Palladium-catalyzed cross-coupling in the synthesis of pyridinyl boxazomycin C analogues

[reaction: see text] Palladium-catalyzed cross-coupling of 2-thiomethylbenzoxazoles with tri-alkylstannyl pyridines efficiently produces pyridinyl boxazomycin C analogues.     

Naphthalene-1,2,3-dithiazolyl and its selenium-containing variants

Synthetic routes to salts of the 3H-naphtho[1,2-d][1,2,3]dithiazolylium cation and its three selenium-containing variants (SSeN, SeSN, and SeSeN) are described. The most efficient and general method involves the intermediacy of bis-acetylated aminothiolates and aminoselenolates. These reagents react smoothly with sulfur and selenium halides to afford the desired ring closure products. Electrochemical reduction of the four cations indicates that corresponding radicals (SSN, SSeN, SeSN, and SeSeN) are stable in solution. The EPR spectra of all four have been recorded, and experimental spin distributions have been cross-matched with those obtained from DFT calculations. The selenium-containing radicals are thermally unstable at or slightly above room temperature, but the all-sulfur species has been isolated and characterized crystallographically. In the solid state, the radicals are associated into cofacial dimers which are closely linked to other dimers by intermolecular S---S, S---N, and C-H---aromatic ring interactions.     

The effect of selenium incorporation on the bandwidth and conductivity of neutral radical conductors

The first example of an undimerized pi-stacked bis-1,2,3-thiaselenazolyl radical displays improved bandwidth and conductivity relative to an isostructural bis-1,2,3-dithiazolyl.     

Enzyme-catalysed nitrate reduction-themes and variations as revealed by protein film voltammetry

Protein film voltammetry has been used to define the catalytic performance of two nitrate reductases: the respiratory nitrate reductase, NarGH, from Paracoccus pantotrophus and the assimilatory nitrate reductase, NarB, from Synechococcus sp. PCC 7942. NarGH and NarB present distinct "fingerprints" of catalytic activity when viewed in this way. Potentials that provide insufficient driving force for significant rates of nitrate reduction by NarB result in appreciable rates of nitrate reduction by NarGH. However, both enzymes display complex modulations in their rate of substrate reduction when viewed across the electrochemical potential domain.     

Practical low-noise stretched-pulse Yb(3+)-doped fiber laser

We report on the development of what we consider to be a practical and highly stable stretched-pulse laser based on Yb(3+) -doped silica fiber. The Fabry-Perot cavity uses nonlinear polarization rotation as the mode-locking mechanism, and a semiconductor saturable-absorber mirror to ensure robust self-starting and incorporates a diffraction grating pair to compensate for the normal dispersion of the fiber. Use of a single-mode grating-stabilized telecommunications-qualified pump laser diode ensures reliable, low-noise operation (~0.05% amplitude fluctuations at 10-Hz measurement bandwidth). The laser generates high-quality, 60-pJ pulses of <110-fs duration at a repetition rate of ~54 MHz (3-mW average power).     

Continuous synthesis of YBa2Cu3O6+x by thermal explosion in a rotary kiln

Continuous synthesis of YBa₂Cu₃O_6+x superconductor was conducted in a rotary kiln. Dense pellets or loose powder of a stoichiometric mixture of copper, barium peroxide, and yttrium oxide were fed into a heated rotary kiln causing ignition on the whole outer surface followed by an inward movement of a combustion front. Following this thermal explosion, the pellet was post-treated (sintered) at 900 to 985°C as it moved along the kiln, and a product containing about 95 wt% YBa₂Cu₃O_6+x was obtained. The impact of the thermal-explosion temperature, the post-treatment temperature, the pellet density, and the total residence time in the kiln on the product quality were studied. The best thermal-explosion temperature was found to be 800°C, the best post-treatment temperature was 985°C, and the total residence time in the kiln of 100 minutes was sufficient for the pellet to reach equilibrium.     

Symmetry breaking and branching patterns in equivariant bifurcation theory II

Communicated by M. Golubitsky     

Reactions of bowhead whales, Balaena mysticetus, to seismic exploration in the Canadian Beaufort Sea

The behavioral reactions of bowhead whales to distant seismic vessels not under our control, a controlled approach by a seismic vessel, and controlled tests with a single airgun were observed. On 21 occasions in the summers of 1980-84, general activities of bowheads exposed to pulses of underwater noise (107-158 dB re: 1 mu Pa) from seismic vessels 6-99 km away were observed. Activities were indistinguishable from those without seismic noise; there was no detectable avoidance. Hints of subtle changes in surfacing, respiration, and diving behavior were unconfirmed, but were consistent with reactions to stronger noise pulses from closer seismic boats. In a test with a full-scale seismic boat (30 airguns totaling 471, source level 248 dB re: 1 mu Pa, closest point of approach = 1 1/2 km), bowheads began to orient away when the airgun array began to fire 7 1/2 km away. However, some whales continued apparent near-bottom feeding until the vessel was 3 km away. Whales were displaced by about 2 km. Reactions were not much stronger than those to any conventional vessel. Tests with one 0.66-1 airgun showed that some bowheads move away from sources of strong seismic impulses even in the absence of boat noise, and that bowheads can detect the direction from which seismic impulses arrive. In general, bowheads exhibit avoidance reactions when they receive seismic pulses stronger than about 160 dB re: 1 mu Pa. Evidence of reactions to lower received levels remains inconclusive.