ICP-MS for elemental speciation studies

The use of inductively coupled plasma mass spectrometry (ICP-MS) coupled with separation techniques for the purpose of elemental speciation has recently gained a lot of attention. Much of this is due to ever improving separation capabilities of Chromatographic techniques, the high sensitivity of ICP-MS, and the continuing development of better interface techniques. Additionally, there is a growing awareness of the need to monitor various species of an analyte, rather than just total analyte concentrations, due to their often varying natures. For the sake of learning from different elemental speciation approaches, this review brings together some selected types of elemental speciation which have been recently seen in literature. These include separations using various forms of liquid chromatography, such as reversed phase, reversed phase ion pairing, micelle, ion exchange, and size exclusion. Elemental speciation employing gas Chromatographie separations and supercritical fluid separations are discussed as well as elemental speciation using capillary electrophoresis.     

Synthesis of 2-substituted benzofurans and indoles using functionalized titanium benzylidene reagents on solid phase

Titanium(IV) benzylidenes bearing a masked oxygen or nitrogen nucleophile in the ortho position were generated from thioacetals, using low-valent titanocene complex, Cp2Ti[P(OEt)3]2. Methylene acetal, alkyl ether, silyl ether, fluoro, tertiary amino, and N-alkyl, N-benzyl, N-prenyl, and N-silyl tert-butyl carbamate groups were tolerated in the titanium alkylidene reagents (Schrock carbenes). Aryl-chlorine bonds were stable to the titanium benzylidene functionality, but there was poor chemoselectivity for the reduction of the thioacetal in the presence of an aryl chloride. The titanium benzylidenes converted Merrifield and Wang resin-bound esters into enol ethers. The oxygen nucleophile was masked as a TMS ether, and when the resin-bound enol ethers bearing this ortho substituent were treated with 1% TFA in dichloromethane, benzofurans were released from resin in high yields. The chameleon catch strategy ensured excellent purity. In a similar way, N-alkylated and N-silylated tert-butyl carbamates were used for the synthesis of N-alkyl and N-Boc indoles, respectively. These traceless solid-phase syntheses of heterocycles are believed to involve postcleavage modification rather than cyclative termination.     

A less formal approach to kaluza-klein formalism

The action integrals (a) and , corresponding respectively to gravitational and gravitational-electromagnetic phenomena, are shown to be related under continuous groups of null translations. This relation motivates a modified Kaluza—Klein formalism for which the classical cylindrical metric preserving transformations (c)y ⁵ = =x ⁵ +f ⁵(x ^j ),y ⁱ =f ⁱ (x ^j ) fori = 1, 2, 3, 4 are replaced by (d)y ⁵ =x ⁵,y ⁱ =f ⁱ (x ^j ,x ⁵). The cylindrical metric of V⁵ is nevertheless preserved under (d), since it is assumed thatV ⁵ admits a metric of the form (corresponding to (a)) and that (d) defines a continuous group of null translations in theV ⁴ metric defined byg _ij whenx ⁵ is considered the group parameter. Application of (d) leads to the cylindrical metric corresponding to (b). The resulting electromagnetic fieldsF _ij =B _i,j –B _j,i are then related to the curvatures of theV ⁴ corresponding tog _ij andh _ij ; in particular it is shown that and . When it is shown thatF _ij is a null electromagnetic field which is generally non-trivial. Some physical and geometric interpretations of the mathematical results are also presented.Dedicated to Professor A. Ostrowski on the occasion of his 75th birthday     

High pressure x-ray diffraction measurements on Mg2SiO4 glass

The structure factors of Mg₂SiO₄ glass have been measured using high energy x-ray diffraction up to pressures of 30.2 GPa, and the equation of state measured up to 12.8 GPa. The average Mg-O coordination numbers were extracted from the experimental pair distribution functions assuming two cases (i) there is no change in Si-O coordination number with pressure and (ii) the average Si-O coordination number increases the same as for pure SiO₂ glass. Both analyses give similar results and show a gradual increase in the average Mg-O coordination number from 5.0 at ambient pressure to ~ 6.6(6) at 30.2 GPa. There is good qualitative agreement between the experimental structure and equation of state data for the glass compared to several recent molecular dynamics simulations carried out on liquid Mg₂SiO₄.