Palladium-catalyzed cross-coupling reactions of in situ generated allylindium reagents with aryl halides

[reaction: see text] In situ generated allylindium reagents from the reaction of 1 equiv of indium with 1.5 equiv of allyl halides could be effective cross-coupling partners in palladium-catalyzed cross-coupling reactions to aryl halides. The best results were obtained with 2% Pd(2)dba(3)CHCl(3) and 16% Ph(3)P in the presence of 3 equiv of LiCl in DMF at 100 degrees C.     

Photoluminescence of AlxGa1−xAs/GaAs quantum well heterostructures grown by molecular beam epitaxy

Low-temperature photoluminescence measurements on nominally undoped Al_xGa_1–xAs/GaAs quantum well heterostructures (QWHs) grown by molecular beam epitaxy (MBE) exemplified the exclusivelyintrinsic free-exciton nature of the luminescence under moderate excitation conditions. Neither any spectroscopic evidence for alloy clustering in the Al_xGa_1–xAs barriers nor any extrinsic luminescence due to recombination with residual acceptors has been detected in single and double QWHs when grown at 670 °C under optimized MBE growth conditions. Carrier confinement in Al_xGa_1–xAs/GaAs QWHs starts at a well width ofL _z30 nm when x0.25. The minor average well thickness fluctuation ofL _z=4×10^–2nm as determined from the excitonic halfwidth allowed the realization of well widths as low asL _z=1 nm and thus a shift of the free-exciton line as high as 2.01 eV which is close to the conduction band edge of the employed Al_0.43Ga_0.57As confinement layer. The measurements further revealed a strongly enhanced luminescence efficiency of the quantum wells as compared to bulk material which is caused by the modified exciton transition probabilities due to carrier localization.     

Trace analysis of volatile polar organics by direct aqueous injection gas chromatography

Summary Procedures for the quantitative analysis of industrial effluents which involve concentration by solvent extraction or the purge-and-trap method are time-consuming, labor-intensive, and prone to error. Direct aqueous injection gas chromatography using an electron-capture detector for the analysis of volatile halocarbons at the ppb level is in routine use in many laboratories. We now discuss the development of a similar protocol for the analysis of volatile polar organics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and tretrahydrofuran using a flame-ionization detector.     

Intraframework potential energy function of zeolites

Potential energy functions suitable for the (Cs_1–xNa_xT₂O₄)-A type zeolite family were obtained from the known crystal structure of Cs₇Na₅-A zeolite. Using these potential functions, several other crystal structures in these family were obtained by molecular mechanical calculations. The activation energy - to -cage transmission of the H₂ molecule and the void volume of Cs₃Na₉-A zeolite were calculated.     

Photoluminescence of Al x Ga1−x As/GaAs quantum well heterostructures grown by molecular beam epitaxy

Nominally undoped Al_xGa_1–xAs grown by molecular beam epitaxy from As₄ species at elevated substrate temperatures of 670°C exhibits well-resolved excitonic fine structure in the low-temperature photoluminescence spectra, if the effective As-to-(Al+Ga) flux ratio on the growth surface is kept within a rather narrow range of clearly As-stabilized conditions. In contrast to previous results on Al_xGa_1–xAs of composition 0.15not to shift in energy by changing the excitation intensity. This implies a simple freeelectron carbon-acceptor recombination mechanism for the line without any participation of a donor. In Al_xGa_1–xAs of composition close to the direct-to-indirect cross-over point, two distinct LO-phonons separated by 34 and 48 meV from the (D ⁰,C ⁰) peak position at x=0.43 were observed which were before only detectable by Raman scattering experiments. The intensity of the carbon-impurity related luminescence lines in bulk-type Al_xGa_1–xAs and GaAs layers was found to be strongly reduced, as compared to the excitonic recombination lines, if the respective active layer was covered by a very thin confinement layer of either GaAs on top of Al_xGa_1–xAs or vice versa grown in the same growth cycle.     

