Foi objetivo do presente estudo avaliar a biodisponibilidade relativa do fósforo a partir de fosfatos comerciais usados na alimentação animal, utilizando-se de 680 pintos de corte, machos, da linhagem Ross, de 1 dia de idade, distribuídos aleatoriamente em 17 tratamentos no período de 21 dias. Foram adicionados dois níveis de fósforo suplementar (0,08 e 0,16%) à dieta basal com baixo nível de fósforo total (0,40%), sendo a fonte padrão de fósforo o fosfato bicálcico quimicamente puro. A biodisponibilidade do fósforo para cada fosfato comercial foi calculada pelo método do "slope ratio" através da regressão dos valores dos parâmetros ósseos (cinzas da tíbia e dedos médio) e desempenho animal (ganho de peso, consumo de ração e conversão alimentar). Os valores de ganho de peso, consumo de ração, conversão alimentar e parâmetros ósseos aumentaram em resposta aos incrementos de P na dieta, independentemente da fonte de fósforo. Valores de BRP foram calculados a partir do peso das cinzas nos dedos médio aos 21 dias, sendo que o mais alto valor foi obtido pelo fosfato monossódico quanto comparado aos demais fosfatos testados. / The relative bioavailability of phosphorus was studied in a trial with 680 male Ross chicks used in a 21 day .Phosphates were added to the basal diet to provide 0,08 and 0,16% supplemental P. The reference standard was a purified grade calcium phosphate dibasics. Slope ratio technique was used to calculate relative bioavailability of phosphorus, based on bone parameters (tibia and toe ash) and body weight gain, feed intake and feed:gain ratio. At day 21, body weight gain, feed intake, feed:gain ratio and bone parameters increased with incremental levels of P in the diet regardless of source. Relative bioavailability of phosphorus based on toe ash was higher from monosodium phosphate as compared with studies phosphates.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / O objetivo deste trabalho foi a síntese e a caracterização físico-química e microestrutural de matrizes cerâmicas porosas à base de hidroxiapatita de cálcio, bem como a avaliação de um pó de hidroxiapatita comercial, com potencialidade para atuarem como matrizes para incorporação de radionuclídeos de fontes radioativas para uso em braquiterapia. Pós de hidroxiapatita de cálcio foram sintetizados por via co-precipitativa de soluções precursoras de cálcio e fosfato em meio básico. As matrizes correspondentes foram obtidas a partir da compactação axial dos pós à baixa pressão e sinterizadas ao ar. Difração de raios X, fluorescência de raios X, espectrofotometria de infravermelho, análise BET, análise térmica TG-DTA e microscópia eletrônica de varredura foram realizadas para caracterização dos pós e matrizes. O iodo foi incorporado nas matrizes através de um inpregnação de solução aquosa de iodeto de sódio. Foi realizada a quantificação de iodo (simulador de radionuclídeo) nas matrizes através da técnica de análise por ativação neutrônica. Verificou-se que as hidroxiapatitas sintetizada e comercial têm características de hidroxiapatitas bioabsorvíveis. As matrizes de hidroxiapatita apresentaram uma baixa densificação. A porosidade total é da ordem de 55%, e a porosidade aberta de 54%. Comparações feitas entre os resultados de incorporação de iodo e as atividades das fontes de braquiterapia comerciais mostram que a matrizes bioabsorvíveis à base de hidroxiapatita têm grande potencial, porque elas podem ser carregadas com uma ampla faixa de atividade. / The aim of this work was the synthesis and physico-chemical and microstructural characterization of pores ceramic matrices of calcium hydroxyapatites, and also the evaluation of a commercial hydroxyapatite powder, and both with the potency do in view of their possible use act as matrices for radionuclide incorporation of bioresorbable radioactive sources for the use of brachytherapy. Calcium hydroxyapatite powders were synthesized by co-precipitation of precursor solutions of calcium and phosphate in basic environment. The corresponding matrices were obtained for uniaxial compaction of powders at low pressure and sinterized in air. X-rays diffraction and fluorescence, infrared spectrphotometry, surface area (BET), thermal analysis (TG-DTA), and scanning electron microscopy were carried out to characterize the powders and the matrices. Iodine was incorporated in the matrices through impregnation of sodium iodine aqueous solution. The amount of incorporated iodine (radionuclide simulator) was done by neutron activation. Both hydroxyapatites have characteristics for bioabsorption. The matrices showed a low densification with total porosity of about 55%, and open porosity of about 54%. Through comparisons done between the results of incorporated iodine and the activities of the commercial brachytherapy sources show that the bioresorbable matrices of hydroxyapatites have great potential.

