196 research outputs found
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Photochemical synthesis of heterocyclic compounds
The aim of our research was to investigate the photocyclisation of N-substituted imide systems, in order to prepare polycyclic heterocyclic photoproducts of potential pharmaceutical interest.
The major group of substrates were N-(dialkylaminoalkyl)succinimides. Irradiation of succinimide Mannich bases (A) leads to two diastereoisomers of 1,3-diazabicyclo[3.3,0]octanes in reasonable yields. The relative stereochemistry was assigned on the basis of spectral data. With substrates (e.g. B) derived from unsymmetrical amines, there is strong orientational preference.
Substrates (e.g. G) derived from an unsymmetrical succinimide gave a mixture of products; the preferred orientation of cyclisation is to the more hindered C-1 carbonyl group.
Using hydantoin substrates (D) which correspond to succinimides in which a methylene group is replaced by a heteroatom, we found that cyclisation occurs only at the C--4 (imide-like) carbonyl group to give diastereoisomers of 1,3,7 - triazabicyclo[3.3,0]octanes.
Glutarimide Mannich bases show many parallels with the succinimide analogues. However, pyrrolidin-2-one Mannich bases did not afford photocyclised products. A minor product (E) is formed by cleavage in the amine fragment.
N-(Dialkylaminoethyl) derivatives of saturated imides (F) give rise to ring-expanded photoproducts. This is in contrast to phthalimide substrates (G; n = 2), where photoproducts with a new piperazine ring are obtained.
Our hypothesis is that an electron-transfer mechanism operates in the aromatic systems, leading to the possibility of medium/large ring formation, but this is not effective in the succinimides which are poorer electron acceptors. To test this, we irradiated a series o f N-(dialkylaminoalkyl) derivatives of imides with a double bond conjugated with the carbonyl groups, and found that these substrates (H) do give photoproducts with new six- or seven-membered rings.
Our results with N-(dialkylaminopropyl)phthallmides (G; n = 3) are not entirely in agreement with earlier reports that medium-ring formation is the major photocyclisation process for phthalimide substrates. Further work is required to extend this comparison of the photocyclisation process for saturated, unsaturated and aromatic N-(dialkylaminoalkyl)imides
Assessing the Impact of the Conservation Reserve Program on Honey Bee Health
Insect pollinators are critically important for maintaining U.S. food production and ecosystem health. The upper Midwest is home to more than 40 percent of all U.S. honey bee colonies and is considered by many beekeepers to be America’s last beekeeping refuge. Beekeepers come to this region because their honey bees require high-quality grassland and bee-friendly agricultural crops to make honey and to improve bee health. Agricultural grassland, such as those enrolled in the Conservation Reserve Program (CRP), support flowers that provide bees with the pollen and nectar they need. In 2014, the U.S. Department of Agriculture (USDA) and the U.S. Geological Survey (USGS) formed a partnership to assess the impact of the CRP on honey bee health and determine how the costeffectiveness of the CRP could be improved to promote pollinator habitat. This USGS assessment has generated important findings that could improve USDA’s program delivery and demonstrates the importance of the CRP to honey bees, beekeepers, agricultural producers, and the public (Otto and others, 2017, 2018)
Asymptotically cylindrical 7-manifolds of holonomy G_2 with applications to compact irreducible G_2-manifolds
We construct examples of exponentially asymptotically cylindrical Riemannian
7-manifolds with holonomy group equal to G_2. To our knowledge, these are the
first such examples. We also obtain exponentially asymptotically cylindrical
coassociative calibrated submanifolds. Finally, we apply our results to show
that one of the compact G_2-manifolds constructed by Joyce by desingularisation
of a flat orbifold T^7/\Gamma can be deformed to one of the compact
G_2-manifolds obtainable as a generalized connected sum of two exponentially
asymptotically cylindrical SU(3)-manifolds via the method given by the first
author (math.DG/0012189).Comment: 36 pages; v2: corrected trivial typos; v3: some arguments corrected
and improved; v4: a number of improvements on presentation, paritularly in
sections 4 and 6, including an added picture
Predicting university performance in psychology: the role of previous performance and discipline-specific knowledge
Recent initiatives to enhance retention and widen participation ensure it is crucial to understand the factors that predict students' performance during their undergraduate degree. The present research used Structural Equation Modeling (SEM) to test three separate models that examined the extent to which British Psychology students' A-level entry qualifications predicted: (1) their performance in years 1-3 of their Psychology degree, and (2) their overall degree performance. Students' overall A-level entry qualifications positively predicted performance during their first year and overall degree performance, but negatively predicted their performance during their third year. Additionally, and more specifically, students' A-level entry qualifications in Psychology positively predicted performance in the first year only. Such findings have implications for admissions tutors, as well as for students who have not studied Psychology before but who are considering applying to do so at university
The latitudes, attitudes, and platitudes of watershed phosphorus management in North America
Phosphorus (P) plays a crucial role in agriculture as a primary fertilizer nutrient—and as a cause of the eutrophication of surface waters. Despite decades of efforts to keep P on agricultural fields and reduce losses to waterways, frequent algal blooms persist, triggering not only ecological disruption but also economic, social, and political consequences. We investigate historical and persistent factors affecting agricultural P mitigation in a transect of major watersheds across North America: Lake Winnipeg, Lake Erie, the Chesapeake Bay, and Lake Okeechobee/Everglades. These water bodies span 26 degrees of latitude, from the cold climate of central Canada to the subtropics of the southeastern United States. These water bodies and their associated watersheds have tracked trajectories of P mitigation that manifest remarkable similarities, and all have faced challenges in the application of science to agricultural management that continue to this day. An evolution of knowledge and experience in watershed P mitigation calls into question uniform solutions as well as efforts to transfer strategies from other arenas. As a result, there is a need to admit to shortcomings of past approaches, plotting a future for watershed P mitigation that accepts the sometimes two-sided nature of Hennig Brandt’s “Devil’s Element.