Morphology and transport properties of protons and methanol through partially sulfonated block copolymers

The morphological changes with different compositions of casting solvents in the membranes of sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) were investigated with small-angle X-ray scattering (SAXS) and transmission electron microscope (TEM). Using the single solvent of tetrahydrofuran (THF) and the solvent mixtures of methanol/THF with different compositions, the casting polymer solutions were prepared for the membrane fabrication. The proton conductivity and the methanol permeability of membranes were measured, and the effect of morphological changes on the casting solvents was discussed through Flory–Huggins theory. It was found that the sulfonated SEBS membranes were transformed from well ordered lamellar to disordered co-continuous structure and the morphological difference caused abrupt enhancement in the proton conductivity and the methanol permeability as the concentration of methanol in the mixed solvents (MeOH/THF) increased.     

The Structure of the Antibiotic Hedamycin. I. Chemical,Physical and Spectral Properties

Interpretation of the chemical and spectral (IR., UV., ¹H- and ¹³C-NMR.) properties of the antitumor antibiotic hedamycin (C₄₁H₅₀N₂O₁₁) suggests that the molecule contains a methyl substituted 1-hydroxyanthraquinone nucleus, an α, β-unsaturated ketone, two sugar-like tetrahydropyran rings ( 4 and 8 ) and an aliphatic chain 2 , presumably with an epoxy group (see the Scheme).     

Ga8Ir4B – ein Gallium-Iridiumborid mit isolierten,annähernd quadratisch planaren Ir4B-Gruppen in einer vom CaF2-Typ abgeleiteten Struktur

Ga₈Ir₄B – a Gallium Iridium Boride with isolated, nearly square planar Ir₄B Groups in a Structure derived from the CaF₂ Type The new compound Ga₈Ir₄B (tetragonal, I4₁/acd, a = 853.69(2) pm, c = 2 105.69(6) pm, Z = 8, 614 reflections, 31 parameters, R = 0.034) was prepared by reaction of the elements at 1 100°C. The structure is derived from the CaF₂ type. It contains isolated Ir₄B groups with boron in an unusual, nearly square planar coordination.     

Identification of flavonoids using liquid chromatography with electrospray ionization and ion trap tandem mass spectrometry with an MS/MS library

Searchable MS/MS spectra libraries, constructed using the results of liquid chromatography coupled with electrospray ionization (ESI) tandem mass spectrometry (LC/MS/MS) with data-dependent acquisition on an ion trap mass spectrometer, are presented with regard to the identification and confirmation of a variety of closely related flavonoids in a set of biological samples. Flavonoids were found to exhibit a maximum amount of structurally specific MS/MS spectra at 45% of normalized collision energy on the instrument used, without wideband activation. These MS/MS spectra were then searched automatically against a 297-substance MS/MS library that contains many previously acquired spectra of standard flavonoids. The possible applications of this powerful technique to biological samples are also discussed. Daidzein and genistein were identified through the MS/MS spectra library while searching through LC/MS/MS data for plant and microbial extracts. Moreover, these compounds proved completely distinguishable from other flavonoids of closely related structures in the MS/MS spectra library, using the NIST MS search program. The applicability of the library-searchable spectra at low concentrations was demonstrated by successful identification of daidzein and genistein at 0.05 and 0.5 microg/mL, respectively.     

Efficient total synthesis of pulchellalactam,a CD45 protein tyrosine phosphatase inhibitor

A new approach to a CD45 protein tyrosine phosphatase inhibitor, pulchellalactam, is described. The key step of the sequence involves addition and elimination of an enolic lactam in a single step and 70% yield, employing an organocuprate reagent. The resulting alpha,beta-unsaturated lactam could be condensed with isobutyraldehyde to produce Z-pulchellalactam or converted into siloxypyrrole, which was subjected to the BF(3) x Et(2)O-promoted coupling reaction with isobutyraldehyde to afford E-pulchellalactam after E1-cB elimination and TFA deprotection. This first total synthesis afforded Z-pulchellalactam in six steps and 32% overall yield from Boc-glycine. The same sequence of reactions could also be applied to the liquid- or solid-phase synthesis of trifunctionalized pulchellalactam derivatives.