Ce travail s'inscrit dans le cadre d'une étude systématique des propriétés physico-chimiques de polyphosphates à l'argent permettant d'avancer sur de nouvelles voies pour les dispositifs tels que l'éclairage, les lasers accordables dans le visible, la radiophotoluminescence. L'objectif de ce travail vise la compréhension des mécanismes de luminescence de l'ion Ag+ dans les composés Na_1-xAg_xLn(PO₃)₄ (Ln = La et Y) dont la structure a été parfaitement déterminée. La luminescence des monocristaux provient des ions Ag⁺, dans des sites isolés et proches de lacunes positives (Ag²⁺) résultant de la photosensibilité aux UV pour les cristaux au lanthane. La luminescence des verres Na_1-xAg_xLa(PO₃)₄ (seuls vitrifiables) a été élucidée grâce à une étude après irradiation et à celle des verres Na_2-xAg_xZnP₂O₇. Elle est due aussi aux ions Ag⁺ dans des sites isolés.

<p>Diabetes mellitus is one of the most threatening epidemics of modern times with rapidly increasing incidence. Vanadium and peroxovanadium compounds have been shown to exert insulin–like actions and, in contrast to insulin, are orally applicable. However, problems with side–effects and toxicity remain. The exact mechanism(s) by which these compounds act are not yet fully known. Thus, a better understanding of the aqueous chemistry of vanadates and peroxovanadates in the presence of various (bio)ligands is needed.</p><p>The present thesis summarises six papers dealing mainly with aqueous speciation in different vanadate – and peroxovanadate – ligand systems of biological and medical relevance. Altogether, five ligands have been studied, including important blood constituents (lactate, citrate and phosphate), a potential drug candidate (picolinic acid), and a dipeptide (alanyl serine) to model the interaction of (peroxo)vanadate in the active site of enzymes. Since all five ligands have been studied both with vanadates and peroxovanadates, the number of systems described in the present work is eleven, including the vanadate – citrate – lactate mixed ligand system. The pH–independent formation constants have been determined for 33 ternary vanadate – ligand, 41 quaternary peroxovanadate – ligand and two vanadate – mixed ligand species in addition to the p<i>K</i>_a values of all five ligands. These constants have been used to model physiological conditions, and the biomedical relevance of the different species is discussed.</p><p>The studies have been performed at 25 ºC in the physiological medium of 0.150 M Na(Cl), i.e. the ionic strength of human blood. No buffers have been used, and wide pH–ranges have usually been covered. The applied experimental techniques comprise mostly ⁵¹V NMR and potentiometry, but ³¹P, ¹³C, ¹H and ¹⁴N NMR as well as EPR and ESI–MS have also been used to gain additional information. Multimethod data have been treated by the least–squares program LAKE and modelling has been carried out by the software package WinSGW.</p><p>Whenever possible, solution structures of the species have been proposed. In addition, simple biological tests have been carried out to determine the stability of the formed peroxovanadate complexes in the presence of human catalase. A brief comparison is given of the different vanadate – ligand and peroxovanadate – ligand systems with emphasis on observed trends and general features.</p>

Diabetes mellitus is one of the most threatening epidemics of modern times with rapidly increasing incidence. Vanadium and peroxovanadium compounds have been shown to exert insulin–like actions and, in contrast to insulin, are orally applicable. However, problems with side–effects and toxicity remain. The exact mechanism(s) by which these compounds act are not yet fully known. Thus, a better understanding of the aqueous chemistry of vanadates and peroxovanadates in the presence of various (bio)ligands is needed. The present thesis summarises six papers dealing mainly with aqueous speciation in different vanadate – and peroxovanadate – ligand systems of biological and medical relevance. Altogether, five ligands have been studied, including important blood constituents (lactate, citrate and phosphate), a potential drug candidate (picolinic acid), and a dipeptide (alanyl serine) to model the interaction of (peroxo)vanadate in the active site of enzymes. Since all five ligands have been studied both with vanadates and peroxovanadates, the number of systems described in the present work is eleven, including the vanadate – citrate – lactate mixed ligand system. The pH–independent formation constants have been determined for 33 ternary vanadate – ligand, 41 quaternary peroxovanadate – ligand and two vanadate – mixed ligand species in addition to the pKa values of all five ligands. These constants have been used to model physiological conditions, and the biomedical relevance of the different species is discussed. The studies have been performed at 25 ºC in the physiological medium of 0.150 M Na(Cl), i.e. the ionic strength of human blood. No buffers have been used, and wide pH–ranges have usually been covered. The applied experimental techniques comprise mostly 51V NMR and potentiometry, but 31P, 13C, 1H and 14N NMR as well as EPR and ESI–MS have also been used to gain additional information. Multimethod data have been treated by the least–squares program LAKE and modelling has been carried out by the software package WinSGW. Whenever possible, solution structures of the species have been proposed. In addition, simple biological tests have been carried out to determine the stability of the formed peroxovanadate complexes in the presence of human catalase. A brief comparison is given of the different vanadate – ligand and peroxovanadate – ligand systems with emphasis on observed trends and general features.

