The rearrangement of some cyclopentanone-aryloximes: synthesis of (±)-aplysin, (±)-filiformin and of their debromo analogues.

Upon acid catalyzed rearrangement after Sheradsky, the aryloximes A gave the tricyclic aminals C, which suffered hydrolysis to lactols E. The unique alcohol 29 was then prepared through a highly stereoselective equilibration-reductive alkylation of the epimeric mixture of lactols 22a,b. Two routes, one of which was stereospecific, allowed cyclization of 29 to (±)-aplysin 34. The yield was 2.5 % from oximes 2a,b. The isomeric epi-aplysin 35 and filiformin 36 were also obtained from 29. The debromo analogues 37,38 and 39 and their trideutero derivatives 41,42 and 43 were synthesized along similar line and allowed unequivocal structure elucidation by NMR spectroscopy.     

EPR Studies of Tl0.5Pb0.5Sr1.6Ba0.4CaCu2?xRuxO7?δ Superconductor

Bulk superconducting samples of type Tl_0.5Pb_0.5Sr_1.6Ba_0.4CaCu_2−x Ru _x O_7−δ, (Tl, Pb)/Sr-1212, with 0.0 ≤ x ≤ 0.525 were prepared by the conventional one-step solid-state reaction technique. The prepared samples were investigated using X-ray powder diffraction, electrical resistivity and electron paramagnetic resonance (EPR) measurements. Enhancement of the phase formation, superconducting transition temperature T _c and hole carriers concentration P was observed up to x = 0.075. For x > 0.075, a reverse trend was observed. EPR spectra were measured at different temperatures (120–290 K) for all prepared samples. The number of spins N participating in the resonance and the paramagnetic susceptibility χ were calculated as a function of both Ru-content and temperature. N and χ increased as the Ru-content increased. A linear relationship between logN and 1/T was established, from which the activation energy E _a was calculated as a function of the Ru-content. The temperature dependence of χ was fitted according to Curie–Weiss type of magnetic behavior. Curie constant C, Curie temperature θ, the effective magnetic moment μ and the electronic specific heat γ were estimated as a function of the Ru-content.     

Cyclopolymerisation. 6. Mitt. Darstellung und Eigenschaften von vernetzten cyclopolymerisierten Polyaminen.

Ohne Zusammenfassung     

Effect of IR laser radiation on the structure and optical properties of PC-PBT/Pd polymer nanocomposite films

ABSTRACT

Bayfol (PC-PBT blend ?lm) is a class of polymeric solid-state nuclear track detector which has a lot of applications in several radiation detection ?elds. It is a bisphenol-A polycarbonate PC blended with polybutylene terephthalate PBT. Bayfol/Palladium (PC-PBT/Pd) nanocomposite films have been deposited using the molding technique. It is worth mentioning that this report is almost the first one dealing with the topic of the changes of physical properties of Bayfol/Pd nanocomposite due to laser exposure. Samples from PC-PBT/Pd (5?wt%) nanocomposite were exposed to IR-pulsed laser of 5-W power, capable of producing 2000 pulses per second with pulse duration of 200?ns at 904?nm. The laser fluences were in the range 2–25?J/cm². The resultant modi?cations in the exposed nanocomposite samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction (XRD), UV spectroscopy and color difference studies. The results indicate the proper dispersion of Pd nanoparticles in the PC-PBT matrix that causes a strong intermolecular interaction between Pd and PC-PBT, resulted in an increase in refractive index and the amorphous phase. Also, it is found that the laser exposure reduces the optical energy gap that could be attributed to the increase in structural disorder of the exposed PC-PBT/Pd nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the exposed samples and the non-exposed one, was increased with increasing the laser fluence, convoyed by a significant increase in the green and yellow color components.     

A Novel Niobium Cluster Aqua Ion with Capping μ4‐Se Ligand

The aqueous solution chemistry of niobium is underexplored, and well characterized aqua complexes are scarce. In this contribution, a new niobium aqua complex was obtained by treatment of Zn‐reduced ethanolic solution of NbCl₅ with HCl in the presence of a selenide source (ZnSe). This is the first example of selenium containing aqua complex of niobium. The yellow‐green aqua complex was isolated by cation‐exchange chromatography and transformed into corresponding isothiocyanate complex by ligand exchange, which was crystallized as (PyH)_4.5[H_1.5Nb₄SeO₅(NCS)₁₀] · 0.5H₂O. X‐ray structural analysis revealed a metal‐metal bonded tetranuclear {Nb₄(μ₄‐Se)(μ₂‐O)₅}⁴⁺ core with a capping μ₄‐Se ligand.     

昆虫信息素研究III: 拟蚜虫警戒素的研究

合成了一系列碳数为十五和十四的倍半萜类蚜虫警戒素,并进行了生物活性测定,从中筛选有效化合物.     

The effect of signal duration on the underwater detection thresholds of a harbor porpoise (Phocoena phocoena) for single frequency-modulated tonal signals between 0.25 and 160 kHz

The underwater hearing sensitivity of a young male harbor porpoise for tonal signals of various signal durations was quantified by using a behavioral psychophysical technique. The animal was trained to respond only when it detected an acoustic signal. Fifty percent detection thresholds were obtained for tonal signals (15 frequencies between 0.25-160 kHz, durations 0.5-5000 ms depending on the frequency; 134 frequency-duration combinations in total). Detection thresholds were quantified by varying signal amplitude by the 1-up 1-down staircase method. The hearing thresholds increased when the signal duration fell below the time constant of integration. The time constants, derived from an exponential model of integration [Plomp and Bouman, J. Acoust. Soc. Am. 31, 749-758 (1959)], varied from 629 ms at 2 kHz to 39 ms at 64 kHz. The integration times of the porpoises were similar to those of other mammals including humans, even though the porpoise is a marine mammal and a hearing specialist. The results enable more accurate estimations of the distances at which porpoises can detect short-duration environmental tonal signals. The audiogram thresholds presented by Kastelein et al. [J. Acoust. Soc. Am. 112, 334-344 (2002)], after correction for the frequency bandwidth of the FM signals, are similar to the results of the present study for signals of 1500 ms duration. Harbor porpoise hearing is more sensitive between 2 and 10 kHz, and less sensitive above 10 kHz, than formerly believed.     

The hearing threshold of a harbor porpoise (Phocoena phocoena) for impulsive sounds (L)

The distance at which harbor porpoises can hear underwater detonation sounds is unknown, but depends, among other factors, on the hearing threshold of the species for impulsive sounds. Therefore, the underwater hearing threshold of a young harbor porpoise for an impulsive sound, designed to mimic a detonation pulse, was quantified by using a psychophysical technique. The synthetic exponential pulse with a 5?ms time constant was produced and transmitted by an underwater projector in a pool. The resulting underwater sound, though modified by the response of the projection system and by the pool, exhibited the characteristic features of detonation sounds: A zero to peak sound pressure level of at least 30?dB (re 1?s(-1)) higher than the sound exposure level, and a short duration (34?ms). The animal's 50% detection threshold for this impulsive sound occurred at a received unweighted broadband sound exposure level of 60?dB re 1?μPa(2)s. It is shown that the porpoise's audiogram for short-duration tonal signals [Kastelein et al., J. Acoust. Soc. Am. 128, 3211-3222 (2010)] can be used to estimate its hearing threshold for impulsive sounds.