reaction resulting in the production of an 'alpha' particle and a lithium recoil ion: 10B(n,'alpha')7Li. The main objective of this work was to verify the feasibility of monitoring the main reactions rates in BNCT using boron thin films and nuclear tracks plastic detectors (PADC) and to estimate, from the reactions rates measured, probabilistic quantities that describe the irradiation field. In addition, it was intended to carry out biological studies of cell survival, and with the detailed description of the field of irradiation and measurements of radiobiological effects, to evaluate possible correlations between the effects of heterogeneity of energy deposition (probabilistic quantities) and fractions of cell survival. Thus, the work was divided into three fundamental experimental parts: the calibration of the setup of boron thin films coupled to PADC detectors (whose importance is the quantification of the 10B atoms present in the thin films used for the measurement of 10B(n,'alpha')7Li reaction rate), the in vitro experiments carried out with irradiations with particles 'alpha' aiming to develop the methodology for cell survival quantification, which would later be used when performing the in vitro experiments with neutrons, which combine the results obtained from the calibrations of the boron thin films and the methods applied for cell survival quantification. From the 'alpha' particles fluences and the 10B(n,'alpha')7Li reaction rates, it was possible to calculate the mean of the Poisson distribution for events happening inside a cell of area A. Simulations were performed for quantifying the number of clusters formed by neighbor cells that were hit by an incident particle. Since this is a problem of many variables (cell survival, poissonian mean, events per cell, cells per cluster and total number of clusters), it was performed a principal components analysis in an attempt to determine which of these variables introduce the greatest variabilities to the problem. It was shown that the cells clusters formation influences cell inactivation, though it was not possible to establish quantitativy models. Therefore, with this work, it was possible to establish a safe methodology for the quantification of the reaction rate of interest in BNCT, and from this, to calculate descriptors that take into account the heterogeneity of energy distribution during irradiation. From data from both in vitro experiments of cells irradiation with 'alpha' particles and with thermal neutrons, it was possible to find correlations with these descriptors of heterogeneity and it is concluded, then, that they can be used as descriptors for biological effects / Doutorado / Física / Doutora em Ciências

Orientador: Sandro Guedes de Oliveira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-20T00:29:22Z (GMT). No. of bitstreams: 1 Smilgys_Barbara_M.pdf: 13526183 bytes, checksum: 6bc7b12944024ced8153260711197b5f (MD5) Previous issue date: 2012 / Resumo: O princípio de funcionamento da Terapia por Captura de Nêutrons pelo Boro (BNCT, Boron Neutron Capture Therapy) é a entrega seletiva de uma maior quantidade de átomos de boro às células cancerígenas do que àquelas saudáveis, seguida da irradiação com nêutrons que irá induzir a emissão de partículas a e íons de recuo de 7Li através da reação nuclear 10B(n,a)7Li. O objetivo deste trabalho é desenvolver uma metodologia para quantificar a taxa da reação de interesse através do uso da montagem de filmes finos de boro acoplados a detectores CR-39, que detectam as partículas a e os íons de recuo de 7Li. Este detector é composto por átomos de hidrogênio, carbono e oxigênio, os quais interagem com nêutrons rápidos e as partículas resultantes destas reações (de espalhamentos e de captura de nêutrons) também são detectadas pelo próprio detector. Deste modo, é possível quantificar, ao mesmo tempo, a reação 10B(n,a)7Li e a contribuição de nêutrons