A comparison of viscosity-concentration relationships for emulsions

Differential effective medium theory (D-EMT) has been used by a number of investigators to derive expressions for the shear viscosity of a colloidal suspension or an emulsion as a function of the volume fraction of the dispersed phase. Pal and Rhodes [R. Pal, E. Rhodes, J. Rheol. 33 (7) (1989) 1021-1045] used D-EMT to derive a viscosity-concentration expression for non-Newtonian emulsions, in which variations among different oil-water emulsions were accommodated by fitting the value of an empirical solvation factor by matching the volume fraction at which the ratio of each emulsion was experimentally observed to have a viscosity 100 times greater than that of the pure solvent. When the particles in suspension have occluded volume due to solvation or flocculation, we show that the application of D-EMT to the problem becomes more ambiguous than these investigators have indicated. In addition, the resulting equations either do not account for the limiting behavior near the critical concentration, that is, the concentration at which the viscosity diverges, or they incorporate this critical behavior in an ad hoc way. We suggest an alternative viscosity-concentration equation for emulsions, based on work by Bicerano and coworkers [J. Bicerano, J.F. Douglas, D.A. Brune, J. Macromol. Sci., Rev. Macromol. Chem. Phys. C 39 (4) (1999) 561-642]. This alternative equation has the advantages that (1) its parameters are more closely related to physical properties of the suspension and (2) it recovers the correct limiting behavior both in the dilute limit and near the critical concentration for rigid particles. In addition, the equation can account for the deformability of flexible particles in the semidilute regime. The proposed equation is compared to the equation proposed by Pal and Rhodes.     

Asymmetric Hydrogenation of Furans and Benzofurans with Iridium–Pyridine–Phosphinite Catalysts

Enantioselective hydrogenation of furans and benzofurans remains a challenging task. We report the hydrogenation of 2‐ and 3‐substituted furans by using iridium catalysts that bear bicyclic pyridine–phosphinite ligands. Excellent enantioselectivities and high conversions were obtained for monosubstituted furans with a 3‐alkyl or 3‐aryl group. Furans substituted at the 2‐position and 2,4‐disubstituted furans proved to be more difficult substrates. The best results (80–97 % conversion, 65–82 % enantiomeric excess) were obtained with monosubstituted 2‐alkylfurans and 2‐[4‐(trifluoromethyl)phenyl]furan. Benzofurans with an alkyl substituent at the 2‐ or 3‐position also gave high conversions and enantioselectivity, whereas 2‐aryl derivatives showed essentially no reactivity. The asymmetric hydrogenation of a 3‐methylbenzofuran derivative was used as a key step in the formal total synthesis of the cytotoxic naphthoquinone natural product (?)‐thespesone.     

The structure of higher homologues of 1,6,6aλ-trithiapentalenes the question of no-bond-single-bond-resonance in five sulfuratom homologues

X-Ray diffraction studies of 1,3-bis(4-methyl-5-phenyl-1,2-dithiol-3-ylidene)propane-2-thione indicates that this compound is not a fully delocalized π-electron system like 1,6,6aλ⁴-trithiapentalene although the S-S distances indicate some degree of delocalization.     

Dissociation energy for C(2) loss from fullerene cations in a storage ring

We have stored positively charged fullerene ions C(+)(n) (n even, from 48 to 70 and 76), C(2+)(60) and C(2+)(70) in an electrostatic storage ring and have measured the rate of emission of neutral fragments as a function of time. In the time range of the measurements, 50 micros to a few milliseconds, the rate decreases strongly due to radiative cooling of the molecules. Using the cooling rate predicted from a dielectric model, we have extracted the dissociation energies for C(2) loss from the measurements. As expected, the energies are largest for the "magic" fullerenes, C(50), C(60), and C(70), and the value of 9.8+/-0.1 eV for C(2) loss from C(+)(60) is in reasonable agreement with theory and with other recent experiments.     

Electrostriction at the LaAlO3/SrTiO3 interface

We present a direct comparison between experimental data and ab initio calculations for the electrostrictive effect in the polar LaAlO(3) layer grown on SrTiO(3) substrates. From the structural data, a complete screening of the LaAlO(3) dipole field is observed for film thicknesses between 6 and 20 uc. For thinner films, an expansion of the c axis of 2% matching the theoretical predictions for an electrostrictive effect is observed experimentally.