Holographic sensors for the determination of ionic strength

Holographic sensors for monitoring ionic strength have been fabricated from charged sulphonate and quaternary ammonium monomers, incorporated into thin, polymeric hydrogel films which were transformed into volume holograms. The diffraction wavelength or reflected colour of the holograms was used to characterise their swelling or de-swelling behaviour as a function of ionic strength in various media. The effects of co-monomer structure, buffer composition, ion composition, pH and temperature were evaluated, whilst the reversibility and reproducibility of the sensor was also assessed. An acrylamide-based hologram containing equal molar amounts of negatively and positively charged monomers was shown to be able to quantify ionic strength independent of the identity of the ionic species present in the test solution. The sensor was fully reversible, free of hysteresis and exhibited little response to pH between 3 and 9 and temperature within the range 20-45 °C. The system was successfully used to quantify the ionic strength of milk solutions, which contain a complex mixture of ions and biological components.     

The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

1,3-dihalo-5,5-dimethylhydantoin/NaNO2 as an efficient heterogeneous system for the N-nitrosation of N,N-dialkylamines under mild conditions

A combination of 1,3-dihalo-5,5-dimethylhydantoin (X = Br, Cl) and sodium nitrite in the presence of wet SiO₂ was used as an effective nitrosating agent for the nitrosation of N,N-dialkyl amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in good to excellent yields.     

Investigation of hypersonic nozzle flow uniformity using NO fluorescence

Planar laser-induced fluorescence visualisation is used to investigate nonuniformities in the flow of a hypersonic conical nozzle. Possible causes for the nonuniformity are outlined and investigated, and the problem is shown to be due to a small step at the nozzle throat. Entrainment of cold boundary layer gas is postulated as the cause of the signal nonuniformity. PACS 47.80.Jk, 47.40.Ki, 47.60.+i     

On the Local Uniqueness of Solutions of Variational Inequalities Under H-Differentiability

In this paper, we give some sufficient conditions for the local uniqueness of solutions to nonsmooth variational inequalities where the underlying functions are H-differentiable and the underlying set is a closed convex set/polyhedral set/box/polyhedral cone. We show how the solution of a linearized variational inequality is related to the solution of the variational inequality. These results extend/unify various similar results proved for C ¹ and locally Lipschitzian variational inequality problems. When specialized to the nonlinear complementarity problem, our results extend/unify those of C ² and C ¹ nonlinear complementarity problems.     

Density of states in a mesoscopic SNS junction

The semiclassical theory of proximity effects predicts a gap E _g～?D/L ² in the excitation spectrum of a long diffusive superconductor/normal-metal/superconductor (SNS) junction. Mesoscopic fluctuations lead to anomalously localized states in the normal part of the junction.As a result, a nonzero, yet exponentially small, density of states (DOS) appears at energies below E _g. In the framework of the supermatrix nonlinear σ model, these prelocalized states are due to the instanton configurations with broken supersymmetry. The exact result for the DOS near the semiclassical threshold is found, provided the dimensionless conductance of the normal part G _N is large. The case of poorly transparent interfaces between the normal and superconductive regions is also considered. In this limit, the total number of subgap states may be large.     

Approximate inverse computation using Frobenius inner product

Parallel preconditioners are presented for the solution of general linear systems of equations. The computation of these preconditioners is achieved by orthogonal projections related to the Frobenius inner product. So, min_M∈??∥AM?I∥ _F and matrix M₀∈?? corresponding to this minimum (?? being any vectorial subspace of ??_n(?)) are explicitly computed using accumulative formulae in order to reduce computational cost when subspace ?? is extended to another one containing it. Every step, the computation is carried out taking advantage of the previous one, what considerably reduces the amount of work. These general results are illustrated with the subspace of matrices M such that AM is symmetric. The main application is developed for the subspace of matrices with a given sparsity pattern which may be constructed iteratively by augmenting the set of non‐zero entries in each column. Finally, the effectiveness of the sparse preconditioners is illustrated with some numerical experiments. Copyright © 2002 John Wiley & Sons, Ltd.     

Structure and stability of 0° domain walls localized at defects in a (001)-crystal plate with combined anisotropy

An analysis is made of the conditions of formation and the stability region of static-soliton-type magnetic nonuniformities in a (001)-crystal plate with combined anisotropy. It is shown that if demagnetizing fields in the plate are taken into account, static solitons can localize at certain defects for appropriate parameters of the material. The soliton stability region was found to be bounded by two extreme values of the material parameters, namely, those at which the soliton is unstable against collapse and at which it expands. It was also found that the soliton stability region differs considerably from that predicted theoretically in the model disregarding the finite size of the sample and the presence of defects. Fiz. Tverd. Tela (St. Petersburg) 40, 1498–1502 (August 1998)     

Effect of phonon scattering from neutral and charged impurity centers on the lattice heat conductivity of PbTe:(Tl, Na)

Experimental data on the effect of thallium and sodium impurities on the lattice heat conductivity of PbTe at room temperature are reported. Because the lattice of lead chalcogenides is strongly polarized near charged impurities, the effect of impurities on the lattice heat conductivity depends substantially on their charge state. This property of the material has been used to determine the charge state of the thallium impurity in PbTe. The results obtained argue for a model of quasi-local thallium-impurity states which assumes low electron-correlation energy at an impurity center. Fiz. Tverd. Tela (St. Petersburg) 40, 1206–1208 (July 1998)