Electron-Hole Correlations and Optical Excitonic Gaps in Quantum-Dot Quantum Wells: Tight-Binding Approach
Electron-hole correlation in quantum-dot quantum wells (QDQW's) is
investigated by incorporating Coulomb and exchange interactions into an
empirical tight-binding model. Sufficient electron and hole single-particle
states close to the band edge are included in the configuration to achieve
convergence of the first spin-singlet and triplet excitonic energies within a
few meV. Coulomb shifts of about 100 meV and exchange splittings of about 1 meV
are found for CdS/HgS/CdS QDQW's (4.7 nm CdS core diameter, 0.3 nm HgS well
width and 0.3 nm to 1.5 nm CdS clad thickness) which have been characterized
experimentally by Weller and co-workers [ D. Schooss, A. Mews, A. Eychmuller,
H. Weller, Phys. Rev. B, 49, 17072 (1994)]. The optical excitonic gaps
calculated for those QDQW's are in good agreement with the experiment.Comment: 3 figures, to appear in Phys.Rev.
Composite Fermion Description of Correlated Electrons in Quantum Dots: Low Zeeman Energy Limit
We study the applicability of composite fermion theory to electrons in
two-dimensional parabolically-confined quantum dots in a strong perpendicular
magnetic field in the limit of low Zeeman energy. The non-interacting composite
fermion spectrum correctly specifies the primary features of this system.
Additional features are relatively small, indicating that the residual
interaction between the composite fermions is weak. \footnote{Published in
Phys. Rev. B {\bf 52}, 2798 (1995).}Comment: 15 pages, 7 postscript figure
Tight-binding study of the influence of the strain on the electronic properties of InAs/GaAs quantum dots
We present an atomistic investigation of the influence of strain on the
electronic properties of quantum dots (QD's) within the empirical tight-binding (ETB) model with interactions up to 2nd nearest neighbors
and spin-orbit coupling. Results for the model system of capped pyramid-shaped
InAs QD's in GaAs, with supercells containing atoms are presented and
compared with previous empirical pseudopotential results. The good agreement
shows that ETB is a reliable alternative for an atomistic treatment. The strain
is incorporated through the atomistic valence force field model. The ETB
treatment allows for the effects of bond length and bond angle deviations from
the ideal InAs and GaAs zincblende structure to be selectively removed from the
electronic-structure calculation, giving quantitative information on the
importance of strain effects on the bound state energies and on the physical
origin of the spatial elongation of the wave functions. Effects of dot-dot
coupling have also been examined to determine the relative weight of both
strain field and wave function overlap.Comment: 22 pages, 7 figures, submitted to Phys. Rev. B (in press) In the
latest version, added Figs. 3 and 4, modified Fig. 5, Tables I and II,.and
added new reference
Review article: the future of microbiome-based therapeutics
Published online 24 May 2022Background: From consumption of fermented foods and probiotics to emerging applications of faecal microbiota transplantation, the health benefit of manipulating the human microbiota has been exploited for millennia. Despite this history, recent technological advances are unlocking the capacity for targeted microbial manipulation as a novel therapeutic.Aim: This review summarises the current developments in microbiome- based medicines and provides insight into the next steps required for therapeutic development.Methods: Here we review current and emerging approaches and assess the capabilities and weaknesses of these technologies to provide safe and effective clinical inter-ventions. Key literature was identified through Pubmed searches with the following key words, ‘microbiome’, ‘microbiome biomarkers’, ‘probiotics’, ‘prebiotics’, ‘synbiotics’, ‘faecal microbiota transplant’, ‘live biotherapeutics’, ‘microbiome mimetics’ and ‘postbiotics’.Results: Improved understanding of the human microbiome and recent technological advances provide an opportunity to develop a new generation of therapies. These therapies will range from dietary interventions, prebiotic supplementations, single probiotic bacterial strains, human donor-derived faecal microbiota transplants, ra-tionally selected combinations of bacterial strains as live biotherapeutics, and the beneficial products or effects produced by bacterial strains, termed microbiome mimetics.Conclusions: Although methods to identify and refine these therapeutics are continually advancing, the rapid emergence of these new approaches necessitates accepted technological and ethical frameworks for measurement, testing, laboratory practices and clinical translation.Emily L. Gulliver, Remy B. Young, Michelle Chonwerawong, Gemma L. D'Adamo, Tamblyn Thomason, James T. Widdop, Emily L. Rutten, Vanessa Rossetto Marcelino, Robert V. Bryant, Samuel P. Costello, Claire L. O'Brien, Georgina L. Hold, Edward M. Giles, Samuel C. Forste
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