Applications of a Concise and General Strategy for the Syntheses of Transtaganolide and Basiliolide Natural Products

Herein are described the total syntheses of all members of the transtaganolide and basiliolide natural product family. Utilitzation of an Ireland–Claisen rearrangement/Diels–Alder cycloaddition cascade (ICR/DA) allowed for rapid assembly of the transtaganolide and basiliolide oxabicyclo[2.2.2]octane core. This methodology is general and was applicable to all members of the natural product family.

A brief introduction outlines all the synthetic progress previously disclosed by Lee, Dudley, and Johansson. This also includes the initial syntheses of transtaganolides C and D, as well as basiliolide B and epi-basiliolide B accomplished by Stoltz in 2011. Lastly, we discuss our racemic synthesis of basililide C and epi-basiliolide C, which utilized an ICR/DA cascade to constuct the oxabicyclo[2.2.2]octane core and formal [5+2] annulation to form the ketene-acetal containing 7-membered C-ring.

Next, we describe a strategy for an asymmetric ICR/DA cascade, by incorporation of a chiral silane directing group. This allowed for enantioselective construction of the C8 all-carbon quaternary center formed in the Ireland–Claisen rearrangement. Furthermore, a single hydride reduction and subsequent translactonization of a C4 methylester bearing oxabicyclo[2.2.2]octane core demonstrated a viable strategy for the desired skeletal rearrangement to obtain pentacyclic transtaganolides A and B. Application of the asymmetric strategy culminated in the total syntheses of (–)-transtaganolide A, (+)-transtaganolide B, (+)-transtaganolide C, and (–)-transtaganolide D. Comparison of the optical rotation data of the synthetically derived transtaganolides to that from the isolated counterparts has overarching biosynthetic implications which are discussed.

Lastly, improvement to the formal [5+2] annulation strategy is described. Negishi cross-coupling of methoxyethynyl zinc chloride using a palladium Xantphos catalyst is optimized for iodo-cyclohexene. Application of this technology to an iodo-pyrone geranyl ester allowed for formation and isolation of the eneyne product. Hydration of the enenye product forms natural metabolite basiliopyrone. Furthermore, the eneyne product can undergo an ICR/DA cascade and form transtaganolides C and D in a single step from an achiral monocyclic precursor.

General-domain compressible Navier-Stokes solvers exhibiting quasi-unconditional stability and high-order accuracy in space and time

This thesis presents a new class of solvers for the subsonic compressible Navier-Stokes equations in general two- and three-dimensional spatial domains. The proposed methodology incorporates: 1) A novel linear-cost implicit solver based on use of higher-order backward differentiation formulae (BDF) and the alternating direction implicit approach (ADI); 2) A fast explicit solver; 3) Dispersionless spectral spatial discretizations; and 4) A domain decomposition strategy that negotiates the interactions between the implicit and explicit domains. In particular, the implicit methodology is quasi-unconditionally stable (it does not suffer from CFL constraints for adequately resolved flows), and it can deliver orders of time accuracy between two and six in the presence of general boundary conditions. In fact this thesis presents, for the first time in the literature, high-order time-convergence curves for Navier-Stokes solvers based on the ADI strategy---previous ADI solvers for the Navier-Stokes equations have not demonstrated orders of temporal accuracy higher than one. An extended discussion is presented in this thesis which places on a solid theoretical basis the observed quasi-unconditional stability of the methods of orders two through six. The performance of the proposed solvers is favorable. For example, a two-dimensional rough-surface configuration including boundary layer effects at Reynolds number equal to one million and Mach number 0.85 (with a well-resolved boundary layer, run up to a sufficiently long time that single vortices travel the entire spatial extent of the domain, and with spatial mesh sizes near the wall of the order of one hundred-thousandth the length of the domain) was successfully tackled in a relatively short (approximately thirty-hour) single-core run; for such discretizations an explicit solver would require truly prohibitive computing times. As demonstrated via a variety of numerical experiments in two- and three-dimensions, further, the proposed multi-domain parallel implicit-explicit implementations exhibit high-order convergence in space and time, useful stability properties, limited dispersion, and high parallel efficiency.

Gauge Invariant Spectral Cauchy Characteristic Extraction of Gravitational Waves in Computational General Relativity

We present a complete system for Spectral Cauchy characteristic extraction (Spectral CCE). Implemented in C++ within the Spectral Einstein Code (SpEC), the method employs numerous innovative algorithms to efficiently calculate the Bondi strain, news, and flux.