Un nouveau modèle de biomembrane de type liposome a été développé à partir de lipides synthétisés comportant une unité biphényle sur leur chaînes sn2 et une chaîne aliphatique sn1 de longueur et insaturation variables. L'anisotropie de susceptibilité magnétique positive de ces molécules induit une déformation en oblate de ces liposomes dits " biphényles " dans le champ magnétique B0. Cette déformation spécifique a été caractérisée par RMN des solides 31P et 2H en faisant varier différents paramètres : l'intensité de B0, l'élasticité membranaire, la température et la taille des liposomes (Helfrich, 1973). Ces vésicules déformées ont pu être observées par microscopies optiques et électroniques et la rémanence de la déformation en dehors de B0 a pu être analysée par diffusion des rayons X aux petits angles (SAXS). Enfin, les premières applications des liposomes biphényles comme nouveau modèle de biomembrane pour analyser la structure et l'orientation (par RMN des solides 15N) de peptides ou protéines membranaires, ont été étudiées.

Au cours de la croissance et de la maturation, le muscle squelettique subit de nombreux changements. Principalement on constate une augmentation considérable de la masse musculaire concomitante à l’augmentation de la capacité de force et plusieurs résultats suggèrent que la maturation affecte la fonction musculaire à la fois au niveau de la commande motrice et du métabolisme énergétique. Pour des raisons éthiques évidentes, la fonction musculaire n’a été que peu étudiée chez l’enfant. Malgré leur caractère strictement non-invasif les techniques de résonance magnétique n’ont été que peu utilisées pour caractériser cette fonction chez l’enfant et les résultats controversés ne permettent pas de dégager un consensus. Dans ce travail la fonction musculaire de l’enfant sain a été étudiée in vivo par Imagerie et Spectroscopie de Résonance Magnétique. Par IRM, nous nous avons mis en évidence que la capacité de force volontaire maximale d’un muscle reste proportionnelle à sa taille de l’enfance à l’âge adulte. Par ailleurs nos résultats obtenus par SRM du P31 ont clairement montré que la capacité oxydative et la production d’ATP mitochondriale était augmentée avant la puberté, illustrant que les enfants sollicitaient plus leur métabolisme aérobie que les adultes pour répondre à la demande énergétique pour une intensité donnée. De plus, nos résultats ont montré que la filière énergétique de la glycolyse anaérobie était pleinement mature dès l’enfance. Enfin, face à la difficulté pour mettre en place des études longitudinales chez l’homme nous avons développé un protocole expérimental permettant le suivi longitudinal de la fonction musculaire au cours du développement chez le rat. / Growth and maturation are accompanied by important changes in skeletal muscle function (e.g. muscle mass and strength dramatically increase). Moreover, some evidences strongly suggest that maturation significantly affects skeletal muscle function both at the neural drive and energetics levels. For ethical reasons, few studies have been performed in children. Despite their non traumatic aspect the MR techniques, it has been barely used in this context. In this work, the skeletal muscle function of healthy children has been characterized in vivo using MRI and 31P-MRS. Our results refuted the hypothesis of a motor drive immaturity in children. We did not report any change in the relationship between muscle volume measured by MRI and maximum isometric strength or in specific strength from childhood to adulthood. The ability of a given muscle volume to produce force seems not to change during growth. Then, we investigated whether development affects muscle energetics using 31P-MRS comparing prepubescent boys and men. Our results showed that, for a similar total energy cost, the aerobic contribution to ATP production was significantly higher in boys and compensated for by a reduced PCr breakdown while glycolysis was similar whatever the age. In addition, the recovery rate of PCr after the standardized exercise was faster in boys illustrating a higher maximal oxidative capacity before puberty. Finally, our understanding of skeletal muscle function in children is still limited by the difficulty to perform longitudinal studies. In that respect, we have initiated an original protocol allowing the longitudinal investigation of the gastrocnemius muscle throughout development in rat.

