Photochemical Reductive trans-Elimination from trans-Diacidotetracyanoplatinate(IV) Complexes

Abstract Upon CT excitation the complex ions trans-[Pt(CN)4N3X]2- and trans-[Pt(CN)4X2]2- (X = Cl and Br) undergo a reductive trans-elimination with formation of [Pt(CN)4]2- and two ligand radicals in the photoprimary step. The formation of a Pt(III) intermediate is not observed. Due to the stability of [Pt(CN)4]2-, recombination reactions regenerating the starting complex are efficient if the ligand radicals are not scavenged. For the azide complexes the high quantum yields for the production of [Pt(CN)4]2- are explained by the instability of azide radicals. For trans-[Pt(CN)4X2]2-, the recombination is efficient in aqueous solution, while in ethanol the halogen atoms are scavenged by hydrogen abstraction. The sequence of steps following CT excitation can be explained by a potential energy diagram.</jats:p

Origin of Rashba-splitting in the quantized subbands at Bi2Se3 surface

We study the band structure of the $\text{Bi}_2\text{Se}_3$ topological insulator (111) surface using angle-resolved photoemission spectroscopy. We examine the situation where two sets of quantized subbands exhibiting different Rashba spin-splitting are created via bending of the conduction (CB) and the valence (VB) bands at the surface. While the CB subbands are strongly Rashba spin-split, the VB subbands do not exhibit clear spin-splitting. We find that CB and VB experience similar band bending magnitudes, which means, a spin-splitting discrepancy due to different surface potential gradients can be excluded. On the other hand, by comparing the experimental band structure to first principles LMTO band structure calculations, we find that the strongly spin-orbit coupled Bi 6$p$ orbitals dominate the orbital character of CB, whereas their admixture to VB is rather small. The spin-splitting discrepancy is, therefore, traced back to the difference in spin-orbit coupling between CB and VB in the respective subbands' regions

Optical Pulse-Phased Photopolarimetry of PSR B0656+14

We have observed the optical pulse profile of PSR B0656+14 in 10 phase bins at a high signal-to-noise ratio, and have measured the linear polarization profile over 30% of the pulsar period with some significance. The pulse profile is double-peaked, with a bridge of emission between the two peaks, similar to gamma-ray profiles observed in other pulsars. There is no detectable unpulsed flux, to a 1-sigma limit of 16% of the pulse-averaged flux. The emission in the bridge is highly (~ 100%) polarized, with a position angle sweep in excellent agreement with the prediction of the Rotating Vector Model as determined from radio polarization observations. We are able to account for the gross features of the optical light curve (i.e., the phase separation of the peaks) using both polar cap and outer gap models. Using the polar cap model, we are also able to estimate the height of the optical emission regions.Comment: 27 pages, 11 figures, accepted by ApJ (scheduled v597 n2, November 10, 2003

CPPD crystal deposition disease in patients with rheumatoid arthritis

The aim of this study was to assess the frequency and the outcome of patients suffering from rheumatoid arthritis in which calcium pyrophosphate dihydrate (CPPD) crystal deposits were found to coexist in synovial fluid analysis. Such association was more frequent than previously believed with CPPD crystals found in 25.8% of 93 patients with rheumatoid arthritis. As a group, a trend toward a worse outcome was suggested by more frequent prostheses of the lower lim

Shuttle flight pressure instrumentation: Experience and lessons for the future

Flight data obtained from the Space Transportation System orbiter entries are processed and analyzed to assess the accuracy and performance of the Development Flight Instrumentation (DFI) pressure measurement system. Selected pressure measurements are compared with available wind tunnel and computational data and are further used to perform air data analyses using the Shuttle Entry Air Data System (SEADS) computation technique. The results are compared to air data from other sources. These comparisons isolate and demonstrate the effects of the various limitations of the DFI pressure measurement system. The effects of these limitations on orbiter performance analyses are addressed, and instrumentation modifications are recommended to improve the accuracy of similar fight data systems in the future

Lethal Parasites in Oysters from Coastal Georgia with Discussion of Disease and Management Implications

Extensive mortalities of oysters, Crassostrea virginica, occurred from 1985 through 1987 in coastal waters of Georgia. Fluid thioglycolate cultures of oysters collected from 16 of 17 locations revealed infections by the apicomplexan parasite Perkinsus marinus. An ascetosporan parasite, Haplosporidium nelsoni, was also observed in histopathological examination of oysters from 4 of the locations. While the range of H. nelsoni currently is recognized as the east coast of the United States from Maine to Florida, this is the first report of the parasite in Georgia waters. This paper documents the occurrence of these two lethal parasites in oysters from coastal waters of Georgia, along with potential disease and management implications. Results of an earlier independent and previously unpublished survey are also discussed which document the presence of P. marinus in Georgia as early as 1966

Integrated Atom Detector Based on Field Ionization near Carbon Nanotubes

We demonstrate an atom detector based on field ionization and subsequent ion counting. We make use of field enhancement near tips of carbon nanotubes to reach extreme electrostatic field values of up to 9x10^9 V/m, which ionize ground state rubidium atoms. The detector is based on a carpet of multiwall carbon nanotubes grown on a substrate and used for field ionization, and a channel electron multiplier used for ion counting. We measure the field enhancement at the tips of carbon nanotubes by field emission of electrons. We demonstrate the operation of the field ionization detector by counting atoms from a thermal beam of a rubidium dispenser source. By measuring the ionization rate of rubidium as a function of the applied detector voltage we identify the field ionization distance, which is below a few tens of nanometers in front of nanotube tips. We deduce from the experimental data that field ionization of rubidium near nanotube tips takes place on a time scale faster than 10^(-10)s. This property is particularly interesting for the development of fast atom detectors suitable for measuring correlations in ultracold quantum gases. We also describe an application of the detector as partial pressure gauge.Comment: 7 pages, 8 figure