Orientador: Alberto Carlos Botazzo Delbem / Coorientador: Juliano Pelim Pessan / Coorientador: Douglas Roberto Monteiro / Banca: Robson Frederico Cunha / Banca: Denise Pedrini Ostini / Banca: Marília Afonso Rabelo Buzalaf / Resumo: O presente estudo teve como objetivo verificar o efeito do hexametafosfato de sódio (HMP), associado ou não ao fluoreto (F), sobre a composição orgânica, inorgânica e no pH do biofilme mistos de S. mutans e C. albicans formados in vitro. Para todos os estudos, os biofilmes foram formados em poços de placas de microtitulação, colocando uma suspensão (1x107 células/mL C. albicans + 1x108 células/mL S. mutans) em saliva artificial suplementada com sacarose (0,4%), a qual tinha metade de seu conteúdo renovada a cada 24 horas. Os biofilmes foram tratados três vezes (72, 78 e 96 horas de formação), por um minuto, com soluções contendo HMP (0.25, 0.5 ou 1%) com ou sem 500 ppm F, além de soluções contendo 500 e 1100 ppm F. A saliva artificial foi utilizada como controle negativo. Para o estudo microbiológico, após o terceiro tratamento foram realizados os testes de quantificação de células cultiváveis (CFU), biomassa total (teste colorimétrico de cristal violeta - CV), atividade metabólica (redução de XTT) e quantificação dos componentes da matriz extracelular (proteína, carboidrato e ácidos nucleicos). Todos os ensaios foram realizados em triplicata, em três ocasiões diferentes. Os resultados foram submetidos à análise de variância a um critério, seguida pelo teste Fisher LSD (p <0.05). O HMP apresentou efeito redutor principalmente na biomassa, metabolismo e nos componentes da matriz extracelular do biofilme. Biofilmes formados por 96 h formam expostos a três diferentes concentraçõ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of the present study was to verify the effect of sodium hexametaphosphate (HMP), associated or not to fluoride (F), on the inorganic, organic composition and pH of the mixed biofilm of S. mutans and C. albicans, formed in vitro. For all studies, the biofilms were formed in wells of microtiter plates by placing a suspension (1 x 107 cells/mL C. albicans + 1x108 cells/mL S. mutans) in artificial saliva supplemented with sucrose (0,4%), which had half of its content renewed every 24 hours. Biofilms were treated three times (72, 78 and 96 hours of formation), for one minute, with solutions containing HMP (0.25, 0.5 or 1%) with or without 500 ppm F, as well as solutions containing 500 and 1100 ppm F. Artificial saliva was used as a negative control. For the microbiological study, the following tests were performed: quantification of cultivable cells (UFC), total biomass (colorimetric crystal violet test - CV), metabolic activity (XTT reduction) and quantification of matrix components (protein, carbohydrate and nucleic acid). All assays were performed in triplicate on three different occasions. The results were submitted to one-way analysis of variance, followed by the Fisher LSD's test (p <0.05). HMP showed a reducing effect mainly on the biomass, metabolism and components of the extracellular matrix of the biofilm. Biofilms formed for 96 h were exposed to three different concentrations of sucrose (10, 20 or 30%) for 1, 3 or 5 min. The pH was measured before exposure to su... (Complete abstract click electronic access below) / Doutor

