Recent advances in CE-MS: Synergy of wet chemistry and instrumentation innovations

CE with MS detection is a hyphenated technique which greatly improves the ability of CE to deal with real samples, especially with those coming from biology and medicine, where the target analytes are present as trace amounts in very complex matrices. CE-MS is now almost a routine technique performed on commercially available instruments. It faces currently a tremendous development of the technique itself as well as of its wide application area. Great interest in CE-MS is reflected in the scientific literature by many original research articles and also by numerous reviews. The review presented here has a general scope and belongs to a series of regularly published reviews on the topic. It covers the literature from the last 2 years, since January 2008 till June 2010. It brings a critical selection of related literature sorted into groups reflecting the main topics of actual scientific interest: (i) innovations in CE-ESI-MS, (ii) use of alternative interfaces, and (iii) ways to enhance sensitivity. Special attention is paid to novel electrolyte systems amenable to CE-MS including nonvolatile BGEs, to advanced CE separation principles such as MEKC, MEEKC, chiral CE, and to the use of preconcentration techniques.     

Thermal and electronic charge transport in bulk nanostructured Zr0.25Hf0.75NiSn composites with full-Heusler inclusions

Bulk Zr_0.25Hf₀₇₅NiSn half-Heusler (HH) nanocomposites containing various mole fractions of full-Heusler (FH) inclusions were prepared by solid state reaction of pre-synthesized HH alloy with elemental Ni at 1073 K. The microstructures of spark plasma sintered specimens of the HH/FH nanocomposites were investigated using transmission electron microscopy and their thermoelectric properties were measured from 300 K to 775 K. The formation of coherent FH inclusions into the HH matrix arises from solid-state Ni diffusion into vacant sites of the HH structure. HH(1–y)/FH(y) composites with mole fraction of FH inclusions below the percolation threshold, y∼0.2, show increased electrical conductivity, reduced Seebeck coefficient and increased total thermal conductivity arising from gradual increase in the carrier concentration for composites. A drastic reduction (∼55%) in κ_l was observed for the composite with y=0.6 and is attributed to enhanced phonon scattering due to mass fluctuations between FH and HH, and high density of HH/FH interfaces.     

Simultaneous large enhancements in thermopower and electrical conductivity of bulk nanostructured half-Heusler alloys

Large reductions in the thermal conductivity of thermoelectrics using nanostructures have been widely demonstrated. Some enhancements in the thermopower through nanostructuring have also been reported. However, these improvements are generally offset by large drops in the electrical conductivity due to a drastic reduction in the mobility. Here, we show that large enhancements in the thermopower and electrical conductivity of half-Heusler (HH) phases can be achieved simultaneously at high temperatures through coherent insertion of nanometer scale full-Heusler (FH) inclusions within the matrix. The enhancements in the thermopower of the HH/FH nanocomposites arise from drastic reductions in the "effective" carrier concentration around 300 K. Surprisingly, the mobility increases drastically, which compensates for the decrease in the carrier concentration and minimizes the drop in the electrical conductivity. Interestingly, the carrier concentration in HH/FH nanocomposites increases rapidly with temperature, matching that of the HH matrix at high temperatures, whereas the temperature dependence of the mobility significantly deviates from the typical T(-α) law and slowly decreases (linearly) with rising temperature. This remarkable interplay between the temperature dependence of the carrier concentration and mobility in the nanocomposites results in large increases in the power factor at 775 K. In addition, the embedded FH nanostructures also induce moderate reductions in the thermal conductivity leading to drastic increases in the ZT of HH(1 - x)/FH(x) nanocomposites at 775 K. By combining transmission electron microscopy and charge transport data, we propose a possible charge carrier scattering mechanism at the HH/FH interfaces leading to the observed anomalous electronic transport in the synthesized HH(1 - x)/FH(x) nanocomposites.     

Energy transfer from Tb3+ to Nd3+ in glycerol:D2O solution and frozen glass

The mechanism of energy transfer from Tb³⁺ to Nd³⁺ in glycerol:D₂O solution at 280 K, 300 K and in its frozen glass at 80 K, 120 K, 190 K and 250 K has been examined. Analysis of the intensity and lifetime measurements of ⁵D₄ level of Tb³⁺ shows that at 280 K and 300 K in solution the transfer rate varies as the square of the Nd³⁺ concentration. This suggests a dipole-dipole transfer in the glycerol:D₂O solution. However, at lower temperatures up to 190 K, where the solution freezes into a glass, the dependence observed is linear at lower Nd³⁺ concentrations and quadratic at higher concentrations. Moreover, the linear concentration dependence becomes more pronounced as the temperature of the glass is increased. This linear concentration dependence of the transfer rate and its temperature dependence have been ascribed to the migrational transfer accompanying the multipolar transfer. The coefficients of both the interactions at the above temperatures have been calculated.     

Convenient direct synthesis of bisformylated calix[4]arenes via ipso substitution

[reaction: see text] A facile synthesis of bisformylated calix[4]arenes via ipso substitution of p-tert-butylcalix[4]arenes through treatment with hexamethylenetetramine/trifluoroacetic acid is described. Under identical conditions, p-tert-butylcalix[4]arene tetramethyl ether 4 gives proximally substituted bisformylated derivative 4a in a pinched cone conformation.     

Synthesis and characterization of Ni-Zn ferrite nanoparticles

Nickel zinc ferrite nanoparticles Ni_xZn_1−xFe₂O₄ (x=0.1, 0.3, 0.5) have been synthesized by a chemical co-precipitation method. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, electron paramagnetic resonance, dc magnetization and ac susceptibility measurements. The X-ray diffraction patterns confirm the synthesis of single crystalline Ni_xZn_1−xFe₂O₄ nanoparticles. The lattice parameter decreases with increase in Ni content resulting in a reduction in lattice strain. Similarly crystallite size increases with the concentration of Ni. The magnetic measurements show the superparamagnetic nature of the samples for x=0.1 and 0.3 whereas for x=0.5 the material is ferromagnetic. The saturation magnetization is 23.95 emu/g and increases with increase in Ni content. The superparamagnetic nature of the samples is supported by the EPR and ac susceptibility measurement studies. The blocking temperature increases with Ni concentration. The increase in blocking temperature is explained by the redistribution of the cations on tetrahedral (A) and octahedral (B) sites.     

Polymer microenvironmental effects on the photophysics of cinchonine dication

Photophysical properties of cinchonine dication (C⁺⁺) have been studied in protic and aprotic polymers by monitoring steady state and time resolved measurements. It is found to be sensitive towards the microenvironment of polymers. Edge excitation red shifted emission (EERS) is observed in all polymeric matrices. However, the magnitude of EERS is relatively high in protic as compared to aprotic polymer. Isobestic point in excitation spectra and three decay components in time resolved measurements indicate more than two trapped chemical species in the heterogeneous environment of the polymer. Solute-polymer interactions are found to produce the third decay channel, unlike in solution phase and may be useful to understand the polymer microenvironment.     

Viscosity Approximation Methods for Generalized Multi-Valued Nonexpansive Mappings with Applications

Abstract

In this article, we study viscosity approximation methods for generalized multi-valued nonexpansive mappings and we present some new results related to strong convergence, variational inequality, convex optimization, split and common split feasibility problems (SFPs). Some numerical computations are also presented to illustrate our results.