Made available in DSpace on 2016-12-08T15:50:04Z (GMT). No. of bitstreams: 1 PGMS14DA022.pdf: 1661890 bytes, checksum: 3147ca0fadcd842b04a10dab73754a64 (MD5) Previous issue date: 2014-05-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The total content of phosphorus (P) is distributed in the soil forms with different degrees of lability, being the distribution of the forms affected by type soils and soil manegement. The work consisted of three studies, being that the first study quantified the stock of the forms of inorganic and organic P in the surface horizon and in 42 profiles soil of six orders in the Santa Catarina State. After collection, the samples were subjected to chemical fractionation of P Hedley. The soils most weathered had higher stock of P total, while the soils less weathered showed higher levels of labile organic P. In the second study was conducted fractionation analysis of P and P nuclear magnetic resonance (NMR) in soil agroecosystems with high organic matter content. The areas were evaluated in apple orchard, native grass and pine plantation. The results of chemical fractionation and NMR of P, showed that the conversion of natural ecosystems to areas cultivated altered the distribution of P forms in soil, where the fractions organic were reduced in culture without the addition of phosphate fertilizer systems. The third study involved the assessment of forms of P in soils with different clay contents that subjected the applications of liquid swine manure. Soil samples were collected in three regions of Santa Catarina State and subjected to chemical fractionation of P. The results showed that the addition of liquid swine manure for long term increased the content of all forms of P evaluated by fractionation, mainly in inorganic forms, with more accumulated in the topsoil. In soils with sandy texture there accumulation of labile P, and in soils clay there accumulation the of forms lower lability / O conteúdo total de fósforo (P) do solo é distribuido em formas com diferentes graus de labilidade. A distribuição das formas de P podem ser afetadas pelo tipo de solo e o manejo adotado durante seu uso. O trabalho foi composto de três estudos. O primeiro estudo quantificou o estoque das formas de P inorgânicas e orgânicas no horizonte superficial e nos perfis de 42 solos de seis ordens no Estado de Santa Catarina (SC). Após a coleta, as amostras foram submetidas ao fracionamento químico de P de Hedley. No segundo estudo foi realizado o fracionamento químico de P e análise de ressonância magnética nuclear de P (RMN) em amostras de solo de áreas de pomar de maçieira, campo nativo e florestamento de pinus com alto teor de matéria orgânica. O terceiro estudo consistiu na avaliação das formas de P em solos com diferentes teores de argila que foram submetidos a aplicações de dejetos líquidos de suínos. As amostras de solo foram coletadas em três regiões do Estado de SC e submetidas ao fracionamento químico de P. No estudo 1 os solos mais intemperizados apresentaram maiores estoque de P total enquanto os solos menos intemperizados apresentaram maiores teores de P lábil e P orgânico. No segundo estudo os resultados do fracionamento químico e RMN de P mostraram que a conversão de ecossistemas naturais em áreas cultivadas alterou a distribuição das formas de P no solo, onde as frações orgânicas foram reduzidas em sistemas de cultivo sem a adição de fertilizantes fosfatados. Os resultados do terceiro estudo mostraram que a adição de dejetos líquidos de suínos por longo prazo aumentou o teor em todas as formas de P avaliadas pelo fracionamento, principalmente em formas inorgânicas, sendo mais acumulado na camada superficial do solo. Nos solos com textura arenosa houve acúmulo de P principalmente nas frações lábeis e em solos de textura argilosa houve acúmulo de P principalmente em formas de menor labilidade

Introduction: There have been few well controlled altitude and hypoxic training studies to date. This thesis investigated the effects of altitude and (sham controlled) intermittent hypoxic training (IHT) on exercise capacity, and the associated physiological adaptations. Methods: Chapter 3 investigated how living and training at 2320 m or at sea level affected total haemoglobin mass (tHb) and race performance in highly trained swimmers. Chapter 4 investigated how IHT or normoxic training affected cardiopulmonary variables and the incremental exercise limit of tolerance (T-Lim), in highly trained runners. Chapter 5 investigated how single-legged IHT or normoxic training affected phosphorus-31 nuclear magnetic resonance spectroscopy assessed muscle energetics. Results: In Chapter 3, tHb increased significantly more after altitude (+0.6 ± 0.4 g•kg-1, or +4.4 ± 3.2%) than after sea level (+0.03 ± 0.1 g•kg-1, or +0.3 ± 1.0%), but the changes in swimming performances were not different between groups, and there were no correlations between tHb and performance changes. In Chapter 4, submaximal heart rate in normoxia decreased significantly more after IHT than after normoxic training (-5 ± 5 vs. -1 ± 5 b∙min-1), and submaximal "V" ̇O2 in hypoxia significantly decreased, only after IHT. T-Lim in hypoxia significantly increased post-IHT, but there were no between group differences. In Chapter 5, the phosphocreatine recovery time constant was speeded significantly more in the IHT compared to the normoxic trained leg, when tested in hypoxia (-25 ± 8% vs. -13 ± 6%), but not in normoxia (-16 ± 15% vs. -9 ± 10%). Conclusions: Altitude training likely increases tHb, but this is not necessarily associated with improved athletic performance. IHT may induce other non-haematological adaptations; potentially an enhanced skeletal muscle oxidative capacity, but evidence for exercise capacity gains is lacking. The precise underlying causes for these adaptations require further investigation, as does any translation to athletic performance.

No description available.

Dans le cadre du confinement des métaux lourds toxiques à savoir Pb et Cd, cette étude a porté sur la recherche de nouveaux verres phosphates présentant des propriétés physico-chimiques optimisées. Des verres de composition (100-x) (50P2O5-15ZnO-35PbO)-xFe2O3 et (100-z) [50P2O5-15ZnO-(35-y)PbO-yCdO]-zAl2O3 ont été élaborés. L'introduction des oxydes de fer et d'aluminium dans les matrices phosphatées entraîne une amélioration des propriétés et en particulier un renforcement de la durabilité chimique, en milieu aqueux, comparable à celle des verres silicates. Ces résultats ont pu être corrélés à la formation d'un réseau mixte fortement réticulé dans lequel les cations présentant une coordinence multiple forment des liaisons covalentes à caractère élevé avec les atomes d'oxygène. Avec une température de transition vitreuse modérée, ces verres sont des candidats potentiels pour le stockage d'éléments lourds toxiques.