Late Transition Metals Supported by Aryl Ethers and Phenoxides Bearing Pendant Phosphines: Mechanistic Insights Relevant to Ether C-O Bond Cleavage

Terphenyl diphosphines bearing pendant ethers were prepared to provide mechanistic insight into the mechanism of activation of aryl C–O bonds with Group 9 and Group 10 transition metals. Chapters 2 and 3 of this dissertation describe the reactivity of compounds supported by the model phosphine and extension of this chemistry to heterogenous C–O bond activation.

Chapter 2 describes the synthesis and reactivity of aryl-methyl and aryl-aryl model systems. The metallation of these compounds with Ni, Pd, Pt, Co, Rh, and Ir is described. Intramolecular bond activation pathways are described. In the case of the aryl-methyl ether, aryl C–O bond activation was observed only for Ni, Rh, and Ir.

Chapter 3 outlines the reactivity of heterogenous Rh and Ir catalysts for aryl ether C–O bond cleavage. Using Rh/C and an organometallic Ir precursor, aryl ethers were treated with H2 and heat to afford products of hydrogenolysis and hydrogenation. Conditions were modified to optimize the yield of hydrogenolysis product. Hydrogenation could not be fully suppressed in these systems.

Appendix A describes initial investigations of bisphenoxyiminoquinoline dichromium compounds for selective C2H4 oligomerization to afford α-olefins. The synthesis of monometallic and bimetallic Cr complexes is described. These compounds are compared to literature examples and found to be less active and non-selective for production of α-olefins.

Appendix B describes the coordination chemistry of terphenyl diphosphines, terphenyl bisphosphinophenols, and biphenyl phosphinophenols proligands with molybdenum, cobalt, and nickel. Since their synthesis, terphenyl diphosphine molybdenum compounds have been reported to be good catalysts for the dehydrogenation of ammonia borane. Biphenyl phosphinophenols are demonstrated provide both phosphine and arene donors to transition metals while maintaining a sterically accessible coordination sphere. Such ligands may be promising in the context of the activation of other small molecules.

Appendix C contains relevant NMR spectra for the compounds presented in the preceding sections.

SNPs in microRNAs and susceptibility to Late-Onset Alzheimer´s disease

Case-control association study of SNPs in microRNAs and susceptibility to Late-Onset Alzheimer´s disease.

Modelagem sedimentar de sistemas deltaicos altamente eficientes: aplicação para o preenchimento sedimentar do terciário superior da bacia de Bengala, porção nordeste da Índia

A bacia de Bengala, localizada a Nordeste da Índia tem uma história evolutiva extraordinária, diretamente controlada bela fragmentação do Gondwana. O início da formação desta bacia é considerada como sendo relacionada ao final do evento da quebra, datado em 126 Ma quando a Índia separou do continente Antártico e da Austrália. Desde então, a placa continental Indiana viajou do pólo sul a uma velocidade muito rápida (16 cm/a) chocando-se com o hemisfério norte e fundindo-se com a Placa Eurasiana. Durante a viagem passou por cima de um hot spot, onde hoje estão localizadas as ilhas Seicheles, resultando em um dos maiores derrames de lava basáltica do mundo, conhecido como Deccan Trap. Na região onde a bacia de Bengala foi formada, não houve aporte significativo de sedimentos siliciclásticos, resultando na deposição de uma espessa plataforma carbonática do Cretáceo tardio ao Eoceno. Após este período, devido a colisão com algumas microplacas e a amalgamação com a Placa Eurasiana, um grande volume sedimentar siliciclástico foi introduzido para a bacia, associado também ao soerguimento da cadeia de montanhas dos Himalaias. Atualmente, a Bacia de Bengala possui mais de 25 km de sedimentos, coletados neste depocentro principal. Nesta dissertação foram aplicados conceitos básicos de sismoestratigrafia na interpretação de algumas linhas regionais. As linhas sísmicas utilizadas foram adquiridas recentemente por programa sísmico especial, o qual permitiu o imageamento sísmico a mais de 35km dentro da litosfera (crosta continental e transicional). O dado permitiu interpretar eventos tectônicos, como a presença dos Seawards Dipping Reflectors (SDR) na crosta transicional, coberto por sedimentos da Bacia de Bengala. Além da interpretação sísmica amarrada a alguns poços de controle, o programa de modelagem sedimentar Beicip Franlab Dionisos, foi utilizado para modelar a história de preenchimento da bacia para um período de 5,2 Ma. O nível relativo do nível do mar e a taxa de aporte sedimentar foram os pontos chaves considerados no modelo. Através da utilização dos dados sísmicos, foi possível reconhecer dez quebras de plataformas principais, as quais foram utilizadas no modelo, amarrados aos seus respectivos tempos geológico, provenientes dos dados dos poços do Plioceno ao Holoceno. O resultado do modelo mostrou que a primeira metade modelada pode ser considerada como um sistema deposicional retrogradacional, com algum picos transgressivos. Este sistema muda drasticamente para um sistema progradacional, o qual atuou até o Holoceno. A seção modelada também mostra que no período considerado o total de volume depositado foi em torno de 2,1 x 106 km3, equivalente a 9,41 x 1014 km3/Ma.