rápidos do fluxo. Essas medidas são fundamentais para os estudos de biodistribuição de átomos de 10B e de microdosimetria dos tecidos irradiados com nêutrons, levando ao planejamento da terapia em si. Os filmes finos de boro foram confeccionados por dois métodos, Deposição de Solução Química (CSD, Chemical Solution Deposition) e deposição por sputtering, e irradiados com nêutrons no reator nuclear IEA-R1 localizado no IPEN/CNEN. Os resultados obtidos para a caracterização e a calibração dos filmes finos de boro, além da calibração dos detectores CR-39 são aqui analisados. Foi possível confeccionar, por ambos os métodos, filmes finos de boro homogêneos e calibrar o sistema de filme fino de boro acoplado a detector CR-39 para a medida da taxa da reação 10B(n,a)7Li e para a determinação da componente rápida do fluxo de nêutrons através do uso de filmes finos de urânio e tório, respectivamente / Abstract: The working principle of the Boron Neutron Capture Therapy (BNCT) is the selective delivery of a greater amount of 10B atoms to the tumor cells than to the healthy ones, followed by neutron irradiation that will induce the emission of a particles and 7Li recoil ions through the nuclear reaction 10B(n,a)7Li. The goal of this work is to develop a methodology to quantify the reaction rate of interest using an assembly of boron thin film coupled to CR-39 detector, which detects the a particles and the 7Li recoil ions. This detector is composed of atoms of hydrogen, carbon and oxygen, which interacts with fast neutrons and the resulting particles from these scattering and capture processes are also detected by the CR-39 detector. In this way, it is possible to quantify, at the same time, the reaction 10B(n,a)7Li and the fast neutrons contribution to the flux. Those measurements are fundamental to the 10B biodistribution studies and tissue microdosimetry, leading to the therapy planning itself. The boron thin films were manufactured using two methods, Chemical Solution Depostion and sputtering deposition, and irradiated with neutrons at the nuclear reactor IEA-R1 located at IPEN/CNEN. The results obtained for the boron thin films characterization and calibration, as well as the CR-39 detectors calibration are analyzed here. It was possible to manufacture with both methods homogeneous boron thin films and to calibrate the assembly of boron thin film coupled to CR-39 detector for measuring the 10B(n,a)7Li reaction rate and determining the fast component of the neutron flux through the use of uranium and thorium thin films, respectively / Mestrado / Física / Mestra em Física

The biological activity of the pharmaceutical drugs often depends on how it fits with a receptor making stereochemistry a key component. Selective reactions can limit or avoid the mixture of enantiomers obtained. One such reaction is the selective reduction of a carbon-carbon double bond in the presence of a carbonyl. Although efficient, current asymmetric synthesis methods have limitations such as harsh reaction conditions, the high costs of chiral catalysts and the toxicity of the metal-based catalysts. Catalysts derived from small organic molecules have become an attractive alternative which have been explored more rigorously in recent years. Using a BINOL-derived boro-phosphate catalyst, we have developed a methodology that selectively reduces the carbon-carbon double bond of linear α, β-unsaturated ketones, exclusively giving the corresponding saturated ketone. To the best of our knowledge, this reaction is the first of its kind to accomplish this transformation and results give high yields of >93% and enantioselectivities >90% at room temperature. Furthermore, the products of this novel reaction can be subjected to a choice electrophile, in example benzaldehyde, to afford diastereoselective tertiary alcohol products with enantioselectivities of >88% and diastereoselectivities of up to 99:1.

