Chemo-, regio-, and enantioselective Pd-catalyzed allylic alkylation of indolocarbazole pro-aglycons

[reaction: see text] Monosubstituted isomerically pure indolopyrrolocarbazole precursors have been prepared via palladium-catalyzed asymmetric allylic alkylation methodology, employing both achiral cyclopentenyl electrophiles and chiral glycal derivatives. Chemoselective allylation of (bis)indole lactam pro-aglycon 3 allows access to N-distally substituted indolopyrrolocarbazole derivatives; glyoxamide precursor 14 provides entry into N-proximally substituted derivatives.     

Microwave oscillator based on Bloch oscillations of electrons in a semiconductor superlattice

We report on a microwave oscillator based on Bloch oscillations of electrons in a semiconductor superlattice. Our GaAs/AlAs superlattice, at room temperature, was coupled electromagnetically by an antenna to a rectangular cavity resonator, and was operated at a current-voltage state of negative differential conductance. We observed generation of microwave radiation at frequencies, depending on the resonator length, between 7 and 30 GHz. Electronic tuning by several percent was possible; the ratio of linewidth to frequency was of the order of 10^?4. A radiation power up to 1 μW (at 10 GHz) was obtained, corresponding to a generator efficiency of the order of 10^?3 for the conversion of electrical power to microwave radiation.     

Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.     

The microscopic investigation of structures of moving flux lines by neutron and muon techniques

We have used a variety of microscopic techniques to reveal the structure and motion of flux line arrangements, when the flux lines in low T _c type II superconductors are caused to move by a transport current. Using small-angle neutron scattering by the flux line lattice (FLL), we are able to demonstrate directly the alignment by motion of the nearest-neighbor FLL direction. This tends to be parallel to the direction of flux line motion, as had been suspected from two-dimensional simulations. We also see the destruction of the ordered FLL by plastic flow and the bending of flux lines. Another technique that our collaboration has employed is the direct measurement of flux line motion, using the ultra-high-resolution spectroscopy of the neutron spin-echo technique to observe the energy change of neutrons diffracted by moving flux lines. The muon spin rotation (μSR) technique gives the distribution of values of magnetic field within the FLL. We have recently succeeded in performing μSR measurements while the FLL is moving. Such measurements give complementary information about the local speed and orientation of the FLL motion. We conclude by discussing the possible application of this technique to thin film superconductors.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Origin of ferromagnetism in iron implanted rutile single crystals

⁵⁷Fe doped titanium oxide monocrystals, prepared by ion implantation at different temperatures and subsequent thermal treatment, were characterized by conversion electron Mössbauer spectrometry, synchrotron radiation x-ray diffraction and superconducting quantum interference device magnetometry. After implantation at room temperature Fe is present in divalent state. Upon annealing in high vacuum Fe^2?+? is reduced to metallic Fe for the most part. After implantation at 623 K most iron is in metallic state. During annealing on air Fe is gradually oxidized from Fe^2?+? to Fe^3?+?. Depending on preparation conditions and thermal treatment the role of different nanosized secondary phases is discussed in terms of their influence on the magnetic properties of Fe:TiO₂. α-Fe nanoparticles are found to be responsible for ferromagnetism observed in TiO₂.     

X-ray investigation of the interface structure of free standing InAs nanowires grown on GaAs [\bar{1}\bar {1}\bar{1}]_{\mathrm{B}}

The heteroepitaxial growth process of InAs nanowires (NW) on GaAs $[\bar{1}\bar{1}\bar{1}]_{\mathrm{B}}$ substrate was investigated by X-ray grazing-incidence diffraction using synchrotron radiation. For crystal growth we applied the vapor–liquid–solid (VLS) growth mechanism via gold seeds. The general sample structure was extracted from various electron microscopic and X-ray diffraction experiments. We found a closed Ga _x In_1?x As graduated alloy layer at the substrate to NW interface which was formed in the initial stage of VLS growth with a Au–Ga–In liquid alloy. With ongoing growth time a transition from this VLS layer growth to the conventional VLS NW growth was observed. The structural properties of both VLS grown crystal types were examined. Furthermore, we discuss the VLS layer growth process.     

THz-field induced nonlinear transport and dc voltage generation in a semiconductor superlattice due to Bloch oscillations

We report on a theoretical analysis of terahertz (THz-) field induced nonlinear dynamics of electrons in a semiconductor superlattice that are capable to perform Bloch oscillations. Our results suggest that for a strong THz-field a dc voltage should be generated. We have analyzed the real-time dynamics using a balance equation approach to describe the electron transport in a superlattice miniband. Taking account of both Bloch oscillations of electrons in a superlattice miniband and dissipation, we studied the influence of a strong THz-field on currently available superlattices at room temperature. We found that a THz-field can lead to a negative conductance resulting in turn in a THz-field induced dc voltage, and that the voltage per superlattice period should show, for varying amplitue of the THz-field, a form of wisted plateaus with the middle points being with high precision equal to the photon energy divided by the electron charge. We show voltage to the finite voltage state, and that in the finite voltage state dynamic localization of the electrons in a miniband occurs.