Solid phase extraction GC/ECD method for the analysis of organochlorine pesticides in wildlife plasma

A gas chromatographic method for the analysis of nine organo-chlorine pesticides in wildlife plasma is described. Reversed-phase solid phase extraction is utilized to extract the organochlorine pesticides from plasma. This is followed by a normal phase solid phase extraction clean-up as the pesticides are recovered by elution with hexane:ethyl ether (1:1) and quantified by gas chromatogra-phy/electron capture detection. Method limits of detection range from 7.0–25 μg/L. The mean recovery for all pesticides is 81%.     

Retardation of E1 transitions and the neutron effective charge in 29Si

The effect of the giant dipole resonance on E1 transition rates is investigated, and an expression is derived which allows E1 effective charges to be calculated using the γ-absorption cross section of the neighbouring even-mass core. It is shown how this expression can be approximated using a sum rule in cases where the absorption cross section is not adequately known. Application is made to ²⁹Si; using wave functions from a particle-core model, calculated E1 transition rates are in excellent agreement with experiment.     

Metal-assisted reactions. Part 9. Rapid replacement of phenolic hydroxyl groups by hydrogen.

Conversion of phenolic ethers to hydrocarbons by catalytic transfer hydrogenation is reported.     

Core-polarization and open-shell effects in E6 transitions

The problem of isomeric E6 transitions recently measured in the fp shell is investigated. In the shell model these E6 decay rates require negative proton polarization charges and are quite anomalous in the context of usually enhanced E2 and E4 transitions. We demonstrate that usual core-polarization mechanisms cannot be invoked to explain the data and that the quadrupole deformations of the open shell that must be taken into account are instrumental in yielding negative P₆ moments.     

High surface area Pd, Pt and Ni ion-exchanged Zr, Ti and Sn(IV) phosphates and their application to selective heterogeneous catalytic hydrogenation of alkenes

Amorphous acidic metal(IV) phosphates of zirconium, titanium and tin have been prepared and hydrogen-exchanged for bivalent Pd, Pt and Ni. These bivalent metals were returned to the zero valent state by reducing them with either hydrogen at 400 °C or with sodium tetrahydroborate at room temperature. The resulting Pd⁰, Pt⁰ and Ni⁰ phosphates were investigated as selective catalysts for heterogeneous hydrogenation of alkenes in solution at normal temperatures and pressures and, for Ni, also in the vapour phase. Quantitative studies on rates of hydrogenation are discussed. The usual methods for preparing metal(IV) phosphates give either crystalline or amorphous solids having low specific surfaces areas. A method has been developed, by which metal(IV) phosphates having large surface areas (lsa) may be prepared easily. These lsa supports take up large amounts of transition metal cations by simple exchange. The enhanced incorporation of Pd, Pt or Ni and increases in surface areas of the phosphate supports have provided some active, selective catalysts. Pd/Ti phosphates were the most active and compared well with commercial Pd on carbon. Ni/Ti phosphate is a very selective catalyst for vapour phase hydrogenation of alkenes and, at slightly higher temperatures, it is an efficient hydrocarbon cracking catalyst.     

Desymmetrization of an Octahedral Coordination Complex Inside a Self‐Assembled Exoskeleton

The synthesis of a centrally functionalized, ribbon‐shaped [6]polynorbornane ligand L that self‐assembles with Pd^II cations into a {Pd₂ L ₄} coordination cage is reported. The shape‐persistent {Pd₂ L ₄} cage contains two axial cationic centers and an array of four equatorial H‐bond donors pointing directly towards the center of the cavity. This precisely defined supramolecular environment is complementary to the geometry of classic octahedral complexes [M(XY)₆] with six diatomic ligands. Very strong binding of [Pt(CN)₆]^2? to the cage was observed, with the structure of the host–guest complex {[Pt(CN)₆]@Pd₂L₄} supported by NMR spectroscopy, MS, and X‐ray data. The self‐assembled shell imprints its geometry on the encapsulated guest, and desymmetrization of the octahedral platinum species by the influence of the D_4h‐symmetric second coordination sphere was evidenced by IR spectroscopy. [Fe(CN)₆]^3? and square‐planar [Pt(CN)₄]^2? were strongly bound. Smaller octahedral anions such as [SiF₆]^2?, neutral carbonyl complexes ([M(CO)₆]; M=Cr, Mo, W) and the linear [Ag(CN)₂]^? anion were only weakly bound, showing that both size and charge match are key factors for high‐affinity binding.     

Birationally rigid singular double quadrics and double cubics

Mathematical Notes - In this paper it is shown that Fano double quadrics of index 1 and dimension at least 6 are birationally superrigid if the branch divisor has at most quadratic singularities of...