Physical properties of materials and their constituents are interrelated. Though the basic structural unit involved also plays a role in deciding the properties, this can be manipulated to a certain extent, by carefully selecting the basic ingredients or by varying the composition. In order to tailor the properties of the materials according to the need, the relationship between the properties and the structure has to be established. Glasses, due to their inherent disorder, don’t have the privilege of using symmetry as enjoyed by their crystalline counterparts. Given their components and composition there is no immediate and easy way of predicting all the observed properties of glasses. This is not considering computer simulations and DFT calculations. Hence we go back to play with nature, i.e., do experiments. Technological applications like LASERs, optic fibers, photosensitive semiconducting thin films, solid state batteries for energy storage etc. have greatly increased the interest in the fundamental properties of disordered materials. Large coefficient of linear expansion of germanate glasses is made use in glass-to-metal seals for ultra high vacuum. More over, many germanate based glasses with specially tailored dispersion properties have been developed. GeO2 based glasses are in fibre optics in the IR region of 1.5 to 1.8 microns. Borate glasses are resistant to thermal and chemical attack. They lower the melting temperature of glasses thus facilitating large scale production.Both borates and germanates have been worked upon extensively. Alkali boro germanate systems are interesting inherently. Borates and Germanates both are glass formers by themselves. The continuous random network formed by this base glass is modified by the presence of alkali ions. It is interesting to see to what extent the alkali ions can maintain the local charge neutrality in their neighborhood by creating non bridging oxygen atoms and how the presence of two formers is stabilizing the glass matrix. Present Work This thesis work is an attempt to understand the structure of alkali borogermanate glasses 25R2O-25GeO2-(50-x)B2O3-xNd2O3:(R=Li, Na, K and Rb; x=0,0.5). A variety of experimental techniques are available to give a good insight of the structure of glass systems. In this thesis, we have carried out  Optical studies at room temperature to probe the environment of RE ion  AC conductivity at high temperature to probe the alkali ion dynamics  11B MASS NMR of doped systems at room temperature to probe the Boron sites  Raman and Mid-IR experiments at room temperature to probe the various structural groups to get a comprehensive understanding of the structure of these glasses. To facilitate the analysis of the data and discussion of the results from these experiments, the thesis is divided in to four chapters excluding the introduction as categorized above and is presented accordingly. The second chapter begins with the preparation of the glass samples and their characterization. We have used Differential Scanning Calorimetry (DSC), powder XRD and elemental analysis using ICP-OES for characterizing the sample. We have also measured the density and refractive index of the glasses under study. After this section, we describe the results from Optical Absorption and Photoluminescence studies. A brief description of Judd-Ofelt (JO) theory used for the analysis of the results is given. We have calculated the optical parameters and JO parameters and the energy levels of Nd ions in the glass matrix based on absorption studies using program written in Matlab. The procedure to calculate these parameters and their relevance in estimating the important quantities like radiative transfers, branching ratios are discussed. The effect of variation of the alkali ions on these properties is also discussed. In the third chapter, we have investigated AC conductivity in these glasses. These experiments are carried out both as a function of frequency (40 Hz - 15 MHz) and temperature (220 C – 500 C) using a home made portable furnace with a temperature controller. The cable compensation using open and short standards were done at the high temperature end. The data has been analyzed in Electric modulus (M*) formalism using Kohlrausch William Watts (KWW) function. The other basic models used in the literature like Debye, Cole-Cole, Cole Davidson and Havriliak Negami are briefly discussed. The frequency dependence of conductivity in these systems has been ascribed to the hopping motion of the alkali ions. Non-symmetric nature of the imaginary part of M* shows an evidence of non-exponential relaxation. Activation energies were estimated from the temperature variation of the KWW and DC. The fit parameters KWW and KWW shows interesting behavior. KWW in LGBNd and NGBNd show an initial increase with increasing temperature reaching a value of 1, while a contrasting behavior is observed in KGBNd and RGBNd. Barton-Nakajima-Namikawa (BNN) plot of the present study gives a value of 0.67 and 0.7 for the slope parameter p for doped and un-doped samples respectively. BNN plot is used to correlate the ac and dc conductivities in the sample. The deviation of the slope parameter from unity may be an indication of different charge carriers for ac and dc transport. Fourth Chapter describes the room temperature 11B MASS NMR studies in Nd doped glass system. The relevant theory of Zeeman, Dipolar, Quadrupolar and Chemical shift interactions are discussed briefly before the results. The principle used in obtaining high resolution NMR in solids by means Sample spinning is also described. NMR line shape for the central transition (1/2  -1/2) of I=3/2 nuclei (11B) was simulated in Mathematica and fitting was tried in Matlab. Using this background we have analyzed the line shape. In the next part, the results of 11B MASS NMR experiments of doped glasses carried out using Bruker DSX300 at 96.3MHz are presented. The fraction of contribution from four and three co-ordinated 11B to NMR line-shape were identified and calculated. The results show unambiguously the presence of two 3 coordinated 11B sites which were differentiated on the basis of the quadrupolar parameters. In the last chapter we discuss the results of Raman and Mid-IR investigations carried out in these glasses at room temperature. These two important techniques are well established in identifying the structural groups in glass systems. Raman bands observed in the range 200 cm-1 to 1600 cm-1 in these glasses are deconvoluted using gaussian peaks and they have been assigned to various modes of possible structural groups. Two broad MIR absorption bands were observed between 600cm-1 - 1600cm-1 in both doped and undoped glasses. Each band was resolved into gaussian peaks. The band shifts and the changes in the intensities are ascribed to the effects of variation of alkali, as the presence of GeO2 (up to 25mol%) is known not to affect the borate bands as it is a former by itself.