Compostos de vanádio são extensivamente estudados, devido suas propriedades redox, eletroquímicas, catalíticas, magnéticas e biológicas. Nesta dissertação tivemos como foco de nosso trabalho o composto VOPO4.2H2O que apresenta uma forma lamelar com suas lamelas unidas por interações de Van der Waals. Essas fracas interações interlamelares fazem do fosfato de vanadila e de seus componentes análogos excelentes matrizes para a síntese de compostos de intercalação. A morfologia do VOPO4.2H2O mostrou-se sensível a alterações de temperatura e tempo durante síntese. Através da alteração destes parâmetros obtivemos um sólido lamelar com um grau de organização inferior a matriz sintetizada à 130oC e 16 horas, devido a existência da fase II-VOPO4 que foi constatada por difração de raios-X. A quantidade de dois mols de água por mol de VOPO4 manteve-se constante segundo as análises termogravimétricas. As imagens de microscopia eletrônica de varredura confirmaram a estrutura lamelar dos produtos, no entanto uma forma rosácea foi constatada em VOPO4/160oC, sugerindo a presença da fase VOHPO4.0,5H2O, precursora da fase (VO)2P2O7 que atua como catalisador seletivo na reação de oxidação do n-butano à anidrido malêico. A intercalação de íons lantanídeos na matriz VOPO4.2H2O produziu sólidos lamelares com cristalinidade inferior a matriz hospedeira, devido a distorção dos octaedros ocasionado pela redução dos íons vanádio (V) à (IV) apresentando uma diminuição na distância interlamelar com concomitante inserção de íons lantanídeos visando o balanceamento de carga na matriz. A reação de intercalação da matriz VOPO4.2H2O utilizando os tensoativos CTAB e CPC apresentaram resultados satisfatórios confirmados por difração de raios-X e espectrofotometria na região infravermelho. A intercalação de poli(óxido de etileno) assistida com brometo de cetiltrimetilamônio mostrou-se mais adequada apresentando sólidos organizados devido as moléculas de CTAB atuarem como agente diretivo. / Vanadium compounds are intensively studied due to their electrochemical, catalytic, magnetic and biological properties. In this work, our goal was to investigate the VOPO4.2H2O (vanadyl phosphate), which has a lamellar structure formed by VOPO4 sheets interconnected by weak interactions. Taking advantage of this structure, it is possible to synthesize several different intercalation compounds in which the guest species can vary from simple ions to polymeric species. The morphology of VOPO4.2H2O is very sensitive to temperature and time of reaction changes. By varying both parameters, several lamellar matrices have been synthesized. X-ray diffraction, thermal analysis and scanning electronic microscopy showed that depending on the synthetic conditions the arrangements VOPO4.2H2O can change the shape. For instance, in one of the experiments, a rose-like structure was produced, suggesting the presence of VOHPO40.5H2O phase, precursor of (VO)2P2O7 phase, which acts as oxidation catalyst of the n-butane to maleic anhydride. Intercalation of lanthanide ions leads to lamellar solids with low crystallinity in relation to the matrix due to octahedric distortion caused by reduction of vanadium ions (VV to VIV). Besides, it was observed a decrease of the interlamellar distance in function of the electroneutrality balance between the lamellar sheets. Intercalation compounds were produced by reacting surfactants molecules directly with the matrix under hydrothermal conditions. Surfactant-assisted intercalation of poly(ethylene oxide) into VOPO4.2H2O was conducted under soft conditions with the surfactant/matrix compound as a suspension in an aqueous polymer solution.

Afin de subvenir aux besoins énergétiques des nouvelles technologies électroniques nomades et miniatures, le développement de microdispositifs de stockage électrochimique d’énergie suffisamment performants telles que les microbatteries (MB) Li-ion est nécessaire. Pour ce faire, l’élaboration de MB Li-ion en topologie tridimensionnelle est une voie attractive qui permet le déploiement de surface spécifique tout en conservant l’empreinte surfacique initiale (de l’ordre du mm2), exacerbant ainsi la densité d’énergie délivrée par la MB. Cette solution est rendue possible grâce au développement de technique de dépôt couches minces telle que l’ALD qui est capable de réaliser des dépôts conformes. Dans le cadre de cette thèse, un électrolyte solide (Li3PO4) a été développé et optimisé de façon conforme, par ALD, sur un substrat de silicium structuré au préalable par des techniques de micro-fabrication. Une électrode positive de type spinelle (LiMn1.5Ni0.5O4) a également été élaborée par pulvérisation cathodique RF. Les performances ont été optimisées en fonction des paramètres de dépôt sur un substrat Si/Al2O3/Pt. Une capacité volumique de 63 µAh.cm-2.µm-1 a ainsi été mesurée pour un dépôt de 420 nm à 0,01 mbar recuit sous air à 700°C. Enfin, un prototype de cellule électrochimique en vue d’un suivi in situ/operando par DRX d’une électrode en couche mince, a été proposé. / In order to address the demand on energetic needs to sustain nomad and miniaturized electronic devices, micro-devices performance for energy storage such as Li-ion microbatteries (MB) have to be improved. An attractive way to meet the required performance consists in using 3D topology increasing the specific surface while keeping the initial surface footprint (in the mm2 range) which is significantly enhancing the delivered energy density of the MB. The development of thin film technologies such as ALD enabling conformal deposition makes it possible. In the framework of this thesis, a solid electrolyte (Li3PO4) has been developed and optimized by ALD, on a 3D micro-architectured silicon substrate obtained by microfabrication techniques. A positive electrode (LiMn1.5Ni0.5O4) has also been developed and optimized as a function of the deposition parameter by RF sputtering deposition on a Si/Al2O3/Pt substrate. A volumetric capacity of 63 µAh.cm-2.µm-1 has been measured for a film of 420 nm thick obtained at 0.01 mbar and then annealed at 700°C under air atmosphere. Finally, a prototype has been proposed to realize an electrochemical cell for the purpose of in situ/operando follow-up by XRD of a thin film electrode deposited on silicon substrate.

