Indium-mediated reaction of nitroethane and aldehydes: characterization of the nucleophilic organoindium species

A novel method for the preparation of 2-nitroalkan-1-ols by an indium-promoted reaction of bromonitromethane and 2-bromonitropropane with a variety of aldehydes was recently reported. Extension of the procedure to 1-bromo-1-nitroethane, which gives rise to a new chiral centre, was considered. On the basis of the diastereoselectivity of the nitroalkanols formed and NMR studies on the reaction mixtures, a mechanistic proposal for the indium-promoted reaction of bromonitroalkanes and aldehydes is discussed. The proposed mechanism allows the prediction of the stereochemical outcome of the present reaction.     

Uncertainty analysis of whole-field phase-differences retrieved from ESPI fringe patterns by using the Fourier transform method (FTM)

We have evaluated the uncertainty associated with the whole-field phase-differences retrieved by using the Fourier transform method (FTM), from a fringe pattern generated by electronic speckle pattern interferometry (ESPI). The phase-differences were induced by applying load to an elastic sample. The FTM involved the Fourier transform application to the fringe pattern, the isolation of the term carrying the phase information by applying a band-pass filter in the spatial frequency domain, and then the inverse Fourier transform application. Since the fringes in the analyzed pattern were adequately open, the FTM outcomes were presumed to be mainly affected by errors in the determination of both the width and the location of the applied filter mask. The influence of these error sources was assessed by using a Monte Carlo-based computer simulation. It implied evaluating the phase-differences a large number of times under the influence of the involved error sources. We found that the phase uncertainty depends strongly on the width of the applied filter mask; the influence of the other error sources considered into the uncertainty propagation was significantly smaller.     

Dynamic phase profile of phase objects based in the use of a quasi-common path interferometer

In this paper, we propose a quasi common-path interferometer based on a two beams configuration (TBC) using simultaneous phase shifting interferometry modulated by polarization that shows insensitivity against external vibration. Due to the fact that the configuration is capable of obtaining two beams whose separation can be varied, according to the characteristics of the grid used, to obtain the interference patterns. It can be used to implement a quasi-common path interferometer that allows the measurement of dynamic events with high accuracy. For demodulate the fringe patterns generated by the optical system we using the conventional four step phase shifting method. Experimental results are also given.     

Fibrant extensions of free G-spaces

We show that any equivariant fibrant extension of a compact free G-space is also free. This result allows us to prove that the orbit space of any equivariant fibrant compact space E is also fibrant, provided that E has only one orbit type.     

Indium-mediated allylation and Reformatsky reaction on glyoxylic oximes under ultrasound irradiation

A novel and more convenient method for the indium-promoted allylation of glyoxylic oximes based on the use of ultrasonic waves is reported. A similar procedure was used to develop the first example reported in the literature of an indium-mediated Reformatsky reaction on oxime ethers.     

Novel method for the estimation of the binding isotherms of ionic surfactants on oppositely charged polyelectrolytes

One of the most important characteristics of the polyelectrolyte/surfactant interaction is the binding isotherm of the surfactant because it provides basic thermodynamic information about the binding mechanism. However, the amount of the surfactant bound to the polymer may crucially affect the surface properties of these systems via changing the thermodynamic activity of the components. Therefore, a knowledge of the binding isotherms can also be useful in tuning the efficiency of commercial products. However, the determination of these isotherms is still subject to significant experimental difficulties. In this letter, we offer a novel method for the estimation of binding isotherms based on electrokinetic measurements. The technique provides a simple and quick way to estimate the bound amount of surfactant that might be useful in both fundamental and industrial research. In principle, the proposed method could also be extended to the determination of the binding isotherms of small ligands on biomacromolecules.     

