Peftjauawybast, king of Nen-nesut : genealogy, art history, and the chronology of late libyan Egypt

This paper argues in detail for the identification of Peftjauawybast, King of Nen-nesut (fl. 728/720 BC ), with Peftjauawybast, High Priest of Ptah in Memphis (fl. c. 790–780 BC2), known from the Apis stela of year 28 of Shoshenq III. This identification ties in with a significant lowering of the accepted dates for the kings from Shoshenq III, Osorkon III and Takeloth III to Shoshenq V, and the material culture associated with them. Such a shift seems to be supported by stylistic and genealogical evidence. As a consequence, it is further suggested that the Master of Shipping at Nen-nesut, Pediese i, was perhaps related by descent and marriage to the family of the High Priests of Memphis and King Peftjauawybast.

Dating and characterizing late holocene earthquakes using paleomagnetics

In this thesis I apply paleomagnetic techniques to paleoseismological problems. I investigate the use of secular-variation magnetostratigraphy to date prehistoric earthquakes; I identify liquefaction remanent magnetization (LRM), and I quantify coseismic deformation within a fault zone by measuring the rotation of paleomagnetic vectors.

In Chapter 2 I construct a secular-variation reference curve for southern California. For this curve I measure three new well-constrained paleomagnetic directions: two from the Pallett Creek paleoseismological site at A.D. 1397-1480 and A.D. 1465-1495, and one from Panum Crater at A.D. 1325-1365. To these three directions I add the best nine data points from the Sternberg secular-variation curve, five data points from Champion, and one point from the A.D. 1480 eruption of Mt. St. Helens. I derive the error due to the non-dipole field that is added to these data by the geographical correction to southern California. Combining these yields a secular variation curve for southern California covering the period A.D. 670 to 1910, with the best coverage in the range A.D. 1064 to 1505.

In Chapter 3 I apply this curve to a problem in southern California. Two paleoseismological sites in the Salton trough of southern California have sediments deposited by prehistoric Lake Cahuilla. At the Salt Creek site I sampled sediments from three different lakes, and at the Indio site I sampled sediments from four different lakes. Based upon the coinciding paleomagnetic directions I correlate the oldest lake sampled at Salt Creek with the oldest lake sampled at Indio. Furthermore, the penultimate lake at Indio does not appear to be present at Salt Creek. Using the secular variation curve I can assign the lakes at Salt Creek to broad age ranges of A.D. 800 to 1100, A.D. 1100 to 1300, and A.D. 1300 to 1500. This example demonstrates the large uncertainties in the secular variation curve and the need to construct curves from a limited geographical area.

Chapter 4 demonstrates that seismically induced liquefaction can cause resetting of detrital remanent magnetization and acquisition of a liquefaction remanent magnetization (LRM). I sampled three different liquefaction features, a sandbody formed in the Elsinore fault zone, diapirs from sediments of Mono Lake, and a sandblow in these same sediments. In every case the liquefaction features showed stable magnetization despite substantial physical disruption. In addition, in the case of the sandblow and the sandbody, the intensity of the natural remanent magnetization increased by up to an order of magnitude.

In Chapter 5 I apply paleomagnetics to measuring the tectonic rotations in a 52 meter long transect across the San Andreas fault zone at the Pallett Creek paleoseismological site. This site has presented a significant problem because the brittle long-term average slip-rate across the fault is significantly less than the slip-rate from other nearby sites. I find sections adjacent to the fault with tectonic rotations of up to 30°. If interpreted as block rotations, the non-brittle offset was 14.0+2.8, -2.1 meters in the last three earthquakes and 8.5+1.0, -0.9 meters in the last two. Combined with the brittle offset in these events, the last three events all had about 6 meters of total fault offset, even though the intervals between them were markedly different.

In Appendix 1 I present a detailed description of my standard sampling and demagnetization procedure.

In Appendix 2 I present a detailed discussion of the study at Panum Crater that yielded the well-constrained paleomagnetic direction for use in developing secular variation curve in Chapter 2. In addition, from sampling two distinctly different clast types in a block-and-ash flow deposit from Panum Crater, I find that this flow had a complex emplacement and cooling history. Angular, glassy "lithic" blocks were emplaced at temperatures above 600° C. Some of these had cooled nearly completely, whereas others had cooled only to 450° C, when settling in the flow rotated the blocks slightly. The partially cooled blocks then finished cooling without further settling. Highly vesicular, breadcrusted pumiceous clasts had not yet cooled to 600° C at the time of these rotations, because they show a stable, well clustered, unidirectional magnetic vector.

Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.

Soberania e acumulação de capital: uma análise crítica de Hugo Grotius, Pasquale Mancini e Hans Kelsen

A soberania já foi conceituada de diversos modos ao longo da história. Apesar disso, não deixou de ser a categoria mais elementar do direito internacional; expressando o fundamento de atuação dos Estados, foi através da soberania que o direito internacional se desenvolveu do Século XVII até os dias de hoje. Isso evidencia uma distinção entre o conteúdo da soberania, quer dizer, o seu modo de manifestação, o seu conceito, que se altera em cada período histórico, de um lado, e, do outro, a forma jurídica internacional expressa pela soberania, que se mantém intacta e que existe independentemente do conteúdo que lhe é dado, quer dizer, o lugar que ela ocupa no direito internacional. Através da análise do conceito de soberania fornecido por três autores clássicos de diferentes períodos históricos Hugo Grotius, Pasquale Mancini e Hans Kelsen o presente trabalho tem por objetivo demonstrar o caráter ideológico de cada teoria e, conseqüentemente, sua inexatidão. Para fazê-lo, foi adotado o método materialista dialético, através do qual a produção de idéias por parte do homem deve ser observada nos limites das suas condições de existência e as idéias produzidas como um reflexo consciente do mundo real. Cuida-se, assim, de observar o direito de superioridade afirmado por Grotius nos limites das condições de existência humana que se alteravam com a transição do feudalismo para capitalismo, e extrai-se o seu sentido da luta entre a Igreja e os monarcas que iam centralizando sob si o poder. Da mesma forma, observa-se o direito de nacionalidade de Mancini sob as condições de existência propiciadas pelo amadurecimento das classes sociais do capitalismo na Europa Ocidental como fruto da Revolução Industrial, extraindo-se seu sentido das lutas revolucionárias por libertação nacional que ali se desenrolavam. O caráter essencialmente limitado da soberania de Kelsen, enfim, será observado no contexto da passagem do capitalismo para sua época imperialista, como um reflexo consciente dos desenvolvimentos experimentados pelo direito internacional no fim do Século XIX e início do Século XX, após a Primeira Guerra Mundial. Assim, além de demonstrar o caráter ideológico e a inexatidão dos conceitos mencionados, busca-se demonstrar que o conteúdo da soberania em cada período histórico analisado encontra sua razão de ser na correspondente fase de desenvolvimento do capitalismo e que a forma jurídica soberania, isto é, o lugar que ela ocupa no direito internacional, é determinado pela necessidade do capitalismo de um instrumento de força que assegure a acumulação de capital, o Estado soberano.

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.

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.