One of the principal fertility problems of calcareous soils is the lack of available phosphates. The factors which control this availability are not completely understood. One hindrance to the solution of the problems involved results from confusion of the concepts of solubility and availability. Availability is the net effect of the chemical state of a plant nutrient element and the ability of the plant to utilize the forms of the element present under the existing chemical and physical environmental conditions. In this paper, the term solubility will be used to designate the chemical solubility of an element in water or in specified extracting reagents. The term physiological availability will be used to designate the ability of the plant to assimilate the soluble forms of the element, and the term net availability will be used to designate the net effect of chemical solubility and physiological availability. These limited definitions seem justified in this study because the sodium and calcium systems investigated are alkaline and plants growing in these systems would probably be largely limited to soluble phosphates. Solubility is known to be one of the main factors which control availability of phosphates, but there is now conclusive evidence as to the importance of physiological availability. Some investigators (26,13)1 have produced evidence which they claim supports the hypothesis that the H2PO4- ion is the only phosphate ion absorbed by plants. Since the relative concentration of this ion decreases as the pH increases above neutrality, they then conclude that physiological availability is largely a function of pH. Other investigators (41,7) have produced evidence which suggests that solubility is probably the only factor which limits the availability of phosphates in alkaline and calcareous soils. The purpose of this study is to add evidence which will help clarify the relative importance of solubility and physiological availability of phosphates in sodium and calcium soils.

Abstract not available

Acyl groups in biochemical reactions are activated as acyl adenylates; such intermediates are generated by a reaction with ATP. Acyl adenylates are mixed carboxylic-phosphoric anhydrides which are potentially useful as biomimetic reagents for acylation reactions in water. These species have been reported to be unstable and have been isolated without purification. Since the adenylate portion is necessarily complex because it originates from ATP, we reasoned that using a simple alkyl group in place of adenosine might allow the biomimetic process to proceed without the difficulties reported. Our laboratory has developed routes towards such acyl phosphate alkyl monoesters and we have used them for several applications. Such materials react rapidly and selectively with amines in order to produce amides. While reactions utilizing lanthanide ions allow for the selective monoacylation of diols through bis-dentate chelates of the lanthanide. However, the efficiency of diol acylation is limited due to significant hydrolysis of the phosphate reagent and the requirement of a stoichiometric amount of the lanthanide ion. Therefore, three distinct approaches towards improving the efficiency of lanthanide promoted acylation were investigated: addition of an inert co-solvent in an attempt to reduce hydrolysis, eliminating the stoichiometric requirement of the lanthanide by addition of MgII, and the development of immobilized lanthanides as catalysts for acylation. Finally, aminoacyl phosphates are biomimetically activated amino acids and in principle should function as peptide synthesis reagents. The stability and solubility of the activated materials in water presents an opportunity to perform aqueous peptide coupling; such a process is limited by the fact that common peptide coupling agents are either insoluble or unstable in water. Therefore, we investigated the reactions of aminoacyl phosphates with amino acid esters. We find that peptides form readily in buffered solutions, establishing a basis for a general protocol for aqueous amino acid coupling and could be adapted for applications such as solid phase peptide synthesis.

Acyl groups in biochemical reactions are activated as acyl adenylates; such intermediates are generated by a reaction with ATP. Acyl adenylates are mixed carboxylic-phosphoric anhydrides which are potentially useful as biomimetic reagents for acylation reactions in water. These species have been reported to be unstable and have been isolated without purification. Since the adenylate portion is necessarily complex because it originates from ATP, we reasoned that using a simple alkyl group in place of adenosine might allow the biomimetic process to proceed without the difficulties reported. Our laboratory has developed routes towards such acyl phosphate alkyl monoesters and we have used them for several applications. Such materials react rapidly and selectively with amines in order to produce amides. While reactions utilizing lanthanide ions allow for the selective monoacylation of diols through bis-dentate chelates of the lanthanide. However, the efficiency of diol acylation is limited due to significant hydrolysis of the phosphate reagent and the requirement of a stoichiometric amount of the lanthanide ion. Therefore, three distinct approaches towards improving the efficiency of lanthanide promoted acylation were investigated: addition of an inert co-solvent in an attempt to reduce hydrolysis, eliminating the stoichiometric requirement of the lanthanide by addition of MgII, and the development of immobilized lanthanides as catalysts for acylation. Finally, aminoacyl phosphates are biomimetically activated amino acids and in principle should function as peptide synthesis reagents. The stability and solubility of the activated materials in water presents an opportunity to perform aqueous peptide coupling; such a process is limited by the fact that common peptide coupling agents are either insoluble or unstable in water. Therefore, we investigated the reactions of aminoacyl phosphates with amino acid esters. We find that peptides form readily in buffered solutions, establishing a basis for a general protocol for aqueous amino acid coupling and could be adapted for applications such as solid phase peptide synthesis.

Reproduction de : Thèse de doctorat : Science et génie des matériaux : Toulouse, INPT : 2006. / Titre provenant de l'écran-titre. Bibliogr. 128 réf.