Polypropylene–clay nanocomposite structure probed by H NMR relaxometry

In this paper, we used low-field nuclear magnetic resonance (NMR) relaxometry and X-ray diffraction techniques to characterize polypropylene and to probe the polypropylene/clay interactions in non-exfoliated and exfoliated polypropylene–clay nanocomposites. Differences in T₁H longitudinal relaxation time data and X-ray diffraction spectra were correlated with the presence of different domains in the samples studied. The results demonstrated the potential of H NMR relaxometry as a tool in the characterization of polymer–clay nanocomposites.     

External non-white noise and nonequilibrium phase transitions

Langevin equations with external non-white noise are considered. A Fokker Planck equation valid in general in first order of the correlation time of the noise is derived. In some cases its validity can be extended to any value of. The effect of a finite in the nonequilibrium phase transitions induced by the noise is analyzed, by means of such Fokker Planck equation, in general, for the Verhulst equation under two different kind of fluctuations, and for a genetic model. It is shown that new transitions can appear and that the threshold value of the parameter can be changed.     

Phase Chemistry and Thermochemstry on Coordination Behavior of Zinc Chloride with Leucine

The solubility property of the ZnCl2-Leu-H2O(Leu=L-a-leucine) system at 298.15K in the whole concentration range was investigatey by the semimicro-phase equilibrium method.The corresponding solubility diagram and refractive index diagram were constructed.The results indicated that there was one complex formed in this system.namely,Zn(Leu)Cl2.The complex is congruently soluble in water.Based on Phase equilibrium data,the complex was prepared.Its composition and properties were characterized by chemical analysis,elemental analysis,IR spectra,and TG-DTG.The thermochemical properties of coordination reaction of zinc chloride with L-a-leucine were investigated by a microcalorimeter.The enthalpies of solution of L-a-leucine in water and its zinc complex at infinite dilution and the enthalpy change of solid-liquid reaction wrer determined at 298.15K.The enthalpy change of soild phase reaction and the standard enthalpy of formation of zinc complex were claculated.On the basis of experimental and calculated results,three thermodynamic parameters(the activation enthalpy,the activation entropy and the activation free energy),the rate constant and three kinetic parameters(the activation energy,the preexponential constant and the reaction order) of the reaction,and the standard enthalpy of formation of Zn(Leu)^2 (aq) were obtained.The results showed that the title reaction took place easily at studied temperature.     

Modulation of proteins adsorption onto the surface of chitosan complexed with anionic copolymers. Real time analysis by surface plasmon resonance

The interpolyelectrolyte complex formation between chitosan and anionic polyacrylic derivatives, bearing sulfonic moieties, as well as the protein adsorption onto the chitosan/polyacrylic complexes were studied by surface plasmon resonance (SPR) optical biosensor. This unique technique allows a real time monitoring of different surface molecular interactions with very high sensitivity. The acrylic macromolecules are two families of copolymers of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and, respectively, 2-hydroxyethylmethacrylate (HEMA) and N,N'-dimethylacrylamide (DMAA). The complexation process was evaluated through the SPR measurements resulting from the flowing of polyacrylic aqueous solution over the sensor previously coated with chitosan. The SPR was able to differentiate strong ionic bonds from other weak and reversible interactions. By means of the coated sensors (uncomplexed and the whole series of complexed chitosan), SPR cold be used for a simple "in vitro" protein adsorption analysis, by flowing aqueous solutions of albumin and fibrinogen. While both proteins were adsorbed on the uncomplexed chitosan, the complexed coatings exhibited different and very promising behaviors. In particular, they showed no adsorption or only selective adsorption of albumin.     

Theoretical Study on Gas—phase Pyrolytic Reactions of N—Ethyl,Isopropyl and N—t—Butyl Substituted 2—Aminopyrazine

Density functional theory (DFT) and ab initio methods were used to study gas‐phase pyrolytic reaction mechanisms of iV‐ethyl, N‐isopropyl and N‐t‐butyl substituted 2‐aminopyrazine at B3LYP/6–31G* and MP2/6–31G*, respectively. Single‐point energies of all optimized molecular geometries were calculated at B3LYP/6–311 + G(2d,p) level. Results show that the pyrolytic reactions were carried out through a unimolecular first‐order mechanism which were caused by the migration of atom H(17) via a six‐member ring transition state. The activation energies which were verified by vibrational analysis and correlated with zero‐point energies along the reaction channel at B3LYP/6–311 + G(2d,p) level were 252.02 kJ. mo^?1 (N‐ethyl substituted), 235.92 kJ‐mol^?1 (N‐t‐isopropyl substituted) and 234.27 kJ‐mol^?1 (N‐t‐butyl substituted), respectively. The results were in good agreement with available experimental data.     

Calcia-supported lanthanide oxides for methane oxidation II. Catalytic properties

Lanthanum and samarium oxides supported on CaO, prepared from lanthanide nitrates or oxides, have been tested for methane oxidation. Samples prepared from the oxides are more active for total oxidation. Those from nitrates lead mainly to C₂ and C₃.

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, CaO, , . , , , — C₂ C₃.

     

A pointwise spectrum and representation of operators

For a self-adjoint operator commuting with an increasing family of projections we study the multifunction an open set of the topology containing , where is the spectrum of on . Let be the measure of maximal spectral type. We study the condition that is essentially a singleton, is not a singleton. We show that if is the density topology and if satisfies the density theorem, in particular if it is absolutely continuous with respect to the Lebesgue measure, then this condition is equivalent to the fact that is a Borel function of . If is the usual topology then the condition is equivalent to the fact that is approched in norm by step functions , where the set of intervals covers the set where is a singleton.

     

Walk-off and pattern selection in optical parametric oscillators

The effect of walk-off in pattern selection in optical parametric oscillators is theoretically examined. We show that a dynamic mechanism also allows us to observe the formation of structures for positive signal detunings. In this regime the pattern that is generated is a periodic array of kinks that separate regions in which one of two stable steady states is alternately selected. This structure can be regarded as a train of dark soliton stripes because the two solutions have opposite signs. The wavelength of the selected pattern is theoretically predicted, and the prediction agrees with the results of the numerical solutions of the equations governing the device.     

Asymptotic analysis of the exponential penalty trajectory in linear programming

We consider the linear program min{cx: Axb} and the associated exponential penalty functionf _r(x) = cx + rexp[(A _ix – b_i)/r]. Forr close to 0, the unconstrained minimizerx(r) off _r admits an asymptotic expansion of the formx(r) = x ^* + rd^* + (r) wherex ^* is a particular optimal solution of the linear program and the error term(r) has an exponentially fast decay. Using duality theory we exhibit an associated dual trajectory(r) which converges exponentially fast to a particular dual optimal solution. These results are completed by an asymptotic analysis whenr tends to : the primal trajectory has an asymptotic ray and the dual trajectory converges to an interior dual feasible solution.Corresponding author. Both authors partially supported by FONDECYT.