This study used LA-ICP-MS on a documented sample of modern teeth to sample from a continuous line across the cementum increments thus creating a temporal line graph of the elemental composition against distance. The knowledge of cementum was extended through (1) a more complete elemental composition analysis and (2) the relation of element distribution to the ultrastructure structure throughout the life of a tooth. This study was exploratory and demonstrated that lead, zinc, mercury, and barium follow the same general line of changes, and most likely represent changes in health and exposure to these metals in the general environment. Copper, manganese and vanadium varied very little. Technological limitations prevented the examination of element levels in any one annulation.

This study used LA-ICP-MS on a documented sample of modern teeth to sample from a continuous line across the cementum increments thus creating a temporal line graph of the elemental composition against distance. The knowledge of cementum was extended through (1) a more complete elemental composition analysis and (2) the relation of element distribution to the ultrastructure structure throughout the life of a tooth. This study was exploratory and demonstrated that lead, zinc, mercury, and barium follow the same general line of changes, and most likely represent changes in health and exposure to these metals in the general environment. Copper, manganese and vanadium varied very little. Technological limitations prevented the examination of element levels in any one annulation.

Fossils recovered from limestones of the lower Cambrian (Stage 2-3) Yanjiahe Formation in Hubei Province, South China, recovered using acetic acid maceration, fracturing, and thin sectioning techniques were examined using a combination of analytical techniques, including energy dispersive spectroscopic (EDS) elemental mapping and micro-focus X-ray computed tomography (micro-CT). One important fossil recovered and analyzed with these techniques is a fossilized embryo. Fossilized animal embryos from lower Cambrian rocks provide a rare opportunity to study the ontogeny and developmental biology of early animals during the Cambrian explosion. The fossil embryos in this study exhibit a phosphatized outer envelope (interpreted as the chorion) that encloses a multicelled blastula-like embryo or a calcitized embryo marked by sets of grooves on its surface. The arrangement of these grooves resembles annulations found on the surface of the Cambrian-Ordovician fossil embryo Markuelia. Previously described late-stage Markuelia embryos exhibit annulations and an introvert ornamented by scalids, suggesting a scalidophoran affinity. In the Yanjiahe fossils illustrated herein, however, the phosphatized chorions and blastulas are not taxonomically or phylogenetically diagnostic, and the late-stage embryo is secondarily calcitized and thus poorly preserved, with only vague grooves indicative of Markuelia-type annulations. Consequently, their taxonomic assignment to the genus Markuelia is uncertain. If they indeed belong to the genus Markuelia, they are the oldest known Markuelia fossils from China, and represent both a new occurrence and possibly a new species. / Master of Science

No description available.

Nous effectué des réactions de cyclisations [3 +2] énantiosélectives entre des allénoates et des énones, catalyseées par des phosphines, donnant accès à des hétérocycles soufrés présentant des motifs moléculaires spirocycliques porteurs de nombreux centres asymétriques. De bons rendements chimiques et des bon excès énantiomériques ont été obtenus en utilisant le (S,S)-FerroPHANE comme le catalyseur chiral.D’autre part, nous avons développé de nouvelles réactions catalysées par les phosphines donnant accès à des hétérocycles azotés. En tenant de la réactivité des phosphines connue dans la Littérature, nous avons envisagé des substrats permettant la combinaison de différents processus catalytique.Des réactions de cyclisation [3+2], catalysées par les phosphines, entre des imines et des diènes conjugués, doublement activés à leurs extrémités, permet d’accéder en une seule étape à des 3-pyrrolines tri-substituées de manière diastéréosélective. Nous avons alors évalué les possibilités et limitation de cette nouvelle voie d’accès aux pyrrolines en mettant en jeu de toute une gamme de diènes et d’imines diversement fonctionnalisés.Nous avons ensuite étudié ce nouveau mode de cyclisation en utilisant des diènes où l’une des deux insaturations est inscrite dans un cycle. Dans le cas de ces substrats cycliques, des composés portant le motif hexahydroisoindol-4-one ont été obtenus de manière très efficace.Enfin, il a été montré que des diènes portant le motif coumarine réagissaient avec des imines en présence de quantités stœchiométriques de phosphine et d'eau pour donner lieu à un processus domino sans précédent: une réaction de aza-Morita-Baylis Hillman suivi d’une réaction de réduction. Ce processus s'est avéré très chimiosélectif et procède avec un excellent contrôle des configurations relatives des deux centres asymétriques contigus nouvellement formés.L’ensemble de ces études ont permis de mettre en valeur l’efficacité de la catalyse par les phosphines nucléophiles pour la formation d’hétérocycles soufrés et azotés, structurellement diversifiés et hautement fonctionnalisés, à partir de matières premières facilement accessibles. / We have applied the enantioselective [3+2] cyclisations between allenoates and enones, under phosphine catalysis, to the asymmetric synthesis of sulfides and sulfoxides displaying unprecedented spirocyclic molecular scaffolds and multiple stereocentres. Notably, good yields and e.e’s were obtained by using (S,S)-FerroPHANE as the chiral catalyst. Then, we established a highly diastereoselective oxidation procedure which converts the enantiomerically enriched spirocyclic sulfides into the corresponding sulfoxides. On the other hand, we have developed new phosphine promoted reactions for the synthesis of nitrogen heterocycles. From the known modes of action of phosphine nucleophiles, we have designed new combinations of properly functionalized substrates that have been processed in the presence of phosphorus catalysts. The [3+2] annulation reaction between imines and acyclic conjugated dienes, properly activated by electron withdrawing groups on both ends, affords a new efficient and diastereoselective approach to functionalized 3-pyrrolines, under phosphine catalysis. We have studied the scope and limitations of this strategy by considering a whole range of differently substituted dienes and imines. As an extension, we have also considered analogous cyclizations between imines and cyclic conjugated dienes in which one of the double bonds is embedded in a cyclic moiety which afforded the functionalized hexahydroisoindol-4-one derivatives. Coumarin derived dienes reacted however with stoichiometric amounts of phosphine and water to give an unprecedented domino process, i.e. a formal aza-Baylis Hillman-reduction sequence. The process proved to be highly chemoselective and allowed an excellent stereochemical control of the relative configurations of two, newly created, contiguous carbon centres.These studies have demonstrated that the phosphine catalysis affords simple and efficient methodologies for the synthesis of structurally diverse and highly functionalized heterocycles, starting from easily available starting materials