Orientador: Rogério Lopes Vieites / Banca: Hélio Grassi Filho / Banca: Elisangela Marques Jeronimo Torres / Resumo: O fornecimento adequado de nutrientes é fundamental para o desenvolvimento e qualidade pós-colheita dos produtos hortícolas. O objetivo desta pesquisa foi avaliar o efeito da adubação nitrogenada e bórica na produção e pós-colheita da beterraba cultivar Tall Top Early Wonder, armazenada em câmara fria a temperatura de 5 ± 1 °C e UR de 85 ± 5 %. O experimento foi conduzido na Fazenda Experimental de São Manuel, localizada no município de São Manuel - SP. O delineamento experimental utilizado foi em blocos inteiramente casualizado, com quatro tratamentos constituídos das combinações entre a adubação com nitrogênio e boro: sem nitrogênio e sem boro (SNSB), sem nitrogênio e com boro (SNCB), com nitrogênio e sem boro (CNSB) e com nitrogênio e com boro (CNCB), em quatro repetições. Os tratamentos com boro (4 Kg ha-1) foram aplicados em dose única na adubação de plantio e os tratamentos com nitrogênio (90 Kg ha-1) em cobertura, parcelada em um terço da dose total aos 15, 30 e 45 dias após o transplante. A fonte de nitrogênio utilizada foi a uréia e de boro o bórax. Avaliou-se na colheita a altura das plantas, massa fresca e seca da raiz e da parte aérea, diâmetro e comprimento da raiz e produtividade. Após a colheita foram avaliadas as variáveis perda de massa fresca, pH, sólidos solúveis, acidez titulável, açúcares redutores, cor, respiração, pigmentos, compostos fenólicos, atividade antioxidante, flavonóides, composição centesimal e aparência. Os resultados demonstram que na colhe... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Adequate nutrient supply is essential to the development and post-harvest quality of vegetables. The objective of this research was to evaluate the effect of nitrogen and boric fertilization on the production and post harvest of the Tall Top Early Wonder beet stored in a cold room at 5 ± 1 ° C and RH of 85 ± 5%. The experiment was conducted at the São Manuel Experimental Farm. The experimental design was a completely randomized block design, with four treatments consisting of nitrogen and boron nitrogen and no boron (SNSB), nitrogen and boron (SNCB), nitrogen and boron (CNSB) and with nitrogen and boron (CNCB) in four replicates. Boron treatments (4 kg ha-1) were applied in a single dose in planting fertilization and treatments with nitrogen (90 kg ha-1) in cover, divided in one third of the total dose at 15, 30 and 45 days after the transplant. The source of nitrogen was urea and boron was used as borax. Plant height, fresh and dry root and shoot mass, root diameter and length and yield and post-harvest loss of fresh weight, pH, soluble solids, titratable acidity, reducing sugars, quantification of the instrumental color, respiration, pigments, phenolic compounds, antioxidant activity, flavonoids, centesimal composition and visual analysis. The results showed that nitrogen yielded an increase in yield, larger roots and more homogeneous to the market, while boron promoted an increase in dry root mass. However, there was no interaction between the nitrogen and boron factors in... (Complete abstract click electronic access below) / Mestre