The separation and determination of niobium and tantalum by partition chromatography

A procedure is outlined for the separation and determination of niobium and tantalum by paper chromatography. A mixture of methyl isobutyl ketone and hydrofluoric acid was used as solvent and the metals were detected by means of 8-hydroxyquinoline. The minimum amount of each element detectable is 20 μg.

The procedure was applied successfully to the quantitative determination of small amounts of niobium and tantalum in a steel.     

A thermogravimetry/differential thermal analysis,evolved gas analysis and pyrolysis/gas chromatography—mass spectrometry study of tetrakis (diethyldithiocarbamato)tin(IV)

The thermal decomposition of tetrakis(diethyldithiocarbamato)tin(IV) has been studied by TG/DTA, EGA and P/GC-MS techniques. From the P/GC-MS analysis, it is apparent that the denticity of the dithiocarbamate ligand influences the mechanism of decomposition. Initially, the monodentate ligands decompose by a radical mechanism to form tetraethylthiuramdisulphide which decomposes further into carbon disulphide and diethylamine. The intermediate formed, bis(diethydithiocarbamato)tin(II), decomposes in two different ways. The bidentate ligands decompose with the liberation of carbon disulphide and tetraethylthiourea, whereas the monodentate ligands, formed as a result of the high temperatures, decompose to produce S-ethyl N,N-diethyldithiocarbamate and ethylisothiocyanate. The overall thermal decomposition mechenism of tetrakis(diethyldithiocarbamato)tin(IV) is complex and the primary decomposition involved both ionic and radical recombination reactions.     

Detecting evolving patterns of self‐organizing networks by flow hierarchy measurement

Hierarchies occur widely in evolving self‐organizing ecological, biological, technological, and social networks, but detecting and comparing hierarchies is difficult. Here we present a metric and technique to quantitatively assess the extent to which self‐organizing directed networks exhibit a flow hierarchy. Flow hierarchy is a commonly observed but theoretically overlooked form of hierarchy in networks. We show that the ecological, neurobiological, economic, and information processing networks are generally more hierarchical than their comparable random networks. We further discovered that hierarchy degree has increased over the course of the evolution of Linux kernels. Taken together, our results suggest that hierarchy is a central organizing feature of real‐world evolving networks, and the measurement of hierarchy opens the way to understand the structural regimes and evolutionary patterns of self‐organizing networks. Our measurement technique makes it possible to objectively compare hierarchies of different networks and of different evolutionary stages of a single network, and compare evolving patterns of different networks. It can be applied to various complex systems, which can be represented as directed networks. © 2011 Wiley Periodicals, Inc. Complexity, 2011     

Viscoelastic suppression of gravity-driven counterflow instability

Attempts to achieve "top kill" of flowing oil wells by pumping dense drilling "muds," i.e., slurries of dense minerals, from above will fail if the Kelvin-Helmholtz instability in the gravity-driven counterflow produces turbulence that breaks up the denser fluid into small droplets. Here we estimate the droplet size to be submillimeter for fast flows and suggest the addition of a shear-thickening or viscoelastic polymer to suppress turbulence. We find in laboratory experiments a variety of new physical effects for a viscoelastic shear-thickening liquid in a gravity-driven counterstreaming flow. There is a progression from droplet formation to complete turbulence suppression at the relevant high velocities. Thick descending columns show a viscoelastic analogue of the viscous buckling instability. Thinner streams form structures resembling globules on a looping filament.     

Solution structure of a DNA duplex containing the potent anti-poxvirus agent cidofovir

Cidofovir (1(S)-[3-hydroxy-2-(phosphonomethoxy)propyl]cytosine, CDV) is a potent inhibitor of orthopoxvirus DNA replication. Prior studies have shown that, when CDV is incorporated into a growing primer strand, it can inhibit both the 3'-to-5' exonuclease and the 5'-to-3' chain extension activities of vaccinia virus DNA polymerase. This drug can also be incorporated into DNA, creating a significant impediment to trans-lesion DNA synthesis in a manner resembling DNA damage. CDV and deoxycytidine share a common nucleobase, but CDV lacks the deoxyribose sugar. The acyclic phosphonate bears a hydroxyl moiety that is equivalent to the 3'-hydroxyl of dCMP and permits CDV incorporation into duplex DNA. To study the structural consequences of inserting CDV into DNA, we have used (1)H NMR to solve the solution structures of a dodecamer DNA duplex containing a CDV molecule at position 7 and of a control DNA duplex. The overall structures of both DNA duplexes were found to be very similar. We observed a decrease of intensity (>50%) for the imino protons neighboring the CDV (G6, T8) and the cognate base G18 and a large chemical shift change for G18. This indicates higher proton exchange rates for this region, which were confirmed using NMR-monitored melting experiments. DNA duplex melting experiments monitored by circular dichroism revealed a lower T(m) for the CDV DNA duplex (46 °C) compared to the control (58 °C) in 0.2 M salt. Our results suggest that the CDV drug is well accommodated and stable within the dodecamer DNA duplex, but the stability of the complex is less than that of the control, suggesting increased dynamics around the CDV.     

Investigation of the electronic band structure of some linear polysilicates

The one-dimensional LCAO tight-binding method was applied to the study of the electronic structure of a model for a regular polymeric orthosilicic acid and its mono-sodium, di-sodium and calcium salts. The silicon d-orbitals are included and the orbital exponent and one-centre repulsion integral for these orbitals, together with the Mulliken-Wolfsberg A parameter, were optimised so as to produce the ‘best’ results for the acid. Replacement of H by metal atoms in the polymer is shown to perturb the system in such a way as to reduce the band gap by a factor of 3 to 4. Further, the non-bridging O atoms, along with the metal atoms themselves, become concentrated in the states bordering the band gap. Density-of-states curves are sharply peaked around the energy gap for all four systems and the peak height increases as the metal atomic number becomes larger.     

Microwave absorption studies of MgB2 superconductor

Microwave absorption studies have been carried out on MgB₂ superconductor using a standard X-band EPR spectrometer. The modulated low-field microwave absorption signals recorded for polycrystalline (grain size ∼ 10 μm) samples suggested the absence of weak-link character. The field dependent direct microwave absorption has been found to obey a ✓H dependence with two different slopes, which indicated a transition from strongly pinned lattice to flux flow regime.