Homoatomic P --> P coordination: a versatile synthetic approach to polyphosphorus dications

Polyphosphorus dications have been synthesised and comprehensively characterised as diphosphine (dppe, dmpe and dpph) linked Ar2P+ Lewis acids (Ar = C6H5); this application of unique homoatomic coordination chemistry provides important building blocks for extended systems.     

Chemicals from forest products by supercritical fluid extraction

Supercritical acetone or methanol extraction of wood gave liquid products with a maximum yield of 74%. Approximately 5% of these complex products was identified as substituted guaiacols and levoglucosan. Acetone extract could substitute for 30% of the phenol in phenolic resins.

Resin and fatty acids were extracted from southern pine and waxes from Douglas-fir bark using supercritical carbon dioxide, nitrous oxide, propane or ethylene. Of these, propane and nitrous oxide gave the best yields.     

Study of cross-conjugated iso-polytriacetylenes and related oligoenynes

Two series of monodisperse cross-conjugated oligomers based on enyne repeat units have been realized. The first class of molecules, iso-polytriacetylenes (iso-PTAs, 2), was divergently synthesized using an iterative sequence of palladium-catalyzed cross-coupling reactions of vinyl triflate 5 with terminal alkynes. The second series of oligoenynes (17-20) are based on an octatetrayne backbone, and result from homocoupling of the differentially protected iso-PTA oligomers 8-11. The longest member of this series, 20, spans ca. 5.6 nm from Si atom to Si atom and is composed of a contiguous sequence of 44 sp and sp(2) carbons. The lowest energy electronic absorption band for iso-PTA dimers in the progression 13 --> 9 --> 16 is consistently red-shifted as a result of extending the cross-conjugated structure. A similar comparison within each series (i.e., 16, 6-7, or 17-20), however, suggests little effect on the electronic characteristics of these molecules as oligomer length is increased. The solid-state properties of one derivative, 17, are also described.     

Copper(II) coordination to ligands immobilized on photoluminescent porous silicon

Increased preorganization can be achieved by immobilizing ligands on solid supports. Photoluminescent porous silicon, which can undergo facile hydrosilylation, was used as a support for open chain neutral N- and O-donor ligands. The abilities of these ligands to bind the divalent metal ions Ni(2+), Cu(2+), Zn(2+), and Pb(2+) are examined. Immobilized ligands selectively complexed Cu(II) over the other metal ions studied. Ligands immobilized on photoluminescent porous silicon also removed a significant amount, up to 98%, of Cu(II) from copper(II)-spiked, organic-rich, seawater samples.     

Ion flotation of zinc using ethylhexadecyldimethylammonium bromide

Zinc ions react with the surfactant ethylhexadecyldimethylammonium bromide (EHDABr) to form a surface active sublate which can be removed from aqueous chloride solutions by ion flotation. A typical ion flotation procedure involves passing air through a 235-ml solution containing 5 ppm Zn²⁺, 2.0 M HCl, and 2.5 × 10^?3M EHDABr at a flow rate of 40 ml/min for 150 min. The procedure is simple and rapid. Cadmium, copper, lead, and nickel ions cause reductions of zinc flotation efficiencies of less than 2.5% under the experimental conditions.     

Determination of the distribution of cannabinoids in cannabis resin from the Lebanon using HPLC. Part III

Samples taken from 61 slabs of cannabis resin originating in The Lebanon were examined by high performance liquid chromatography. The slabs were derived from seizures of cannabis resin made over a three-year period. From a study of 14 of these samples, taken from bags which bore a number of identical stamp marks, it was shown that there was a correlation between the cannabinoid distribution and the marks. The remaining 47 samples of cannabis resin, all of which were from bags with different marks, were each found to have a unique cannabinoid distribution. Such an examination can therefore be used to aid investigations where evidence of a common origin is sought.     

Electron-impact ionization of CCl4 and CCl2F2

Absolute partial and total cross sections for electron-impact ionization of CCl4 and CCl2F2 are reported for electron energies from threshold to 1000 eV. The product ions are mass analyzed using a time-of-flight mass spectrometer and detected with a position-sensitive detector whose output demonstrates that all product ion species are collected with equal efficiency irrespective of their initial kinetic energies. Data are presented for production of CCl3(+), CCl2(+), CCl+, C+, Cl2(+), and CCl3(2+) from CCl4; and for production of CCl(2)F+, CClF2(+), CClF(+), (CCl+ + CF2(+)), Cl+, CF+, F+, and C+ from CCl2F2. Data are also reported for formation of (CCl2(+),Cl+) and (CCl+, Cl+) ion pairs from CCl4. The total cross section for each target is obtained as the sum of the partial cross sections. The overall uncertainty in the absolute cross sections for most of the singly charged ions is +/- 5-7 %. The present partial cross sections for lighter fragment ions are found to be considerably greater than had been previously reported but the most recent total cross section measurements agree well with those reported here. Neither the binary-encounter-Bethe theory nor the Deutsch-Mark theory reproduces the experimental cross sections correctly for both targets.     

Use of γ-γ Coincidence Spectrometry in the Geochemical Study of Diamictites from South Africa

We used - coincidence spectrometry to investigate the possible presence of a meteoritical component in 27 samples of South African diamictites. Recently, several studies have suggested that some tillites/diamictites may represent impact breccias, but a petrographical study by our group found no evidence for the presence of impact-characteristic shocked minerals. The siderophile elements, such as Cr, Co, Ni, and, especially, the platinum group elements, have high abundances in meteorites, but low abundances in terrestrial crustal rocks. The Ir content of the diamictites was measured with the new iridium coincidence spectrometer (ICS) at the University of Vienna, with detection limits of around 0.02 ppb. No enrichments in the contents of Ir and other siderophile elements compared to average crustal concentrations were found; thus, no unequivocal evidence for an impact origin of these diamictites of the South African Dwyka Group can be documented.