Finite differences and a coupled analytic technique with applications to explosions and earthquakes

An analytic technique is developed that couples to finite difference calculations to extend the results to arbitrary distance. Finite differences and the analytic result, a boundary integral called two-dimensional Kirchhoff, are applied to simple models and three seismological problems dealing with data. The simple models include a thorough investigation of the seismologic effects of a deep continental basin. The first problem is explosions at Yucca Flat, in the Nevada test site. By modeling both near-field strong-motion records and teleseismic P-waves simultaneously, it is shown that scattered surface waves are responsible for teleseismic complexity. The second problem deals with explosions at Amchitka Island, Alaska. The near-field seismograms are investigated using a variety of complex structures and sources. The third problem involves regional seismograms of Imperial Valley, California earthquakes recorded at Pasadena, California. The data are shown to contain evidence of deterministic structure, but lack of more direct measurements of the structure and possible three-dimensional effects make two-dimensional modeling of these data difficult.

Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF₂)) are discussed. Pt(POP-BF₂) was obtained by reaction of [Pt₂(POP)₄]^4- with neat boron trifluoride diethyl etherate (BF₃·Et₂O). While Pt(POP-BF₂) and [Pt₂(POP)₄]^4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T₁) of both Pt(POP-BF₂) and [Pt₂(POP)₄]^4- exhibit long lifetimes (ca. 0.01 ms at room temperature) and substantial zero-field splitting (40 cm^-1), Pt(POP-BF₂) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S₁), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF₂) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF₂), both in solution and as a microcrystalline powder, form the theme of Chapter II.

In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO₂ to CO by [(L)Mn(CO)₃]^- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)₄]^+/0. Because the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^- is faster, maximum TOF (TOF_max) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)₃(CO₂H)]⁰ to [(bpy)Mn(CO)₃(CO₂H)]^-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOF_max. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO₂ reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a ~ 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)₃(CO₂H)]^-.

An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.

Dynamics of the East Asian Summer Monsoon in Present and Future Climates

This thesis aims at enhancing our fundamental understanding of the East Asian summer monsoon (EASM), and mechanisms implicated in its climatology in present-day and warmer climates. We focus on the most prominent feature of the EASM, i.e., the so-called Meiyu-Baiu (MB), which is characterized by a well-defined, southwest to northeast elongated quasi-stationary rainfall band, spanning from eastern China to Japan and into the northwestern Pacific Ocean in June and July.

We begin with an observational study of the energetics of the MB front in present-day climate. Analyses of the moist static energy (MSE) budget of the MB front indicate that horizontal advection of moist enthalpy, primarily of dry enthalpy, sustains the front in a region of otherwise negative net energy input into the atmospheric column. A decomposition of the horizontal dry enthalpy advection into mean, transient, and stationary eddy fluxes identifies the longitudinal thermal gradient due to zonal asymmetries and the meridional stationary eddy velocity as the most influential factors determining the pattern of horizontal moist enthalpy advection. Numerical simulations in which the Tibetan Plateau (TP) is either retained or removed show that the TP influences the stationary enthalpy flux, and hence the MB front, primarily by changing the meridional stationary eddy velocity, with reinforced southerly wind on the northwestern flank of the north Pacific subtropical high (NPSH) over the MB region and northerly wind to its north. Changes in the longitudinal thermal gradient are mainly confined to the near downstream of the TP, with the resulting changes in zonal warm air advection having a lesser impact on the rainfall in the extended MB region.

Similar mechanisms are shown to be implicated in present climate simulations in the Couple Model Intercomparison Project - Phase 5 (CMIP5) models. We find that the spatial distribution of the EASM precipitation simulated by different models is highly correlated with the meridional stationary eddy velocity. The correlation becomes more robust when energy fluxes into the atmospheric column are considered, consistent with the observational analyses. The spread in the area-averaged rainfall amount can be partially explained by the spread in the simulated globally-averaged precipitation, with the rest primarily due to the lower-level meridional wind convergence. Clear relationships between precipitation and zonal and meridional eddy velocities are observed.

Finally, the response of the EASM to greenhouse gas forcing is investigated at different time scales in CMIP5 model simulations. The reduction of radiative cooling and the increase in continental surface temperature occur much more rapidly than changes in sea surface temperatures (SSTs). Without changes in SSTs, the rainfall in the monsoon region decreases (increases) over ocean (land) in most models. On longer time scales, as SSTs increase, rainfall changes are opposite. The total response to atmospheric CO^2 forcing and subsequent SST warming is a large (modest) increase in rainfall over ocean (land) in the EASM region. Dynamic changes, in spite of significant contributions from the thermodynamic component, play an important role in setting up the spatial pattern of precipitation changes. Rainfall anomalies over East China are a direct consequence of local land-sea contrast, while changes in the larger-scale oceanic rainfall band are closely associated with the displacement of the larger-scale NPSH. Numerical simulations show that topography and SST patterns play an important role in rainfall changes in the EASM region.