Spectral CCE was envisioned to ensure physically accurate gravitational wave-forms computed for the Laser Interferometer Gravitational wave Observatory (LIGO) and similar experiments, while working toward a template bank with more than a thousand waveforms to span the binary black hole (BBH) problem’s seven-dimensional parameter space.

The Bondi strain, news, and flux are physical quantities central to efforts to understand and detect astrophysical gravitational wave sources within the Simulations of eXtreme Spacetime (SXS) collaboration, with the ultimate aim of providing the first strong field probe of the Einstein field equation.

In a series of included papers, we demonstrate stability, convergence, and gauge invariance. We also demonstrate agreement between Spectral CCE and the legacy Pitt null code, while achieving a factor of 200 improvement in computational efficiency.

Spectral CCE represents a significant computational advance. It is the foundation upon which further capability will be built, specifically enabling the complete calculation of junk-free, gauge-free, and physically valid waveform data on the fly within SpEC.

Deep near-infrared spectroscopy of high-redshift galaxies: the physical growth of passive systems

The assembly history of massive galaxies is one of the most important aspects of galaxy formation and evolution. Although we have a broad idea of what physical processes govern the early phases of galaxy evolution, there are still many open questions. In this thesis I demonstrate the crucial role that spectroscopy can play in a physical understanding of galaxy evolution. I present deep near-infrared spectroscopy for a sample of high-redshift galaxies, from which I derive important physical properties and their evolution with cosmic time. I take advantage of the recent arrival of efficient near-infrared detectors to target the rest-frame optical spectra of z > 1 galaxies, from which many physical quantities can be derived. After illustrating the applications of near-infrared deep spectroscopy with a study of star-forming galaxies, I focus on the evolution of massive quiescent systems.

Most of this thesis is based on two samples collected at the W. M. Keck Observatory that represent a significant step forward in the spectroscopic study of z > 1 quiescent galaxies. All previous spectroscopic samples at this redshift were either limited to a few objects, or much shallower in terms of depth. Our first sample is composed of 56 quiescent galaxies at 1 < z < 1.6 collected using the upgraded red arm of the Low Resolution Imaging Spectrometer (LRIS). The second consists of 24 deep spectra of 1.5 < z < 2.5 quiescent objects observed with the Multi-Object Spectrometer For Infra-Red Exploration (MOSFIRE). Together, these spectra span the critical epoch 1 < z < 2.5, where most of the red sequence is formed, and where the sizes of quiescent systems are observed to increase significantly.

We measure stellar velocity dispersions and dynamical masses for the largest number of z > 1 quiescent galaxies to date. By assuming that the velocity dispersion of a massive galaxy does not change throughout its lifetime, as suggested by theoretical studies, we match galaxies in the local universe with their high-redshift progenitors. This allows us to derive the physical growth in mass and size experienced by individual systems, which represents a substantial advance over photometric inferences based on the overall galaxy population. We find a significant physical growth among quiescent galaxies over 0 < z < 2.5 and, by comparing the slope of growth in the mass-size plane dlogR_e/dlogM_∗ with the results of numerical simulations, we can constrain the physical process responsible for the evolution. Our results show that the slope of growth becomes steeper at higher redshifts, yet is broadly consistent with minor mergers being the main process by which individual objects evolve in mass and size.

By fitting stellar population models to the observed spectroscopy and photometry we derive reliable ages and other stellar population properties. We show that the addition of the spectroscopic data helps break the degeneracy between age and dust extinction, and yields significantly more robust results compared to fitting models to the photometry alone. We detect a clear relation between size and age, where larger galaxies are younger. Therefore, over time the average size of the quiescent population will increase because of the contribution of large galaxies recently arrived to the red sequence. This effect, called progenitor bias, is different from the physical size growth discussed above, but represents another contribution to the observed difference between the typical sizes of low- and high-redshift quiescent galaxies. By reconstructing the evolution of the red sequence starting at z ∼ 1.25 and using our stellar population histories to infer the past behavior to z ∼ 2, we demonstrate that progenitor bias accounts for only half of the observed growth of the population. The remaining size evolution must be due to physical growth of individual systems, in agreement with our dynamical study.

Finally, we use the stellar population properties to explore the earliest periods which led to the formation of massive quiescent galaxies. We find tentative evidence for two channels of star formation quenching, which suggests the existence of two independent physical mechanisms. We also detect a mass downsizing, where more massive galaxies form at higher redshift, and then evolve passively. By analyzing in depth the star formation history of the brightest object at z > 2 in our sample, we are able to put constraints on the quenching timescale and on the properties of its progenitor.

