Exchange reactions control for selective separation of glyoxylic acid in technological mixtures of glyoxal oxidation

Separation of glyoxylic acid from unpurified multicomponent technological mixtures, resulting in the process of direct oxidation of glyoxal, and preparation of sodium glyoxylate are developed. The mixtures are treated with an optimal amount of CaCO_3, which has to be prespecified by acidic–basic titration of the technological mixtures. Both separation of glyoxylic acid and preparation of sodium glyoxylate take place owing to ionic exchange reactions: calcium glyoxylate is easily converted into glyoxylic acid by action of oxalic acid. Reaction with Na₂CO₃ leads to the formation of sodium glyoxylate.     

Reorganization of perylene bisimide J-aggregates: from delocalized collective to localized individual excitations

Water-induced reorganization of individual one-dimensional J-aggregates of perylene bisimide (PBI) dyes was observed by fluorescence microscopy. Fluorescence spectra and decay kinetics of individual J-aggregates immobilized on glass surfaces were measured under a dry nitrogen atmosphere and under humid conditions. The fluorescence properties of PBI J-aggregates arisen from collective excitons under dry nitrogen atmosphere were changed to those of non-interacting dye monomers when water vapor was introduced into the environment (sample chamber). Time-dependent changes of the fluorescence spectra and lifetimes upon exposure to water vapor suggest an initial coordination of water molecules at defect sites leading to the formation of H-type dimer units that act as exciton quenchers, and a subsequent slower disintegration of the hydrogen-bonded J-aggregate into monomers that lack resonance coupling. Our present studies resulted in a direct demonstration of how drastically the optical properties of molecular ensembles and characteristics of their excited states can be changed by delicate reorganization of dye molecules at nanometre scales.     

Fast automated NMR spectroscopy of short-lived biological samples

Faster than death: NMR techniques that make use of nonlinear sampling and hyperdimensional processing enable the recording of complete NMR data sets for the automated assignment of the backbone and side-chain resonances of short-lived protein samples of cell lysates.     

Preparation and studies of new phosphorus‐containing diols as potential flame retardants

Several new phosphorus‐containing potential flame retardants (FRs) were prepared and evaluated for heat release reduction potential, by incorporation of the molecules into polyurethane samples, generated from methylene diphenyl diisocyanate and 1,3‐propane diol. The potential FRs were all prepared from commercial diisocyanates, with the phosphorus‐containing substructure introduced as a semicarbazone. All of the target structures were diols, to facilitate their incorporation into a polyurethane main chain. The polyurethane samples were prepared via copolymerization, and analysis clearly demonstrated that the potential FRs were chemically incorporated, prior to heat release testing. The heat‐release reduction potential of these substances was evaluated using the microcombustion calorimeter. Results demonstrated that both heat release reduction potential and char formation were structure dependent. Some of the compounds containing an aromatic core had more effect on char formation (higher char yields) and peak heat‐release rate (lowered heat release) than just phosphorus content alone.     

Fatty Acids from a Glass Sponge <Emphasis Type="Italic">Aulosaccus</Emphasis> sp. Occurrence of New Cyclopropane-Containing and Methyl-Branched Acids

In order to identify new structures, the free fatty acids from an extract of a glass sponge Aulosaccus sp. (from the north‐west Pacific) belonging to one of the least chemically investigated classes (Hexactinellida), were fractionated by RP‐HPLC and analyzed by NMR spectroscopy and GC–MS of their pyrrolidine derivatives, methyl(ethyl) esters and their dimethyl disulfide adducts. One hundred and twenty‐three C₁₂–C₃₁ acids (including nine new compounds) were detected, one hundred and ten of these compounds have not been found previously in glass sponges. The levels of common methylene‐interrupted polyenes, monoenes of the (n–7) family and less common branched‐chain components proved to be high. New acids were shown to be 5,13‐dimethyl‐tetradec‐4‐enoic, cis‐10,11‐methylene‐heptadecanoic, 10,12‐dimethyl‐octadecanoic, cis‐12,13‐methylene‐nonadecanoic, (14E)‐13‐methyl‐eicos‐14‐enoic, 19‐methyl‐eicos‐13‐enoic, cis‐20,21‐methylene‐heptacosanoic, 27‐methyl‐octacos‐21‐enoic and (22Z)‐nonacos‐22‐enoic. Some important mass spectrometric characteristics of pyrrolidides of homologous cyclopropane fatty acids are reported and discussed.     

Practical Application of the Probabilistic‐Statistical Model of the Suspension Separation in Hydrocyclones

An effective practical approach that allows not only a significant reduction in the scope of practical experiments in the course of studying suspension separation processes in hydrocyclones, but also makes it possible to assess the intensity of random components of the processes and define the interrelation between such components and hydrodynamics of flows in a hydrocyclone is presented. Within the frames of the developed probabilistic‐statistical model of suspension separation in hydrocyclones on the basis of statistical self‐similarity properties, a relationship was found between determined and random components of the processes. This allowed transitioning from three‐parameter probability density functions for suspension particles in hydrocyclones to two‐parameter functions; thus significantly improving the efficiency of practical application of the developed model.     

Investigation of ZnFe2O4 spinel ferrite nanocrystalline screen-printed thick films for application in humidity sensing

Zinc ferrite nanocrystalline powder was obtained by solid state synthesis of starting zinc oxide and hematite nanopowders. Field emission scanning electron microscopy and transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy confirmed the formation of nanocrystalline zinc-ferrite powder with a mixed spinel structure with small amounts of remaining zinc oxide and hematite as impurities. Thick film paste was formed and screen printed on test interdigitated PdAg electrodes on alumina substrate. Formation of a porous nanocrystalline structure was confirmed by scanning electron microscopy and Hg porosimetry. Humidity sensing properties of zinc ferrite thick films were investigated by monitoring the change in impedance in the relative humidity interval 30%-90% in the frequency range 42 Hz-1 MHz at room temperature (25°C) and 50°C. At 42 Hz at both analyzed temperatures the impedance reduced ~46 times in the humidity range 30%-90%. The dominant influence of grain boundaries was confirmed by analysis of complex impedance with an equivalent circuit.