Design of tailored strategies for preservation and re-use of information about heritage

[EN] This paper is an outcome of the following dissertation:

Climate adaptation and the fifth amendment of the United States Constitution: How do adaptation strategies impact regulatory takings claims?

As the impacts and potential of climate change are realized at the governance level, states are moving towards adaptation strategies that include greater regulatory restrictions on development within coastal zones. The purpose of this paper is to outline the impacts of existing and planned regulatory mechanisms on the Fifth Amendment to the United States Constitution, which prevents the government taking of private property for public use without just compensation. A short history of regulatory takings is explained, and the potential legal issues surrounding mitigation and adaptation measures for coastal communities are discussed. The goal is to gain an understanding of the legal issues that must be resolved by governments to effectively deal with regulatory takings claims as coastal mitigation and adaptation plans are implemented. (PDF contains 3 pages)

Cooperative learning strategies to teach nutrition to geriatric nursing staff

[EN] The objective of this study was to test the hypothesis that cooperative learning strategies will help to increase nutrition knowledge of nurses and nursing assistants caring for the elderly in different institutional communities of the Basque Country, Spain. The target population was a sample of volunteers, 16 nurses and 28 nursing assistants. Training consisted of 12 nutrition education sessions using cooperative strategies conducted over a period of 3 consecutive weeks. The assessment instruments included two pretest and two posttest questionnaires with questions selected in multiplechoice format. The first questionnaire was about general knowledge of applied nutrition (0-88 point scale) and the second one on geriatric nutrition knowledge (0-18 point scale). Data were analyzed using SPSS vs. 11.0. The outcomes indicated a significant increase in general nutrition knowledge (difference between the pre- and posttest mean score: 14.5±10.1; P<0.001) and in geriatric nutrition knowledge for all participants (difference between the pre- and post-test mean score: 4.6±4.6; P<0.001). So the results indicated that cooperative learning strategies could improve the nutrition knowledge of nursing staff. Additionally, the results of this study provide direction to continuing nutrition education program planners regarding appropriate content and methodology for programs.

New strategies for the total synthesis of aza-propellane natural products

The propellane alkaloids comprise a large class of natural products that possess varying degrees of structural complexity and biological activity. The earliest of these to be isolated was acutumine, a chlorinated alkaloid that has been shown to exhibit selective T-cell cytotoxicity and antiamnesic properties. Alternatively, the hasubanan family of natural products has garnered considerable attention from the synthetic community in part due to its structural similarities to morphine. While these alkaloids have been the subject of numerous synthetic studies over the last forty years, very few enantioselective total syntheses have been reported to date.

As part of a research program directed towards the synthesis of various alkaloid natural products, we have developed a unified strategy for the preparation of the hasubanan and acutumine alkaloids. Specifically, a highly diastereoselective 1,2-addition of organometallic reagents to benzoquinone-derived tert-butanesulfinimines was established, which provides access to enantioenriched 4-aminocyclohexadienone products. This methodology enabled the enantioselective construction of functionalized dihydroindolones, which were found to undergo intramolecular Friedel-Crafts conjugate additions to furnish the propellane cores of several hasubanan alkaloids. As a result of these studies, the first enantioselective total syntheses of 8-demethoxyrunanine and cepharatines A, C, and D were accomplished in 9-11 steps from commercially available starting materials.

More recent efforts have focused on applying the sulfinimine methodology to the synthesis of a more structurally complex propellane alkaloid, acutumine. Extensive studies have determined that a properly functionalized dihydroindolone undergoes a photochemical [2+2] cycloaddition followed by a lactone fragmentation/Dieckmann cyclization to establish the carbocyclic framework of the natural product. The preparation of more appropriately oxidized propellane intermediates is currently under investigation, and is anticipated to facilitate our synthetic endeavors toward acutumine.

Design strategies for ultra-high efficiency photovoltaics

While concentrator photovoltaic cells have shown significant improvements in efficiency in the past ten years, once these cells are integrated into concentrating optics, connected to a power conditioning system and deployed in the field, the overall module efficiency drops to only 34 to 36%. This efficiency is impressive compared to conventional flat plate modules, but it is far short of the theoretical limits for solar energy conversion. Designing a system capable of achieving ultra high efficiency of 50% or greater cannot be achieved by refinement and iteration of current design approaches.

This thesis takes a systems approach to designing a photovoltaic system capable of 50% efficient performance using conventional diode-based solar cells. The effort began with an exploration of the limiting efficiency of spectrum splitting ensembles with 2 to 20 sub cells in different electrical configurations. Incorporating realistic non-ideal performance with the computationally simple detailed balance approach resulted in practical limits that are useful to identify specific cell performance requirements. This effort quantified the relative benefit of additional cells and concentration for system efficiency, which will help in designing practical optical systems.

