Layered droplet microstructures in sheared emulsions: finite-size effects

We investigate the influence of confinement on the steady state microstructure of emulsions sheared between parallel plates, in a regime where the average droplet dimension is comparable to the gap width between the confining walls. Utilizing droplet velocimetry, we find that the droplets can organize into discrete layers under the influence of shear. The number of layers decreases from two (at relatively higher shear rates) to one (at lower shear rates), as the drops grow slightly larger due to coalescence. We argue that the layering and overall composition profile may be controlled by the interplay of droplet collisions (which can cause separation of droplet centers in the velocity gradient direction), droplet migration toward the centerline (due to wall effects), and droplet packing constraints. We also study the effects of mixture composition on droplet microstructure, and summarize these results in the form of a morphology diagram in the parameter space of mass fraction and shear rate. We find that formation of strings of the suspended phase (reported earlier by our group in flow-visualization studies on confined emulsions) is observed over a broad composition window. We also find a stable (nontransient) morphology wherein the droplets are arranged in highly ordered pearl-necklace chain structures.     

Interaction of an ultrasonic wave with a bubbly mixture

The interaction of an ultrasonic wave with a bubbly two-phase flow is studied both experimentally and theoretically. Brief theoretical reviews of acoustic wave generation by a piston and of the interaction of a plane wave with a single bubble are given. A theory relating ultrasonic wave transmission through a bubbly flow with two-phase flow parameters, notably the bubble size and the volumetric interfacial area, is derived and compared with preliminary data. The theoretical and experimental limitations concerning the application of ultrasonic transmission measurements to the study of bubbly flow are discussed in detail, and recommendations for future work in this area are made.Nomenclature A projected cross-sectional area of a bubble - a bubble radius - a _T emitter radius - c speed of sound - d equivalent bubble diameter - I intensity - I ₀ incident intensity - J ₀ Bessel function of zero order - J ₀ Bessel function of first order - j ₁ spherical Bessel function of the first kind and of order l - k wave number - n _l spherical Bessel function of the second kind (Nishi's notation) - n number of bubbles per unit volume or per unit area - P ₀ pressure amplitude at the emitter; equilibrium pressure in the liquid - p pressure perturbation - r spherical coordinate, radial distance to the x-axis - S total scattering cross-sectional area, surface of the piston - S _i scattering cross-sectional area of the i-th bubble - T transmittance - t time - U complex source strength divided by the source area - W ratio of radial distance from the axis on the emitter surface to the radius of the emitter - x axis coinciding with the direction of propagation of the plane wave; distance between the transducers - void fraction - interfacial area per unit volume - spherical coordinate - ultrasonic wavelength - density - angular frequency     

On the Frequency of Zeros of Solutions of Second Order Linear Differential Equations

We consider the equation \(\rm f^{\prime\prime}+{A}(z){f}=0\) with linearly independent solutions f₁,₂, where A(z) is a transcendental entire function of finite order. Conditions are given on A(z) which ensure that max{λ(f₁),λ(f₂)} = ∞, where λ(g) denotes the exponent of convergence of the zeros of g. We show as a special case of a further result that if P(z) is a non-constant, real, even polynomial with positive leading coefficient then every non-trivial solution of \(\rm f^{\prime\prime}+{e}^P{f}=0\) satisfies λ(f) = ∞. Finally we consider the particular equation \(\rm f^{\prime\prime}+({e}^Z-K){f}=0\) where K is a constant, which is of interest in that, depending on K, either every solution has λ(f) = ∞ or there exist two independent solutions f₁, f₂ each with λ(f_i) ≤ 1.     

Coherent single pion production by antineutrino charged current interactions and test of PCAC

The cross section for coherent production of a single π^? meson in charged current antineutrino interactions on neon nuclei has been measured in BEBC to be (175±25) 10^?40 cm²/neon nucleus, averaged over the energy spectrum of the antineutrino wide band beam at the CERN SPS; this corresponds to (0.9±0.1) % of the total charged current \(\bar v_\mu \) cross section. The distributions of kinematical variables are in agreement with theoretical predictions based on the PCAC hypothesis and the meson dominance model; in particular, theQ ² dependence is well described by a propagator containing a massm=(1.35±0.18) GeV. The absolute value of the cross section is also in agreement with the model. This analysis thus provides a test of the PCAC hypothesis in the antineutrino energy range 5–150 GeV.     

‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

Transfer hydrogenation using recyclable polyurea-encapsulated palladium: efficient and chemoselective reduction of aryl ketones

A robust and recyclable palladium catalyst [Pd0EnCat] has been prepared by ligand exchange of polyurea-encapsulated palladium(II) acetate with formic acid, resulting in deposition of Pd(0) in the support material; Pd0EnCat is shown to be a highly efficient transfer hydrogenation catalyst for chemoselective reduction of a wide range of aryl ketones to benzyl alcohols.     

Simultaneous determination of clebopride and a major metabolite N-desbenzylclebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry

A procedure for the simultaneous assay of clebopride and its major metabolite N-desbenzylclebopride in plasma has been developed. The method utilizes capillary gas chromatography-negative-ion chemical ionization mass spectrometry with selected-ion monitoring of characteristic ions. Employing 2-ethoxy analogues as internal standards, the benzamides were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyric anhydride produced volatile mono- and diheptafluorobutyryl derivatives of clebopride and N-desbenzylclebopride, respectively. The methane negative-ion mass spectra of these derivatives exhibited intense high-mass ions ideal for specific quantitation of low levels in biological fluids. Using this procedure the recovery of the drug and metabolite from human plasma was found to be 84.4 +/- 1.5% (n = 3) and 77.4 +/- 4.7% (n = 3), respectively, at 0.5 ng/ml. Measurement of both compounds down to 0.10 ng/ml with a coefficient of variation of less than 10.5% is described. Plasma levels are reported in four volunteers up to 24 h following oral administration of 1 mg of clebopride malate salt.