Probing the Mechanisms of Enantioselective Hydrogenation of Simple Olefins with Chiral Rhodium Catalysts in the Presence of Anions

The strong influence of various anions upon the hydrogenation of 2-phenyl-1-butene, catalyzed by chiral rhodium catalysts was investigated. Both sulfonates and halides exert large increases in the enantioselectivity when [Rh{(−)-bdpp}(NBD)]ClO4 (bdpp=2,4-bis(diphenylphosphino)pentane, NBD=2,5-norbornadiene) is used as the catalyst precursor at high pressures (70 atm) of dihydrogen in nonpolar solvents. A dihydride mechanism similar to that for Wilkinson\u27s catalyst [RhCl(PPh3)3] was shown to be operating at both high- and low-pressure conditions through a combination of catalytic studies, 31P, 1H and parahydrogen-induced polarization (PHIP) NMR experiments. With sulfonate and in neat methanol, however, a mechanistic switch takes place from a dihydride route (dihydrogen addition before olefin binding) at high pressure to an unsaturate route (olefin binding before dihydrogen addition) at low pressures (\u3c30 \u3eatm). Olefin isomerization is inhibited by halide addition, but occurs with sulfonate and in neat methanol through what is most likely a π-allyl mechanism. A detailed understanding of the effects of addition of these anions is crucial for development of new classes of catalysts capable of efficient enantioselective reduction of prochiral olefins lacking a secondary polar binding group

Phase Space Energization of Ions in Oblique Shocks

Examining energization of kinetic plasmas in phase space is a growing topic of interest, owing to the wealth of data in phase space compared to traditional bulk energization diagnostics. Via the field-particle correlation (FPC) technique and using multiple means of numerically integrating the plasma kinetic equation, we have studied the energization of ions in phase space within oblique collisionless shocks. The perspective afforded to us with this analysis in phase space allows us to characterize distinct populations of energized ions. In particular, we focus on ions which reflect multiple times off the shock front through shock-drift acceleration, and how to distinguish these different reflected populations in phase space using the FPC technique. We further extend our analysis to simulations of three-dimensional shocks undergoing more complicated dynamics, such as shock ripple, to demonstrate the ability to recover the phase space signatures of this energization process in a more general system. This work thus extends previous applications of the FPC technique to more realistic collisionless shock environments, providing stronger evidence of the technique's utility for simulation, laboratory, and spacecraft analysis.Comment: 9 pages, 5 figure

Restoration of rotational invariance of bound states on the light front

We study bound states in a model with scalar nucleons interacting via an exchanged scalar meson using the Hamiltonian formalism on the light front. In this approach manifest rotational invariance is broken when the Fock space is truncated. By considering an effective Hamiltonian that takes into account two meson exchanges, we find that this breaking of rotational invariance is decreased from that which occurs when only one meson exchange is included. The best improvement occurs when the states are weakly bound.Comment: 20 pages, 6 figures, uses feynMF; changed typos, clarified use of angular momentu

Virtual coatings application system

A virtual coatings application system has several features to enhance the realism of simulated spray painting. The system generally includes a display screen on which is defined a virtual surface (such as a truck door) that is intended to be virtually painted or coated by the user. Alternatively, the system includes a head-mounted display unit that displays a virtual spray painting environment in which the virtual surface is defined. The user operates an instrumented spray gun controller that outputs one or more signals representing data as to the status of the controls on the spray gun controller. The system also has a motion tracking system that tracks the position and orientation of the spray gun controller with respect to the virtual surface. Simulation software generates virtual spray pattern data in response to at least the data from the spray gun controller and the position and orientation data received from the tracking system. Virtual spray pattern images are displayed in real time on the virtual surface in accordance with the accumulation of virtual spray pattern data at each location on the virtual surface

Blastomycosis in Ontario, 1994–2003

Clinicians in Ontario should be aware of symptoms and areas where disease is endemic

Instrumental performance and results from testing of the BLAST-TNG receiver, submillimeter optics, and MKID arrays

Polarized thermal emission from interstellar dust grains can be used to map magnetic fields in star forming molecular clouds and the diffuse interstellar medium (ISM). The Balloon-borne Large Aperture Submillimeter Telescope for Polarimetry (BLASTPol) flew from Antarctica in 2010 and 2012 and produced degree-scale polarization maps of several nearby molecular clouds with arcminute resolution. The success of BLASTPol has motivated a next-generation instrument, BLAST-TNG, which will use more than 3000 linear polarization sensitive microwave kinetic inductance detectors (MKIDs) combined with a 2.5m diameter carbon fiber primary mirror to make diffraction-limited observations at 250, 350, and 500 $\mu$m. With 16 times the mapping speed of BLASTPol, sub-arcminute resolution, and a longer flight time, BLAST-TNG will be able to examine nearby molecular clouds and the diffuse galactic dust polarization spectrum in unprecedented detail. The 250 $\mu$m detector array has been integrated into the new cryogenic receiver, and is undergoing testing to establish the optical and polarization characteristics of the instrument. BLAST-TNG will demonstrate the effectiveness of kilo-pixel MKID arrays for applications in submillimeter astronomy. BLAST-TNG is scheduled to fly from Antarctica in December 2017 for 28 days and will be the first balloon-borne telescope to offer a quarter of the flight for "shared risk" observing by the community.Comment: Presented at SPIE Millimeter, Submillimeter, and Far-Infrared Detectors and Instrumentation for Astronomy VIII, June 29th, 201

An open source, FPGA-based LeKID readout for BLAST-TNG: Pre-flight results

We present a highly frequency multiplexed readout for large-format superconducting detector arrays intended for use in the next generation of balloon-borne and space-based sub-millimeter and far-infrared missions. We will demonstrate this technology on the upcoming NASA Next Generation Balloon-borne Large Aperture Sub-millimeter Telescope (BLAST-TNG) to measure the polarized emission of Galactic dust at wavelengths of 250, 350 and 500 microns. The BLAST-TNG receiver incorporates the first arrays of Lumped Element Kinetic Inductance Detectors (LeKID) along with the first microwave multiplexing readout electronics to fly in a space-like environment and will significantly advance the TRL for these technologies. After the flight of BLAST-TNG, we will continue to improve the performance of the detectors and readout electronics for the next generation of balloon-borne instruments and for use in a future FIR Surveyor. Read More: http://www.worldscientific.com/doi/abs/10.1142/S225117171641003