Osteometric analysis of the scapula and humerus of Rangifer tarandus and Cervus elaphus : A contribution to the discrimination of Late Pleistocene cervids

Fossil remains of reindeer (Rangifer tarandus) occurring outside their present range are an important indicator of formerly cold climatic conditions, but are easily confused with those of the red deer (Cervus elaphus). The locality of Kiputz IX has yielded one of the best-preserved Late Pleistocene reindeer populations of the southern Pyrenees, occurring in association with Bison priscus and the much more abundant Cervus elaphus. Fossil remains from this site are mostly complete and not affected by human intervention, thus creating the perfect conditions for reliable osteometric analyses. Here, we quantify diagnostic morphological features of the scapula and the humerus of Cervus elaphus and Rangifer tarandus to establish the potential of these bones to aid in interspecific discrimination. In the case of the scapula, the best species discriminator is the ratio of the minimum anteroposterior diameter of the scapular neck and the development of the articular process, while the breadth of the trochlea is the best discriminator in the case of the humerus.

Island life in the Cretaceous - faunal composition, biogeography, evolution, and extinction of land-living vertebrates on the Late Cretaceous European archipelago

The Late Cretaceous was a time of tremendous global change, as the final stages of the Age of Dinosaurs were shaped by climate and sea level fluctuations and witness to marked paleogeographic and faunal changes, before the end-Cretaceous bolide impact. The terrestrial fossil record of Late Cretaceous Europe is becoming increasingly better understood, based largely on intensive fieldwork over the past two decades, promising new insights into latest Cretaceous faunal evolution. We review the terrestrial Late Cretaceous record from Europe and discuss its importance for understanding the paleogeography, ecology, evolution, and extinction of land-dwelling vertebrates. We review the major Late Cretaceous faunas from Austria, Hungary, France, Spain, Portugal, and Romania, as well as more fragmentary records from elsewhere in Europe. We discuss the paleogeographic background and history of assembly of these faunas, and argue that they are comprised of an endemic 'core' supplemented with various immigration waves. These faunas lived on an island archipelago, and we describe how this insular setting led to ecological peculiarities such as low diversity, a preponderance of primitive taxa, and marked changes in morphology (particularly body size dwarfing). We conclude by discussing the importance of the European record in understanding the end-Cretaceous extinction and show that there is no clear evidence that dinosaurs or other groups were undergoing long-term declines in Europe prior to the bolide impact.

The effect of organotin and copper sulfate on the late development and presettlement behavior of the hard clam Mercenaria mercenaria

The effect of organotin compounds and copper, commonly used as antifouling agent, were studied on Mercenaria mercernaria larvae. They were reared under usual hatchery conditions until they reached 190 um in diameter. The larvae were subjected to four compounds, tributylin chloride (TBT), monobutyltin chloride (MBT), trimethyltin chloride (TMT), cupric sulfate (CuSo4) plus control. Mortality was measured at 24, 48 h, and 96h. Behavioral and/or metamorphic changes were recorded in triplicate at 24-48 and 96 h. The appearance in swimming larvae of a functional foot was considered a sign of competence to set and was recorded as a "pediveliger". Swimming larvae were considered as larvae that have not yet reached their total development and they were recorded as "swimming". Larvae that did not show foot or swimming activity and were static but alive on the bottom were recorded as "bottom". TBT was found to completely inhibit swimming activity at sublethal concentrations throughout the period of observation. Copper and MBT inhibited swimming from 48 h, TMT did not inhibit swimming activity at any of the times recorded. The four compounds ranked in order of decreasing toxicity were TBT>TMT>CU>MBT.

The western blue groper (Achoerodus gouldii), a protogynous hermaphroditic labrid with exceptional longevity, late maturity, slow growth, and both late maturation and sex change

The western blue groper (Achoerodus gouldii) is shown to be a temperate protogynous hermaphrodite, which spawns between early winter and mid-spring. Because A. gouldii changes body color at about the time of sex change, its color can be used as a proxy for sex for estimating the size and age at sex change and for estimating growth when it is not possible to use gonads for determining the sex of this fish. The following characteristics make A. gouldii highly susceptible to overfishing: 1) exceptional longevity, with a maximum age (70 years) that is by far the greatest yet estimated for a labrid; 2) slow growth for the first 15 years and little subsequent growth by females; and 3) late maturation at a large total length (TL50 = 653 mm) and old age (~17 years) and 4) late sex change at an even greater total length (TL50 = 821 mm) and age (~35 years). The TL50 at maturity and particularly at sex change exceeded the minimum legal total length (500 mm) of A. gouldii and the lengths of many recreationally and commercially caught fish. Many of these characteristics are found in certain deep-water fishes that are likewise considered susceptible to overfishing. Indeed, although fishing effort for A. gouldii in Western Australia is not particularly high, per-recruit analyses indicate that this species is already close to or fully exploited.