1,163 research outputs found
The Synthesis of Functionalised beta-Lactams
N-t-Butyldimethylsilyl imines were prepared readily by oxidation of the corresponding primary amines. The application of N-t-butyl-dimethylsilyl imines to the synthesis of monocyclic beta-lactams was examined via the ester-imine condensation reaction with silyl ketene acetals. Initial choice of Znl2 as Lewis acid for this reaction proved fruitful in certain instances. This reaction, performed in the presence of t-BuOH to suppress reaction of the initially formed N-metallo beta-amino ester with a further molecule of activated imine, followed by treatment with Grignard reagent, displays a modest trans selectivity in the product beta-lactams. However, difficulties were encountered during utilization of more highly functionalised N-t-butyldimethylsilyl imines. As a result, a second Lewis acid system was investigated. Utilization of trimethylsilyl trifluoromethanesulphonate (TMSOTf) as the Lewis acid component produced, in a one-pot process, a range of beta-lactams in a trans-selective manner. Chemical yields resulting from this approach were comparable to those achieved using Znl2 as Lewis acid and the diastereoselectivities found showed a modest increase over those induced in the earlier approach. Low temperature quenching of the derived from treatment of a non-enolisable aldehyde with lithium hexamethyldisilazide resulted in formation of the corresponding N,N,O-tris(trimethylsilyl) amine acetal. Treatment of these compounds with TMSOTf provides access to the same reactive iminium species as found in the reaction between N-silyl imines and TMSOTf and, as such, provides an alternative route to beta-lactam synthesis. Two functionalised silyl ketene acetals were prepared. Attempts to incorporate these substrates into the ester-imine condensation process met with only partial success. The cyclic silyl ketene acetal derived from delta-valerolactone was incorporated into a beta-lactam nucleus, although some atypical characteristics were observed in this system. As an alternative source of the electrophilic iminium species generated in the reaction between an imine or amine acetal with a Lewis acid, the reactivity of enamines was examined. Lewis acid catalysis did allow access to beta-amino esters from enamines, although certain aspects of this process are, as yet, unexplained
Diversity of Decline-Rate-Corrected Type Ia Supernova Rise Times: One Mode or Two?
B-band light-curve rise times for eight unusually well-observed nearby Type
Ia supernovae (SNe) are fitted by a newly developed template-building
algorithm, using light-curve functions that are smooth, flexible, and free of
potential bias from externally derived templates and other prior assumptions.
From the available literature, photometric BVRI data collected over many
months, including the earliest points, are reconciled, combined, and fitted to
a unique time of explosion for each SN. On average, after they are corrected
for light-curve decline rate, three SNe rise in 18.81 +- 0.36 days, while five
SNe rise in 16.64 +- 0.21 days. If all eight SNe are sampled from a single
parent population (a hypothesis not favored by statistical tests), the rms
intrinsic scatter of the decline-rate-corrected SN rise time is 0.96 +0.52
-0.25 days -- a first measurement of this dispersion. The corresponding global
mean rise time is 17.44 +- 0.39 days, where the uncertainty is dominated by
intrinsic variance. This value is ~2 days shorter than two published averages
that nominally are twice as precise, though also based on small samples. When
comparing high-z to low-z SN luminosities for determining cosmological
parameters, bias can be introduced by use of a light-curve template with an
unrealistic rise time. If the period over which light curves are sampled
depends on z in a manner typical of current search and measurement strategies,
a two-day discrepancy in template rise time can bias the luminosity comparison
by ~0.03 magnitudes.Comment: As accepted by The Astrophysical Journal; 15 pages, 6 figures, 2
tables. Explanatory material rearranged and enhanced; Fig. 4 reformatte
Evidence for a Spectroscopic Sequence Among SNe Ia
In this Letter we present evidence for a spectral sequence among Type Ia
supernovae (SNe Ia). The sequence is based on the systematic variation of
several features seen in the near-maximum light spectrum. This sequence is
analogous to the recently noted photometric sequence among SNe Ia which shows a
relationship between the peak brightness of a SN Ia and the shape of its light
curve. In addition to the observational evidence we present a partial
theoretical explanation for the sequence. This has been achieved by producing a
series of non-LTE synthetic spectra in which only the effective temperature is
varied. The synthetic sequence nicely reproduces most of the differences seen
in the observed one and presumably corresponds to the amount of 56Ni produced
in the explosion.Comment: To appear in Astrophysical Journal Letters, uuencoded, gzipped
postscript file, also available from http://www.nhn.uoknor.edu/~baron
Constraining the Progenitor Companion of the Nearby Type Ia SN 2011fe with a Nebular Spectrum at +981 Days
We present an optical nebular spectrum of the nearby Type Ia supernova
2011fe, obtained 981 days after explosion. SN 2011fe exhibits little evolution
since the +593 day optical spectrum, but there are several curious aspects in
this new extremely late-time regime. We suggest that the persistence of the
~\AA\ feature is due to Na I D, and that a new emission feature at
~\AA\ may be [Ca II]. Also, we discuss whether the new emission
feature at ~\AA\ might be [Fe I] or the high-velocity hydrogen
predicted by Mazzali et al. The nebular feature at 5200~\AA\ exhibits a linear
velocity evolution of per 100 days from at least
+220 to +980 days, but the line's shape also changes in this time, suggesting
that line blending contributes to the evolution. At days after
explosion, flux from the SN has declined to a point where contribution from a
luminous secondary could be detected. In this work we make the first
observational tests for a post-impact remnant star and constrain its
temperature and luminosity to and
. Additionally, we do not see any evidence for narrow H
emission in our spectrum. We conclude that observations continue to strongly
exclude many single-degenerate scenarios for SN 2011fe.Comment: 11 pages, 10 figures, published by MNRA
Indoor localisation through object detection within multiple environments utilising a single wearable camera
The recent growth in the wearable sensor market has stimulated new opportunities within the domain of Ambient Assisted Living, providing unique methods of collecting occupant information. This approach leverages contemporary wearable technology, Google Glass, to facilitate a unique first-person view of the occupants immediate environment. Machine vision techniques are employed to determine an occupant’s location via environmental object detection. This method provides additional secondary benefits such as first person tracking within the environment and lack of required sensor interaction to determine occupant location. Object recognition is performed using the Oriented Features from Accelerated Segment Test and Rotated Binary Robust Independent Elementary Features algorithm with a K-Nearest Neighbour matcher to match the saved key-points of the objects to the scene. To validate the approach, an experimental set-up consisting of three ADL routines, each containing at least ten activities, ranging from drinking water to making a meal were considered. Ground truth was obtained from manually annotated video data and the approach was previously benchmarked against a common method of indoor localisation that employs dense sensor placement in order to validate the approach resulting in a recall, precision, and F-measure of 0.82, 0.96, and 0.88 respectively. This paper will go on to assess to the viability of applying the solution to differing environments, both in terms of performance and along with a qualitative analysis on the practical aspects of installing such a system within differing environments
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