A consistent picture emerges from our analyses: massive galaxies form at very early epochs, are quenched on short timescales, and then evolve passively. The evolution is passive in the sense that no new stars are formed, but significant mass and size growth is achieved by accreting smaller, gas-poor systems. At the same time the population of quiescent galaxies grows in number due to the quenching of larger star-forming galaxies. This picture is in agreement with other observational studies, such as measurements of the merger rate and analyses of galaxy evolution at fixed number density.

Bassenthwaite Lake: a general assessment of environmental and biological features and their susceptibility to change

Bassenthwaite (Lake) is one of the larger Cumbrian lakes, certainly one of the most distinctive, and of considerable conservation and amenity value. Although its shores lack sizeable settlements, its main inflow receives sewage effluent from a major tourist centre (Keswick) and is subject to episodic floods. These influences, the growing development of leisure activities at the lake (e.g. sailing, time-share units), and recent road-construction, have led to past appraisals of ecological impacts and lake management. The lake has not been the subject of intense and long-term ecological study, but much scattered information exists that is relevant to future management decisions. In the present Report, commissioned by North West Water, such information - published and unpublished - is surveyed. Especial attention is given to evidence bearing on susceptibility to change, affecting the lake environment and its biota or species of conservation interest. Extensive use has been made of the results of a recent (1986-7) seasonal survey by the FBA.

A general assessment of environmental and biological features of Windermere and their susceptibility to change

Bassenthwaite (Lake) is one of the larger Cumbrian lakes, certainly one of the most distinctive, and of considerable conservation and amenity value. Although its shores lack sizeable settlements, its main inflow receives sewage effluent from a major tourist centre (Keswick) and is subject to episodic floods. These influences, the growing development of leisure activities at the lake (e.g. sailing, time-share units), and recent road-construction, have led to past appraisals of ecological impacts and lake management. The lake has not been the subject of intense and long-term ecological study, but much scattered information exists that is relevant to future management decisions. In the present Report, commissioned by North West Water, such information - published and unpublished - is surveyed. Especial attention is given to evidence bearing on susceptibility to change, affecting the lake environment and its biota or species of conservation interest. Extensive use has been made of the results of a recent (1986-7) seasonal survey by the FBA.

Lurking in ULIRGs: Molecular Gas in local Merging Galaxies

Mergers and interacting galaxies are pivotal to the evolution of galaxies in the universe. They are the sites of prodigious star formation and key to understanding the starburst processes: the physical and chemical properties and the dynamics of the molecular gas. ULIRGs or Ultraluminous Infrared Galaxies are a result of many of these mergers. They host extreme starbursts, AGNs, and mergers. They are the perfect laboratory to probe the connection between starbursts, black hole accretion and mergers and to further our understanding of star formation and merging.

NGC 6240 and Arp 220 can be considered the founding members of this very active class of objects. They are in different stages of merging and hence are excellent case studies to further our understanding about the merging process. We have imaged the dense star-forming regions of these galaxies at sub-arcsec resolution with CARMA C and B Configurations (2" and 0.5 - 0.8"). Multi-band imaging allows excitation analysis of HCN, HCO⁺, HNC, and CS along with CO transitions to constrain the properties of the gas. Our dataset is unique in that we have observed these lines at similar resolutions and high sensitivity which can be used to derive line ratios of faint high excitation lines.

Arp 220 has not had confirmed X-ray AGN detections for either nuclei. However, our observations indicate HCN/HNC ratios consistent with the chemistry of X-ray Dominated Regions (XDRs) -- a likely symptom of AGN. We calculated the molecular Hydrogen densities using each of the molecular species and conclude that assuming abundances of HNC and HCO⁺ similar to those in galactic sources are incorrect in the case of ULIRGs. The physical conditions in the dense molecular gas in ULIRGs alter these abundances. The derived H2 volume densities are ~ 5 x 10⁴ cm^-3 in both Arp 220 nuclei and ~ 10⁴ cm^-3 in NGC 6240.

E. U. Magisterio de Vitoria-Gasteiz. Plan general Practicum I. Comisión de prácticas, 21 de marzo de 2011

[ES]La adaptación de la Universidad Española al Espacio Europeo de Educación Superior (EEES) ha supuesto un cambio en los estudios universitarios que se advierte en su estructura (títulos de grado de cuatro años,) y que debe manifestarse también en las metodologías utilizadas. En los estudios de Magisterio la nueva ordenación de las enseñanzas ha supuesto la unificación de las anteriores especialidades en dos títulos de grado: Maestro de Educación Infantil y Maestro de Educación Primaria. En estos nuevos títulos las Prácticas de Enseñanza continúan teniendo un importante papel y constituyen un momento privilegiado de integración entre la teoría y la realidad de las aulas. El Practicum es el conjunto de actividades en las que diversas instituciones colaboran con la Escuela Universitaria de Magisterio, a fin de poner al alumnado en contacto con el mundo profesional. Supone la inmersión de los estudiantes en centros educativos con la finalidad de conocerlos directamente, integrar conocimientos teórico-prácticos, y adquirir competencias profesionales en todos los ámbitos de actuación.

