A new, mild synthesis of N-sulfonyl ketimines via the palladium-catalyzed isomerization of aziridines

[reaction: see text] A new method for the synthesis of N-tosylketimines via the palladium-catalyzed isomerization of N-tosylaziridines is described. The mild reaction conditions tolerate the presence of a variety of functional groups including ketones, esters, and acetals. The reactions are believed to proceed via the oxidative addition of the aziridine to Pd(0) and represent the first examples of transformations involving Pd(0)-mediated oxidative additions of aziridines that do not proceed through allylpalladium intermediates.     

Measurement of a phonon hot spot in photoexcited Si

High frequency phonons are produced by the thermalization of photoexcited electronhole pairs in a semiconductor. Inelastic and elastic scattering processes determine the frequency down-conversion and diffusion of this thermal energy. Simple estimates of the anharmonic and isotope scattering processes suggest that the acoustic phonons will undergo a quasi-diffusive propagation process. In particular, non-equilibrium phonons high-resolution phonon-imaging experiments presented here show well defined ballistic pulses and sharp phonon-focusing caustics. We explain this discrepancy in terms of a phonon hot spot which acts to efficiently down-convert the high-frequency phonons very near the excitation spot. We present the first measurements of the size of a phonon hot spot, which depends upon excitation power.     

A Simplified Method for the Measurement of Insoluble Solids in Pretreated Biomass Slurries

The biochemical conversion of cellulosic biomass to liquid transportation fuels includes the breakdown of biomass into its soluble, fermentable components. Pretreatment, the initial step in the conversion process, results in heterogeneous slurry comprised of both soluble and insoluble biomass components. For the purpose of tracking the progress of the conversion process, it is important to be able to accurately measure the fraction of insoluble biomass solids in the slurry. The current standard method involves separating the solids from the free liquor and then repeatedly washing the solids to remove the soluble fraction, a laborious and tedious process susceptible to operator variations. In this paper, we propose an alternative method for calculating the fraction of insoluble solids which does not require a washing step. The proposed method involves measuring the dry matter content of the whole slurry as well as the dry matter content in the isolated liquor fraction. We compared the two methods using three different pretreated biomass slurry samples and two oven-drying techniques for determining dry matter content, an important measurement for both methods. We also evaluated a large set of fraction insoluble solids data collected from previously analyzed pretreated samples. The proposed new method provided statistically equivalent results to the standard washing method when an infrared balance was used for determining dry matter content in the controlled measurement experiment. Similarly, in the large historical data set, there was no statistical difference shown between the wash and no-wash methods. The new method is offered as an alternative method for determining the fraction of insoluble solids.     

Saxophonists tune vocal tract resonances in advanced performance techniques

The acoustical impedance spectrum was measured in the mouths of saxophonists while they played. During bugling and while playing in the very high or altissimo range, experienced players tune a strong, but relatively broad, peak in the tract impedance to select which peak in the bore impedance will determine the note. Less experienced players are unable to produce resonances with impedance peaks comparable in magnitude to those of the bore and consequently are unable to play these notes. Experienced players can also tune their tracts to select which combinations of notes are played simultaneously in multiphonics or chords, and to produce pitch bending, a technique in which notes are produced at frequencies far from those of the peak of impedance of the instrument bore. However, in normal playing in the standard range, there is no consistent tuning of the tract resonances. The playing frequency, in all cases, lies close to the peak in the impedance of the reed in parallel with the series combination of the impedances measured in the mouth and the instrument bore on either side of the reed (ZMouth+ZBore)∥ZReed.     

Rotation reversal bifurcation and energy confinement saturation in tokamak Ohmic L-mode plasmas

Direction reversals of intrinsic toroidal rotation have been observed in diverted Alcator C-Mod Ohmic L-mode plasmas following electron density ramps. For low density discharges, the core rotation is directed cocurrent, and reverses to countercurrent following an increase in the density above a certain threshold. Such reversals occur together with a decrease in density fluctuations with 2 cm(-1)≤k(θ)≤11 cm(-1) and frequencies above 70 kHz. There is a strong correlation between the reversal density and the density at which the Ohmic L-mode energy confinement changes from the linear to the saturated regime.     

Palladium catalyzed asymmetric sulfonylation mediated chiral β-hydroxy- and β-(o-diphenylphosphino)benzoyloxy (o-diphenyl phosphino)benzamides

The palladium catalyzed asymmetric allylic sulfonylation reaction has been investigated employing β-hydroxy- and β-(o-diphenylphosphino)benzoyloxy (o-diphenyl phosphino)benzamides as chiral, non-racemic ligands. The bisphosphine β-benzoyloxybenzamide ligands proved to be the best ligands for this process. Competitive transition states for the (1S,2R)-norephedrine derived ligand 14 are compared and a rationale is provided for the observed enantioselectivities.     

Solid-State 13C-NMR spectral evidence for charge transfer complex formation in aromatic diimides and dianhydrides

Solution and solid-state proton decoupled ¹³C-NMR spectra were determined on two diimides derived from 4, 4′-oxydiphthalic anhydride. Comparison of the individual diimide spectra to that of a mixture of the two diimides indicates that ordering of these materials occurs in the solid state via charge transfer complex formation. A similar study was conducted using two isomeric dianhydrides, 4, 4′-isophthaloyldiphthalic anhydride (IDPA) and 4, 4′-terephthaloyldiphthalic anhydride (TDPA). The solution spectra of these compounds are similar and are those which would be expected for these compounds. However, their solid state spectra differ from each other. The solid-state spectrum of TDPA resembles its solution spectrum, whereas, that of IDPA differs greatly from its solution spectrum and indicates charge transfer complex formation occurs with this molecule. This difference is explained in terms of the stereochemistry of the two isomeric dianhydrides.     

BRDF reference standards for the infrared

A comparison between various recommended reference standards of diffuse reflectance in the IR is presented. It is shown that at a wavelength of 10.6 μm sulfur is the most Lambertian of the tested samples, although its powdery consistence makes it less suitable for use as a standard. Flame sprayed aluminum, with or without gold coating, also approaches a Lambertian surface and is suitable for use as a standard for BRDF measurements at 10.6 μm. Results for the BRDF of sulfur, gold-coated sandpaper, a commercial diffuse gold surface (by Labsphere) and flame sprayed aluminum are presented.     

Multiple Equilibrium States of Slightly Extensible Elastic Strings

We consider the equilibrium states of elastic strings loaded transversely by their own weight. We are interested in the relation between the equilibrium states of inextensible strings and those of strings which are nonlinearly elastic and slightly extensible. The inextensible string has a unique concave equilibrium state while the concave equilibrium states of a nonlinearly elastic string come in pairs. In this paper we explore the relation between the two models. This revised version was published online in August 2006 with corrections to the Cover Date.