14 research outputs found
An electrospray ionization mass spectrometry study of azidoacetic acid/transition metal complexes: Complexation of azidoacetic acid with transition metals
RationaleThe complexation behavior of transition metals with organic azides by electrospray ionization (ESI) tandem mass spectrometry (MS/MS) is not completely understood. In this study, fragmentation patterns of complex ions having azidoacetic acid coordinated to Ni/Co/Fe were elucidated. The role of transition metals in the mediation of ligand rearrangements in gas phase is experimentally supported.MethodsThe complexation of some transition metals, nickel, cobalt and iron, by azidoacetic acid was studied by means of ESI and MS/MS. Fragmentation patterns were discerned via consecutive MS/MS experiments on an ion trap mass spectrometer and confirmed by highâresolution (HR) Fourier transform ion cyclotron resonance MS. Density functional theory (DFT) calculations were used to characterize the major ions observed in MS.ResultsOnly singly positively charged complex ions were detected presenting various stoichiometries. MS/MS and theoretical calculations allowed us to confirm assignments and coordination sites. Structural evidence suggested that the azidoacetic acid can behave as monodentate and/or bidentate and coordination through the oxygen and nitrogen atoms are both possible. Experimental evidence strongly points to a role of Ni/Co/Fe, in oxidative state (I), in mediating CâC bond activation in the gas phase.ConclusionsMS/MS and HRMS experiments were able to elucidate azidoacetic acid complexation with Ni/Co/Fe and several gasâphase processes involving metal reduction and rearrangements. The definition of the coordination pattern dictated by the competition between the nitrogen and the oxygen atoms is also dependent on the metal centre in a very dynamic process.<br/
New Glyptodont from the Codore Formation (Pliocene), FalcĂłn State, Venezuela, its relationship with the Asterostemma problem, and the paleobiogeography of the Glyptodontinae
One of the basal Glyptodontidae groups is represented by the Propalaehoplophorinae (late Oligocene â middle Miocene), whose genera (Propalaehoplophorus, Eucinepeltus, Metopotoxus, Cochlops, andAsterostemma) were initially recognized in Argentinian Patagonia. Among these,Asterostemma was characterized by its wide latitudinal distribution, ranging from southernmost (Patagonia) to northernmost (Colombia, Venezuela) South America. However, the generic assignation of the Miocene species from Colombia and Venezuela (A.? acostae, A. gigantea, andA. venezolensis) was contested by some authors, who explicitly accepted the possibility that these species could correspond to a new genus, different from those recognized in southern areas. A new comparative study of taxa from Argentinian Patagonia, Colombia and Venezuela (together with the recognition of a new genus and species for the Pliocene of the latter country) indicates that the species in northern South America are not Propalaehoplophorinae, but represent the first stages in the cladogenesis of the Glyptodontinae glyptodontids, the history of which was heretofore restricted to the late Miocene â early Holocene of southernmost South America. Accordingly, we propose the recognition of the new genusBoreostemma for the species from northern South America and the restriction ofAsterostemma to the Miocene of Patagonia. Thus, the available data indicate that the Glyptodontinae would in fact have arisen in the northernmost regions of this continent. Their arrival to more southerly areas coincides with the acme of the âAge of Southern Plainsâ. The Propalaehoplophorinae are geographically restricted to Patagonia
Nematode parasites of marsupials and small rodents from the Brazilian Atlantic Forest in the State of Rio de Janeiro, Brazil
Asociaciones FaunĂsticas del Cuaternario de San Francisco, Provincia de CĂłrdoba, Argentina. Implicancias BioestratigrĂĄficas y TaxonĂłmicas
PaleoecologĂa de los Bonapartherioidea (Marsupialia, Polydolopimorphia, Bonapartheriiformes)
North American Glyptodontines (Xenarthra, Mammalia) in the Upper Pleistocene of northern South America
The Glyptodontidae is one of the most conspicuous groups in the Pleistocene megafauna of the Americas. The Glyptodontinae were involved in the Great American Biotic Interchange (GABI) and their earliest records in North America are about 3.9 Ma, suggesting an earlier formation of the Panamanian landbridge. Taxonomically it is possible to recognize two Pleistocene genera of Glyptodontinae:Glyptodon (ca. 1.8 â 0.008 Ma), restricted to South America, andGlyptotherium (ca. 2.6 â 0.009 Ma), including records in both North and Central America. Here we present the first report of the genusGlyptotherium in South America, from the Late Pleistocene of several fossil localities in FalcĂłn State, northwestern Venezuela. A comparative analysis of the material, represented by cranial and postcranial parts, including the dorsal carapace and caudal rings, suggests a close affinity withGlyptotherium cylindricum (Late Pleistocene of Central Mexico). This occurrence in the latest Pleistocene of the northernmost region of South America Supports the bidirectional faunal migration during the GABI and the repeated re-immigration from North America of South American clades, as has been reported in other members of the Cingulata (e.g., Pampatheriidae)
Electroweak measurements in electronâpositron collisions at w-boson-pair energies at lep
Contains fulltext :
121524.pdf (preprint version ) (Open Access