Water temperature studies on the R. North Tyne after impoundment by Kielder dam. 1. General introduction and background data

This report describes the general background to the project, defines the stations from which data sets have been obtained and lists the available data. The project had the following aims: To develop a more accurate and less labour-intensive system for the collection and processing of water temperature data from a number of stations within a stream/river system, and to use the River North Tyne downstream of the Kielder impoundment as a test bed for the system. This should yield useful information on the effects of impoundment upon downstream water temperatures.

E. U. Magisterio de Vitoria-Gasteiz. Plan general Practicum II. Comisión de prácticas, 21 de marzo de 2012

[ES]El Módulo de Practicum se organiza en dos materias: Prácticas escolares (38 créditos ECTS), y Trabajo fin de grado (12 créditos ECTS). Las prácticas escolares se realizarán en los dos ciclos de Educación Infantil (0-3, 3-6) y en los tres de Primaria (1ª-2º, 3º-4º, 5º-6º). Al tratarse de un Practicum progresivo, los estudiantes de los grados de Magisterio cursan la materia a lo largo del segundo, tercer y cuarto curso (Practicum I, Practicum II y Practicum III) con contenidos que tienen continuidad y que suponen un nivel de competencia superior respecto el anterior. El Practicum supone para el alumnado una oportunidad de adquirir e integrar las habilidades, los conocimientos, las competencias y la práctica necesarios para el ejercicio de su profesión, así como una ocasión para reflexionar de forma individual y grupal acerca del aprendizaje realizado. El Practicum I pretende que el alumnado establezca un primer contacto como futuros profesionales con un centro escolar, y realice una observación de carácter global, integrando los conocimientos aprendidos en la Escuela de Magisterio, ajustándolos a la diversidad del aula, a la escuela y al entorno social de ésta, y dedicando una especial atención al tratamiento de género. El Practicum II, al que se refiere esta guía, corresponde al tercer curso y se centra en el desarrollo docente de experiencias de enseñanza y aprendizaje con alumnado de la etapa, la implicación en la vida del ciclo y etapa y el ejercicio de la autocrítica y la reflexión en relación al propio desarrollo formativo y profesional. Se pretende que los estudiantes reflexionen de forma crítica sobre su conocimiento práctico inicial puesto en acción en esos contextos y sobre las condiciones que determinan su forma de pensar y actuar. El Practicum III está relacionado con las menciones (minor) y con la participación en proyectos de innovación.

E. U. Magisterio de Vitoria-Gasteiz. Plan general Practicum III. Comisión de prácticas, 4 de julio de 2014

[ES]Las Prácticas Escolares se realizarán en los dos ciclos de Educación Infantil (0-3, 3-6) y en los tres de Educación Primaria (1º-2º, 3º-4º, 5º-6º). Al tratarse de un Prácticum progresivo, cada estudiante cursa la materia a lo largo del segundo, tercer y cuarto curso (Prácticum I, Prácticum II y Prácticum III) con contenidos que tienen continuidad y que suponen un nivel de competencia superior respecto el anterior. Además, el alumnado que en 4º curso se matricule en el minor de Educación Física deberá realizar su periodo de prácticas junto a una maestra o maestro especialista en esta materia, quien tutorizará sus prácticas. El Prácticum supone para el alumnado una oportunidad de adquirir e integrar las habilidades, los conocimientos, las competencias y la práctica necesarios para el ejercicio de su profesión, así como una ocasión para reflexionar de forma individual y grupal acerca del aprendizaje realizado y de la práctica llevada a cabo.

Intensity-moments characterization of general pulsed paraxial beams with the Wigner distribution function

On the basis of the space-time Wigner distribution function (STWDF), we use the matrix formalism to study the propagation laws for the intensity moments of quasi-monochromatic and polychromatic pulsed paraxial beams. The advantages of this approach are reviewed. Also, a least-squares fitting method for interpreting the physical meaning of the effective curvature matrix is described by means of the STWDF. Then the concept is extended to the higher-order situation, and what me believe is a novel technique for characterizing the beam phase is presented. (C) 1999 Optical Society of America [S0740-3232(99)001009-1].