Thermal and dilute-solution properties of zwitterionic copolymers

We report the synthesis, characterization, thermal and dilute-solution properties of zwitterionic copolymers of the sulfobetaine type, where the proportion of ionic groups is varied over a wide range. Two different structures are considered: poly (2-vinyl pyridine sulfopropyl betaine) and poly (4-vinyl pyridine sulfopropyl betaine). Synthesis is carried out to obtain random copolymers which are further characterized and their ionic content determined. At low proportions of ionic groups, the behavior is similar to that observed in ionomers, with substantial differences between the two structures, Increased interaction among the zwitterionic groups at higher charge densities is evidenced, which leads to the formation of clusters and agglomerates. An increase in the intrinsic viscosity with salt content in aqueous solutions is also observed. This behavior is analogous to that of homopolymers with 100% ionic content, but with particular features of interest.     

Electrical resistivity, optical and magnetic properties of the layered oxyselenide SmCuOSe

The electrical and magnetic properties of the tetragonal phase SmCuOSe are reported as a function of the temperature. The optical properties were studied by means of diffuse reflectance spectrum in the UV-Vis range. The electrical resistivity measurements as well as diffuse reflectance spectrum show that SmCuOSe is a semiconductor with an optical band gap (E_g) of 2.6 eV. In this phase, Cu is at its monovalent oxidation state and, as such, it does not contribute to the total magnetic moment, whereas Sm is in its 3+ oxidation state, with a large VanVleck contribution due to the admixture of the fundamental state with higher energy levels.     

Carboxylate-bridged copper(II)-lanthanide(III) complexes [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n)(Ln = Dy,Ho, Er,Y; oda = oxydiacetate)

The hydrothermal reaction of Ln(2)O(3) (Ln = Dy and Ho), Cu(OAc)(2).2H(2)O, and oxydiacetic acid in the approximate mole ratio of 1:3:8 resulted in the formation of two new members of the isostructural series of polymers formulated as [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n), crystallizing in the hexagonal crystal system, space group P6/mcc (No. 192). Temperature-dependent magnetic susceptibilities and EPR spectra are reported for the heterometallic compounds Cu-Dy 1, Cu-Ho 2, Cu-Er 3, and Cu-Y 4. The results are discussed in terms of the structure of the compounds, the electronic properties of the lanthanide ions, and the exchange interactions between the magnetic ions.     

Diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide

The Taylor–Aris chromatographic technique was employed for the determination of diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide from 313.16 to 333.16 K and pressures between 15 and 35 MPa. As expected, the diffusivities rise when temperature increases and pressure decreases. Numerous predictive equations are compared with experimental data: Lai–Tan, Liu–Ruckenstein cluster formula, Woerlee, Hippler–Schubert–Troe, Catchpole–King, Eaton–Akgerman, He, He–Yu, Liu–Silva–Macedo, Funazukuri and coworkers, Dariva–Coelho–Oliveira, Zhu–Lu–Zhou–Wang–Shi and the Liu–Ruckenstein RHS formula. The equations of He, He–Yu and Catchpole–King are the best of all, but cannot be used in the whole range of temperatures and solvent densities.     

Direct versus resonances mediated F+OH collisions on a new 3A" potential energy surface

A theoretical study of the F(2P) + OH(2Pi) --> HF(1Sigma+) + O(3P) reactive collisions is carried out on a new global potential energy surface (PES) of the ground 3A" adiabatic electronic state. The ab initio calculations are based on multireference configuration interaction calculations, using the aug-cc-pVTZ extended basis sets of Dunning et al. A functional representation of the PES shows no nominal barrier to reaction, contrary to previous results by others. Wave packet and quasiclassical trajectory calculations have been performed for this PES to study the F + OH(v = 0,j) reactive collision. The comparison was performed at fixed and constant values of the total angular momentum from 0 to 110 and relative translational energy up to 0.8 eV. The reaction presents a dynamical barrier, essentially due to the zero-point energy for the bending vibration near the saddle point. This determines two different reaction mechanisms. At energies higher than approximately 0.125 eV the reaction is direct, while below that value it is indirect and mediated by heavy-light-heavy resonances. Such resonances, also found in the simulations of the photodetachment spectrum of the triatomic anion, manifest themselves in the quasiclassical simulations, too, where they are associated to periodic orbits.     

13C NMR quantification of mono and diacylglycerols obtained through the solvent‐free lipase‐catalyzed esterification of saturated fatty acids

In the present investigation, we studied the enzymatic synthesis of monoacylglycerols (MAG) and diacylglycerols (DAG) via the esterification of saturated fatty acids (stearic, palmitic and an industrial residue containing 87% palmitic acid) and glycerol in a solvent‐free system. Three immobilized lipases (Lipozyme RM IM, Lipozyme TL IM and Novozym 435) and different reaction conditions were evaluated. Under the optimal reaction conditions, esterifications catalyzed by Lipozyme RM IM resulted in a mixture of MAG and DAG at high conversion rates for all of the substrates. In addition, except for the reaction of industrial residue at atmospheric pressure, all of these products met the World Health Organization and European Union directives for acylglycerol mixtures for use in food applications. The products were quantified by ¹³C NMR, with the aid of an external reference signal which was generated from a sealed coaxial tube filled with acetonitrile‐d3. After calibrating the area of this signal using the classical external reference method, the same coaxial tube was used repeatedly to quantify the reaction products. Copyright © 2012 John Wiley & Sons, Ltd.