Synthesis of pyridine fused polycyclic amines using sequential ring-closing metathesis and radical cyclisation reactions

The syntheses of novel pyridine fused polycyclic bridgehead amines are described using sequential ring-closing metathesis (RCM) and 5-exo-trig intramolecular radical cyclisation reactions. Critical to the success of the two sequential steps were the RCM catalyst and/or the nature of the nitrogen atom.     

Interfacial properties of acidified skim milk

The purpose of this study is to investigate the tension properties and dilatational viscoelastic modulus of various skim milk proteins (whole milk, EDTA-treated milk, beta-casein, and beta-lactoglobulin) at an oil/water interface at 20 degrees C. Measurements are performed using a dynamic drop tensiometer for 15,000 s. The aqueous bulk phase is a skim milk simulated ultrafiltrate containing 11 x 10(-3) g L(-1) milk protein. At pH 6.7, beta-casein appears as the best to decrease the interfacial tension, whereas beta-lactoglobulin leads to the highest interfacial viscoelastic modulus value. Whole milk was almost as surface-active as individual beta-casein in terms of the final (steady-state) lowering of the interfacial tension, but the rate of tension lowering was smaller. EDTA treatment improved the rate of tension lowering of whole milk. The acidification of milk, from previous measurements, would lead to the enhancement of surface activity. At t=15,000 s, the order of effectiveness is pH 4.3 > pH 5.3 = pH 5.6 > pH 6.7 whole milk, suggesting that pH 4.3 whole milk is the best surface active. As compared to pH 6.7 whole milk, the use of pH 5.3 and pH 5.6 milk as surface active would result in the use of milk containing more free beta-casein born of pH-dissociated casein micelles.     

Analysis of polymer films by diffuse reflectance FTIR spectroscopy: Characterization of terminal carboxyl functionalities

Fourier transform infrared (FTIR) spectroscopy in the diffuse reflectance mode was used to study polyethylene terephthalate (PET) films. The polymer film (12 μm, molecular weight M₁ = 18,000) was placed on a finely powdered KBr matrix, used as a reference. Infrared spectra exhibited a new band at 1684 cm^?1, not usually reported in the literature. This band is assigned to the C? O stretching vibration of a terminal acidic function in the presence of internal hydrogen bonds. In the carbonyl region, artifacts created by specular reflection are also discussed. The assignment of the band at 1684 cm^?1 is confirmed by transmission measurements on the overtone of carbonyl group (3335 cm^?1), using polymer films with thicknesses greater than 200 μm and by comparison with polymer of different molecular weight. These acidic functions can be used to monitor the rate of polymerization. It is therefore possible to obtain information on the polymerization rate of PET films, using diffuse reflectance and transmission analysis, directly on the solid. © 1992 John Wiley & Sons, Inc.     

Electron and hole trapped defects produced by thermoreduction or irradiation in Stabilized Zirconia

Abstract

When undoped Yttrium Stabilized Zirconia is exposed either to reducing atmospheres or to electrical currents it becomes coloured. In this paper we present the results of a systematic study applying optical and EPR techniques to zirconia single crystals stabilized by calcium or yttrium, in which defects were produced by several methods including X-irradiation or reduction at different temperatures. Two EPR signals and three absorption bands have been related with three defects involving holes trapped in oxygen ions and electrons trapped in zirconium ions. The photothermal stability of the defects has been studied. Taking into account their spectroscopical properties and statistical considerations we propose novel models for these defects.     

Influence of temperature on the (liquid + liquid) equilibria of {3-methyl pentane + cyclopentane + methanol} ternary system at T = (293.15, 297.15, and 299.15) K

In order to show the influence of temperature on the (liquid + liquid) equilibria (LLE) of the {3-methyl pentane (1) + cyclopentane (2) + methanol (3)} ternary system, equilibrium results at T = (293.15, 297.15, and 299.15) K are reported. The effect of the temperature on the (liquid + liquid) equilibrium is determined and discussed. Experimental results show that this ternary system is completely homogeneous beyond T = 300 K. All chemicals were quantified by gas chromatography using a thermal conductivity detector. The tie line results were satisfactorily correlated by the Othmer and Tobias method, and the plait point coordinates for the three temperatures were estimated. Experimental values for the ternary system are compared with values calculated by the NRTL and UNIQUAC equations, and predicted by means of the UNIFAC group contribution method. It is found that the UNIQUAC and NRTL models provide similar good correlations of the solubility curve at these three temperatures. Finally, the UNIFAC model predicts binodal band type curves in the range of temperatures studied here, similar to those observed for systems classified by Treybal as type 2, instead of type 1 as experimentally observed. Distribution coefficients were also analysed through distribution curves.     

Temperature dependence of the Cs colloids absorption bands

Temperature dependence of the absorption bands due to Cs colloidal particles has been measured for colloids of different radii in additively colored CsBr and CsI. Large reversible shifts in the peak positions of the colloid bands are detected when we measure them at temperatures ranging between RT and LNT. The results are discussed and a tentative explanation based on the thermal change of Cs metal dielectric constants is proposed.