Efforts to improve the quality of the solar cells themselves focused on the development of tunable lattice constant epitaxial templates. Initially intended to enable lattice matched multijunction solar cells, these templates would enable increased flexibility in band gap selection for spectrum splitting ensembles and enhanced radiative quality relative to metamorphic growth. The III-V material family is commonly used for multijunction solar cells both for its high radiative quality and for the ease of integrating multiple band gaps into one monolithic growth. The band gap flexibility is limited by the lattice constant of available growth templates. The virtual substrate consists of a thin III-V film with the desired lattice constant. The film is grown strained on an available wafer substrate, but the thickness is below the dislocation nucleation threshold. By removing the film from the growth substrate, allowing the strain to relax elastically, and bonding it to a supportive handle, a template with the desired lattice constant is formed. Experimental efforts towards this structure and initial proof of concept are presented.

Cells with high radiative quality present the opportunity to recover a large amount of their radiative losses if they are incorporated in an ensemble that couples emission from one cell to another. This effect is well known, but has been explored previously in the context of sub cells that independently operate at their maximum power point. This analysis explicitly accounts for the system interaction and identifies ways to enhance overall performance by operating some cells in an ensemble at voltages that reduce the power converted in the individual cell. Series connected multijunctions, which by their nature facilitate strong optical coupling between sub-cells, are reoptimized with substantial performance benefit.

Photovoltaic efficiency is usually measured relative to a standard incident spectrum to allow comparison between systems. Deployed in the field systems may differ in energy production due to sensitivity to changes in the spectrum. The series connection constraint in particular causes system efficiency to decrease as the incident spectrum deviates from the standard spectral composition. This thesis performs a case study comparing performance of systems over a year at a particular location to identify the energy production penalty caused by series connection relative to independent electrical connection.

Reproduction in Gammarus (Crustacea, Amphipoda): female strategies

This paper attempts to review the literature on Gammarus and examine how it allocates its internal resources when producing eggs. There is an extensive literature on the fecundity of freshwater species but almost nothing is known about the sizes and energy contents of the eggs. More is known for saltwater species, in which the mean number of eggs per brood is inversely proportional to mean egg size and directly proportional to the female's body size. Theoretical aspects of egg size, numbers and reproductive effort are examined, along with the relation between sizes of eggs, broods and female body size. The reproductive effort and breeding cycles of both saltwater and freshwater species are reviewed, and reproductive strategies assessed.

Life-history strategies of pike in a high-altitude loch in Scotland

Pike, Esox lucius, are present in Loch Callater at their highest altitude and most extreme habitat in the British Isles, with subarctic winter conditions and extended winter ice-cover. The response of pike in this environment is slower growth, due to a shorter growing season and the low availability of forage fish, giving the poorest reported length-at-age for pike in the British Isles. All pike were mature or had spawned in the same year, with gravid ovaries in April and normal recovering ovaries in June-July. As in other lochs with few prey fishes, the larger pike ate small items such as invertebrates.

Strategies for the Stereoselective Synthesis of Carbon Quaternary Centers via Transition Metal-Catalyzed Alkylation of Enolate Compounds

Notwithstanding advances in modern chemical methods, the selective installation of sterically encumbered carbon stereocenters, in particular all-carbon quaternary centers, remains an unsolved problem in organic chemistry. The prevalence of all-carbon quaternary centers in biologically active natural products and pharmaceutical compounds provides a strong impetus to address current limitations in the state of the art of their generation. This thesis presents four related projects, all of which share in the goal of constructing highly-congested carbon centers in a stereoselective manner, and in the use of transition-metal catalyzed alkylation as a means to address that goal.

The first research described is an extension of allylic alkylation methodology previously developed in the Stoltz group to small, strained rings. This research constitutes the first transition metal-catalyzed enantioselective α-alkylation of cyclobutanones. Under Pd-catalysis, this chemistry affords all–carbon α-quaternary cyclobutanones in good to excellent yields and enantioselectivities.

Next is described our development of a (trimethylsilyl)ethyl β-ketoester class of enolate precursors, and their application in palladium–catalyzed asymmetric allylic alkylation to yield a variety of α-quaternary ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to allyl β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of our fluoride-triggered β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.

Lastly, our development of an Ir-catalyzed asymmetric allylic alkylation of cyclic β-ketoesters to afford highly congested, vicinal stereocenters comprised of tertiary and all-carbon quaternary centers with outstanding regio-, diastereo-, and enantiocontrol is detailed. Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated products with pinpoint stereochemical control of both chiral centers. The chemistry is then extended to include acyclic β-ketoesters and similar levels of selective and functional group tolerance are observed. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands.