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.

Uptake and factors that influence the use of 'sit less, move more' occupational intervention strategies in Spanish office employees

Background: Little is known about the types of 'sit less, move more' strategies that appeal to office employees, or what factors influence their use. This study assessed the uptake of strategies in Spanish university office employees engaged in an intervention, and those factors that enabled or limited strategy uptake. Methods: The study used a mixed method design. Semi-structured interviews were conducted with academics and administrators (n = 12; 44 +/- 12 mean SD age; 6 women) at three points across the five-month intervention, and data used to identify factors that influenced the uptake of strategies. Employees who finished the intervention then completed a survey rating (n = 88; 42 +/- 8 mean SD age; 51 women) the extent to which strategies were used [never (1) to usually (4)]; additional survey items (generated from interviewee data) rated the impact of factors that enabled or limited strategy uptake [no influence (1) to very strong influence (4)]. Survey score distributions and averages were calculated and findings triangulated with interview data. Results: Relative to baseline, 67% of the sample increased step counts post intervention (n = 59); 60% decreased occupational sitting (n = 53). 'Active work tasks' and 'increases in walking intensity' were the strategies most frequently used by employees (89% and 94% sometimes or usually utilised these strategies); 'walk-talk meetings' and ` lunchtime walking groups' were the least used (80% and 96% hardly ever or never utilised these strategies). 'Sitting time and step count logging' was the most important enabler of behaviour change (mean survey score of 3.1 +/- 0.8); interviewees highlighted the motivational value of being able to view logged data through visual graphics in a dedicated website, and gain feedback on progress against set goals. 'Screen based work' (mean survey score of 3.2 +/- 0.8) was the most significant barrier limiting the uptake of strategies. Inherent time pressures and cultural norms that dictated sedentary work practices limited the adoption of 'walk-talk meetings' and ` lunch time walking groups'. Conclusions: The findings provide practical insights into which strategies and influences practitioners need to target to maximise the impact of 'sit less, move more' occupational intervention strategies.

Academic spin-offs incubation strategies: the case of the Andalusian region

[EN] The objective of this paper is to analyze the incubation strategies developed in the universities of Andalusia, a relatively low-income region of Spain, to promote the creation of university spin-offs. These strategies are also compared to the incubation models noted in the literature. The performance of the university spin-offs created and its relation to the incubation strategies developed by the university are also analysed. The analysis is based on data from a survey of nine public universities that carry out strategies for the promotion of university spin-offs. The result of the analysis shows that university spin-off incubation strategies in Andalusia present specific characteristics not covered by certain models that are well-known in the literature on innovation. Then, a new stage in the process of the university spin-off incubation is proposed. We consider it to be a pre-strategic stage to the academic spin-off incubation strategies. The analysis also finds certain environmental factors associated to those spin-offs promoted by Andalusian universities that achieve the highest level of performance. This result suggests that previous to making any decision involving investment into developing incubation strategies, universities should gauge whether they have sufficient resources and the possibilities of connecting with a Technology Park.

Final Evaluation Memorandum: Strategies for Resolving Low Dissolved Oxygen and Methylmercury Events in Northern Suisun Marsh

The purpose of the project is to improve our understanding about best management practices that can be utilized on diked managed wetlands in Suisun Marsh for reducing the occurrence of low dissolved oxygen (DO) and high methylmercury (MeHg) events associated primarily with fall flood-up practices. Low DO events are of concern because they can lead to undue stress and even mortality of sensitive aquatic organisms. Elevated MeHg levels are of concern because MeHg is a neurotoxin that bio-magnifies up the food chain and can cause deleterious effects to higher trophic level consumers such as piscivorous fish, birds, and mammals (including humans). This study involved two years (2007-2008) of intensive field data collection at two managed wetland sites in northwest Suisun Marsh and their surrounding tidal sloughs, an area with prior documented low DO events. In addition, the study collected limited soils and water quality field data and mapped vegetation for three managed wetland sites in the central interior of Suisun Marsh, for the purpose of examining whether wetlands at other locations exhibit characteristics that could indicate potential for similar concerns. In Year 1 of the study, the objective was to identify the baseline conditions in the managed wetlands and determine which physical management conditions could be modified for Year 2 to reduce low DO and MeHg production issues most effectively. The objective of Year 2 was to evaluate the effectiveness of these modified management actions at reducing production of low DO and elevated MeHg conditions within the managed wetlands and to continue improving understanding of the underlying biogeochemical processes at play. This Final Evaluation Memorandum examined a total of 19 BMPs, 14 involving modified water management operations and the remaining five involving modified soil and vegetation management practices. Some of these BMPs were previously employed and others have not yet been tested. For each BMP this report assesses its efficacy in improving water quality conditions and potential conflicts with wetland management. It makes recommendations for further study (either feasibility assessments or field testing) and whether to consider for future use. Certain previously used BMPs were found to be important contributors to poor water quality conditions and their continued use is not recommended. Some BMPs that could improve water quality conditions appear difficult to implement in regards to compatibility with wetland management; these BMPs require further elaboration and feasibility assessment to determine whether they should be field tested. In practice for any given wetland, there is likely a combination of BMPs that would together have the greatest potential to address the low DO and high MeHg water quality concerns. Consequently, this report makes no sweeping recommendations applicable to large groups of wetlands but instead promotes a careful consideration of factors at each wetland or small groups of wetlands and from that assessment to apply the most effective suite of BMPs. This report also identifies a number of recommended future actions and studies. These recommendations are geared toward improving the process understanding of factors that promote low DO and high MeHg conditions, the extent of these problems in Suisun Marsh, the regulatory basis for the DO standards for a large estuarine marsh, the economics of BMPs, and alternative approaches to BMPs on diked managed wetlands that may address the water quality issues. The most important of these recommendations is that future BMP implementation should be carried out within the context of rigorous scientific evaluation so as to gain the maximum improvement in how to manage these water quality issues in the diked managed wetlands of Suisun Marsh.

Going for the jugular : strategies of resistance in the fiction of Helena Maria Viramontes

O objetivo desta dissertação é analisar contos selecionados e o romance Under the Feet of Jesus da escritora chicana Helena María Viramontes, enfocando a apropriação de mitos astecas e lendas mexicanas protagonizados por figuras femininas, históricas ou míticas, como La Manlinche, La Llorona e The Hungry Woman. Esta re-visão crítica do passado tem um papel vital para as chicanas, reais e ficcionais, ao enfrentarem o domínio patriarcal, colonial e neocolonial. Devido à complexidade gerada pela ausência de linearidade narrativa, tanto nos contos como no romance, tornou-se necessária uma breve análise das estratégias narrativas a fim de ilustrar como tais estratégias estão intrinsecamente ligadas à apresentação fragmentada da vida dos trabalhadores migrantes. Foi igualmente indispensável examinar as demais práticas narrativas da autora tais como focalização, desconstrução, simultaneidade e justaposição, assim como o elo, por ela proposto em Under the Feet of Jesus, entre leitura, identidade, e engajamento com o mundo para promover a transformação social