Thiophene-fluorene derivatives with high three-photon absorption activities and their application to optical power limiting

The three-photon absorption (3PA) properties of two thiophene-fluorene derivatives (abbreviated as MOTFTBr and ATFTBr) have been determined by using a Q-switched Nd:YAG laser pumped wish 38ps pulses at 1064nm in DMF. The measured 3PA cross-sections are 152x10(-78)cm(6)s(2) and 139x10(-78)cm(6)s(2), respectively. The optimized structures were obtained by AM1 calculations and the results indicate that these two molecules show nonplanar structures, and attaching different donors has different effects on the molecular structure. The charge density distributions during the excitation were also systematically studied by using AM1 method. In addition, an obvious optical power limiting effect induced by 3PA has been demonstrated for both derivatives.

Theoretical investigation on the one- and two-photon absorption properties for a series of symmetrical charge transfer fluorene-phenylene and fluorene-thiophene derivatives

One- and two-photon absorption properties of a series of fluorene derivatives with symmetrical charge transfer D-IT-D and A-IT-A structural motifs have been theoretically investigated with ZINDO/S method. The optimized structures and the characterization of frontier molecular orbitals were obtained by using AMI calculations. Two-photon absorption properties of molecules have been studied using three-state model. The calculation results have shown that fluorene-thiophene derivatives exhibit larger two-photon absorption cross-section as compared with other studied molecules. To illustrate the results, the crucial effects of thiophene ring on fluorenethiophene derivatives and the net charge changes on the pi-conjugated bridges are analyzed theoretically. (c) 2006 Elsevier B.V. All rights reserved.

Thermal analyses, spectral characterization and structural interpretation of Yb3+ doped TeO2-ZnO-ZnCl2 glasses

Bulk-lasses have been prepared in the TeO2-ZnO-ZnCl2 systems. Their characteristic temperatures were determined and analyzed. Raman and FT-IR spectra were used to analyze the effect of ZnCl2 on the structure and spectral properties of tellurite glasses and OH- groups in this glass system. The spectroscopic properties including absorption spectra, emission cross-sections and fluorescence lifetimes of Yb3+ in TeO2-ZnO-ZnCl2 were measured and calculated. It is demonstrated that the progressive replacement less than 20 mol% of TeO2 by ZnCl2 improves the thermal stability, removes the OH- groups, turns TeO4 bipyramidal arrangement into TeO3 (and/or TeO3+1) trigonal pyramids structures and results in the decrease of the symmetry of the structure, which increases the emission cross-sections and lifetimes. But when the content of ZnCl2 up to 30 mol%, the glass system becomes more hygroscopic and introduces more OH- groups, which decrease the emission cross-sections and shorten the lifetimes. The results show that the glass system with (TeO2)-Te-69-(ZnO)-Zn-10-20ZnCl(2)-1Yb(2)O(3) is a desirable component for active laser media for high power generation. (c) 2005 Elsevier B.V. All rights reserved.

Investigando as políticas de assistência e proteção à infância : psicologia e ações do Estado

Esta tese consiste em uma investigação bibliográfica e documental sobre as políticas de assistência e proteção à infância no Brasil. Com relação a esta questão, pesquisei fios de nossa história desde o período colonial até o final da chamada Era Vargas. Inicio este percurso histórico num momento em que o abandono de crianças não era considerado um problema, e funcionavam engrenagens de proteção por proximidade; caminho até os anos de 1930, quando médicos e juristas se mobilizam no sentido de organizar a assistência e a proteção ao menor de idade, contribuindo para a criação de outros modelos de atendimento à infância, baseados na assistência social e na proteção de Estado. Neste ponto, faço uma breve análise da chegada de Getúlio Vargas ao governo e de sua permanência nele até 1945. Em seguida discuto as mudanças ocorridas na estrutura das relações entre capital e trabalho na sociedade capitalista européia, quando o social se configurou enquanto um novo domínio de saber que possibilitou a emergência dos chamados profissionais do social, apontando similaridades com o processo ocorrido no Brasil durante a Era Vargas. A análise se foca, então, nos movimentos de criação e implementação de ações específicas para tratar da criança dita desassistida durante o Estado Novo, implementadas a partir do funcionamento de dois órgãos: o Departamento Nacional da Criança (DNCr) criado em 1940 para coordenar todas as atividades relativas a proteção à maternidade, à infância e à adolescência e o Serviço de Assistência a Menores (S.A.M.) criado em 1941 para superintender todo o serviço de amparo a menores desvalidos e delinqüentes, buscando sempre identificar que noções de psicologia que se faziam aí presentes. À guisa de conclusão, compartilho descobertas, encontros e desencontros proporcionados pela realização deste trabalho.

DLK1 and DLK2 characterization in mouse salivary gland development

103 p.; 102 p.

Diet composition and prey selection of the introduced grouper species peacock hind (Cephalopholis argus) in Hawaii

The introduced grouper species peacock hind (Cephalopholis argus), was the dominant large-body piscivore on the Main Hawaiian Island (MHI) reefs assessed by underwater visual surveys in this study. However, published data on C. argus feeding ecology are scarce, and the role of this species in Hawaiian reef ecosystems is presently not well understood. Here we provide the first comprehensive assessment of the diet composition, prey electivity (dietary importance of prey taxa compared to their availability on reefs), and size selectivity (prey sizes in the diet compared to sizes on reefs) of this important predator in the MHI. Diet consisted 97.7% of fishes and was characterized by a wide taxonomic breadth. Surprisingly, feeding was not opportunistic, as indicated by a strongly divergent electivity for different prey fishes. In addition, whereas some families of large-body species were represented in the diet exclusively by recruit-size individuals (e.g., Aulostomidae), several families of smaller-body species were also represented by juveniles or adults (e.g., Chaetodontidae). Both the strength and mechanisms of the effects of C. argus predation are therefore likely to differ among prey families. This study provides the basis for a quantitative estimate of prey consumption by C. argus, which would further increase understanding of impacts of this species on native fishes in Hawaii.

Meres and mosses conservation plan: Rostherne Mere

This is a report on the Conservation Plan for Rostherne Mere. The project primarly involved collating existing information from a variety of sources, supplemented by a limited amount of survey work commissioned for the project, including identification of the surface water catchment, water flows, and land use within the catchment. The section 1 outlines the physical situation of the Site of Special Scientific Interest (SSSI), its geological setting and hydrological regime. A summary of the ecological characteristics, conservation interest and objectives is provided in Section 2, and the issues affecting the site are identified in Section 3. . Operations and mechanisms for addressing the issues are suggested in Section 4, compiled from field visits, information held on file by English Nature and the Environment Agency, and English Nature. The last Section 5 provides a brief summary of the site’s condition and a discussion of the issues and operations suggested. A summary table is provided of the recommended actions for each site. Supporting information on the hydrology and aquatic ecology (where relevant) is provided in appendices.

The role of substrate, flow and larval supply to recruitment of the red abalone (Haliotis rufescens)

Precipitous declines in wild populations of the red abalone Haliotis rufescens and the eventual closure of the commercial and southern recreational fishery have led to renewed interest in supplementing wild stocks with hatchery-raised individuals. Most work to date has focused on releasing small juveniles and has had limited success. Although much is known about larval settlement, juvenile survivorship and growth of abalone, there is scanty information on natural processes in the field. The failure of many regulated fisheries worldwide suggests that both the larval and juvenile stages may be important in determining the future population, and that early juvenile mortality is more important than previously believed. This paper presents a series of experiments designed to examine factors and mechanisms that could affect settlement, survivorship, and growth of larvae and early post-settlers in the field. Laboratory trials under different flow regimes showed that red abalone larvae settled preferentially on substrates encrusted with coralline algae, and that settlement was rapid when exposed to crusts compared to other surfaces. Urchin grazing of films appeared to facilitate abalone settlement but only when urchins were removed. Initial field experiments showed that released larvae settled on natural cobble rock, and that settlement was at least one order of magnitude greater when settlement habitats were tented. I then examined post-settlement survivorship at one and two days after settlement, and found that although there was a large amount of variation, on average 10% of released larvae were found as newly-settled recruits after 1 day. Survivorship and growth of recruits were followed over at least one month in both Spring and Fall. Abalone settled at higher densities, survived better and grew faster in the warmer Fall months than in the Spring. The density of month-old abalone recruits was correlated with density of naturally-occurring gastropods in the Spring, but not in the Fall. These results suggest that settlement and survivorship can be extremely variable across space and time, and that oceanographic and local biotic conditions play a role and should be considered when planning larval seeding.