Determination of rare earths in geological samples by neutron activation analysis

The significance of rare earth distribution patterns in trace element geochemistry is briefly reviewed. Established methods for their determination at the Reactor Centre by instrumental and radiochemical techniques are described, and examples of recent applications discussed.     

Van der Waals surface graphs and molecular shape

A van der Waals surface graph is the graph defined on a van der Waals surface by the intersections of the atomic van der Waals spheres. A van der Waals shape graph has a vertex for each atom with a visible face on the van der Waals surface, and edges between vertices representing atoms with adjacent faces on the van der Waals surface. These are discrete invariants of three‐dimensional molecular shape. Some basic properties of van der Waals surface graphs are studied, including their relationship with the Voronoi diagram of the atom centres, and a class of molecular embeddings is identified for which the dual of the van der Waals surface graph coincides with the van der Waals shape graph. This revised version was published online in July 2006 with corrections to the Cover Date.     

Free energy, energy, and entropy of swelling in Cs-, Na-, and Sr-montmorillonite clays

A Monte Carlo method for grand canonical and grand isoshear ensemble simulations has been used to characterize the free energy, energy, and entropy of clay mineral swelling. The Monte Carlo approach was found to be more efficient at simulating water content fluctuations in the highly constrained clay environment than a previously developed molecular dynamics method. Swelling thermodynamics calculated for Cs-, Na-, and Sr-montmorillonite clays indicate a strong dependence of swelling on the interlayer ion identity, in agreement with various experimental measurements. The Sr clay swells most readily, and both the Na and Sr clays prefer expanded states (two-layer hydrate or greater) when in contact with bulk water. In contrast, swelling is inhibited in the Cs clay. Differences in swelling behavior are traced directly to the tendency of the different ions to hydrate. The swelling free energies are decomposed into their energetic and entropic components, revealing an overall energetic driving force for the swelling phenomena. Entropic effects provide a smaller, mediating role in the swelling processes. The results provide a unique molecular perspective on experimentally well-characterized swelling phenomena.     

A hybrid quantum dot-antibody fragment fluorescence resonance energy transfer-based TNT sensor

We demonstrate the use of luminescent QDs conjugated to antibody fragments to develop solution-phase nanoscale sensing assemblies, based on fluorescence resonance energy transfer (FRET) for the specific detection of the explosive 2,4,6-trinitrotoluene (TNT) in aqueous environments. The hybrid sensor consists of anti-TNT specific antibody fragments attached to a hydrophilic QD via metal-affinity coordination. A dye-labeled TNT analogue prebound in the antibody binding site quenches the QD photoluminescence via proximity-induced FRET. Analysis of the data collected at increasing dye-labeled analogue to QD ratios provided an insight into understanding how the antibody fragments self-assemble on the QD. Addition of soluble TNT displaces the dye-labeled analogue, eliminating FRET and resulting in a concentration-dependent recovery of QD photoluminescence. Sensor performance and specificity were evaluated.     

Photoelectron dynamics of the cooper minimum in free molecules

The general properties of the Cooper minimum in molecules are reviewed. Experimental results from synchrotron radiation together with theoretical calculations are presented on both the partial cross sections and angular distribution parameters, β. A detailed examination of HCl is used as an example. Previously unpublished results on CCl _n H_4?n , CCl _n F_4?n , ethylene dichloride, I₂ and ICl are included. The Cooper minimum is largely discussed as a perturbation from atomic behavior, and is examined as a function of atomic number. The Cooper minimum is also examined as a function of chemical environment. Finally, needs for future research are briefly described.     

The determination of rf values of metallic ions using diethyl ether as solvent

The R_F values of some metallic ions have been determined by partition chromatography on filter paper, employing as solvents, diethyl ether saturated with normal hydrochloric, hydrobromic, sulphuric and nitric acids respectively.     

A determinate model of thrust-augmenting ejectors

A theoretical analysis of the compressible flow through a constant-area jet-engine ejector in which a primary jet mixes with ambient fluid from a uniform free stream is pursued. The problem is reduced to a determinate mathematical one by prescribing the ratios of stagnation properties between the primary and secondary flows. For some selections of properties and parameters more than one solution is possible and the meaning of these solutions is discussed by means of asymptotic expansions. Our results further show that while under stationary conditions the thrust-augmentation ratio assumes a value of 2 in the large area-ratio limit, for a free-stream Mach number greater than 0.6 very little thrust augmentation is left. Due to the assumptions made, the analysis provides idealized values for the thrust-augmentation ratio and the mass flux entrainment factor.