The atmospheric photolysis of E-2-hexenal, Z-3-hexenal and E,E-2,4-hexadienal

The atmospheric photolysis of E-2-hexenal, Z-3-hexenal and E,E-2,4-hexadienal has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. E-2-Hexenal and E,E-2,4-hexadienal were found to undergo rapid isomerization to produce Z-2-hexenal and a ketene-type compound (probably E-hexa-1,3-dien-1-one), respectively. Both isomerization processes were reversible with formation of the reactant slightly favoured. Values of j(E-2-hexenal)/j(NO(2)) = (1.80 +/- 0.18) x 10(-2) and j(E,E-2,4-hexadienal)/j(NO(2)) = (2.60 +/- 0.26) x 10(-2) were determined. The gas phase UV absorption cross-sections of E-2-hexenal and E,E-2,4-hexadienal were measured and used to derive effective quantum yields for photoisomerization of 0.36 +/- 0.04 for E-2-hexenal and 0.23 +/- 0.03 for E,E-2,4-hexadienal. Although photolysis appears to be an important atmospheric degradation pathway for E-2-hexenal and E,E-2,4-hexadienal, the reversible nature of the photolytic process means that gas phase reactions with OH and NO(3) radicals are ultimately responsible for the atmospheric removal of these compounds. Atmospheric photolysis of Z-3-hexenal produced CO, with a molar yield of 0.34 +/- 0.03, and 2-pentenal via a Norrish type I process. A value of j(Z-3-hexenal)/j(NO(2)) = (0.4 +/- 0.04) x 10(-2) was determined. The results suggest that photolysis is likely to be a minor atmospheric removal process for Z-3-hexenal.     

BH,CH,and BC Bond Activation: The Role of Two Adjacent Agostic Interactions

Tuning the nature of the linker in a L～BHR phosphinoborane compound led to the isolation of a ruthenium complex stabilized by two adjacent, δ‐C? H and ε‐B_sp2? H, agostic interactions. Such a unique coordination mode stabilizes a 14‐electron “RuH₂P₂” fragment through connected σ‐bonds of different polarity, and affords selective B? H, C? H, and B? C bond activation as illustrated by reactivity studies with H₂ and boranes.     

Investigations of the Properties of l-Histidine in Aqueous NaCl Solutions at Different Temperatures

Density and viscosity experimental data for l-histidine in NaCl aqueous solutions were obtained at different salt and different amino acid concentrations in the range of temperatures between 293.15 and 323.15 K. The results have been correlated and analyzed in order to evaluate the influence of electrolyte concentration and temperature on the volumetric and viscometric properties of the solutions. The apparent molar volumes and the transfer volumes of l-histidine in aqueous NaCl solutions at different salt and amino acid molalities over entire temperature range were calculated from experimental density data. The viscosity experimental data have been analyzed with Jones–Dole equation and the Falkenhagen (A) and the Jones–Dole coefficient (B) have been calculated in order to evaluate the interactions occurring in the systems. The B viscosity coefficients were found to be positive for all conditions, showing a kosmotropic effect of solutes, indicating an alignment of zwitterions with ions/water dipoles. A comparison of standard partial molar volumes for some amino acids in water and NaCl aqueous solutions shows that they increase with molecular mass and complexity of the lateral side chain of the amino acid.     

Work Hardening Effects in Gellan Gum Gels1

Abstract

Gellan gum is a bacterial polysaccharide that is marketed as a broad spectrum gelling agent. The shear and Young's moduli, and the fracture strength of gellan gels increase with increasing ionic strength, pass through maxima and then decrease to zero at higher ionic strength. The position of the maxima depend on the valency of added counterions and are virtually independent of polymer concentration. At low ionic strength the measured rheological parameters show small variability but these values become increasingly variable with increasing ionic strength. Stress relaxation experiments were carried out in order to examine the mechanical behaviour of gellan gels and to explain these effects. At low ionic strength the gels approximate to elastic solids whereas at high ionic strength the increased stress relaxation is colloid-like in behaviour. However, unlike colloidal dispersions, the magnitude of the stress relaxation decreases on successive applications of stress and the relaxation modulus increases. The gels work harden. Such behaviour is attributed to a heterogeneous structure within the gel.