New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Measurement of vocal-tract influence during saxophone performance

This paper presents experimental results that quantify the range of influence of vocal tract manipulations used in saxophone performance. The experiments utilized a measurement system that provides a relative comparison of the upstream windway and downstream air column impedances under normal playing conditions, allowing researchers and players to investigate the effect of vocal-tract manipulations in real time. Playing experiments explored vocal-tract influence over the full range of the saxophone, as well as when performing special effects such as pitch bending, multiphonics, and "bugling." The results show that, under certain conditions, players can create an upstream windway resonance that is strong enough to override the downstream system in controlling reed vibrations. This can occur when the downstream air column provides only weak support of a given note or effect, especially for notes with fundamental frequencies an octave below the air column cutoff frequency and higher. Vocal-tract influence is clearly demonstrated when pitch bending notes high in the traditional range of the alto saxophone and when playing in the saxophone's extended register. Subtle timbre variations via tongue position changes are possible for most notes in the saxophone's traditional range and can affect spectral content from at least 800-2000 Hz.     

Characterization of woodwind instrument toneholes with the finite element method

A method is proposed to determine the transfer matrix parameters of a discontinuity in a waveguide with the finite element method (FEM). This is used to characterize open and closed woodwind instrument toneholes and develop expressions for the shunt and series equivalent lengths. Two types of toneholes are characterized: Unflanged toneholes made of thin material, such as found on saxophones and concert flutes, and toneholes drilled through a thick material, such as found on most instruments made of wood. The results are compared with previous tonehole models from the literature. In general, the proposed expressions provide a better fit across a wide range of frequencies and tonehole sizes than previous results. For tall toneholes, the results are in general agreement with previous models. For shorter tonehole heights, some discrepancies from previous results are found that are most important for larger diameter toneholes. Finally, the impact of a main bore taper (conicity) on the characterization of toneholes was investigated and found to be negligible for taper angles common in musical instruments.     

Numerical simulations of fluid-structure interactions in single-reed mouthpieces

Most single-reed woodwind instrument models rely on a quasistationary approximation to describe the relationship between the volume flow and the pressure difference across the reed channel. Semiempirical models based on the quasistationary approximation are very useful in explaining the fundamental characteristics of this family of instruments such as self-sustained oscillations and threshold of blowing pressure. However, they fail at explaining more complex phenomena associated with the fluid-structure interaction during dynamic flow regimes, such as the transient and steady-state behavior of the system as a function of the mouthpiece geometry. Previous studies have discussed the accuracy of the quasistationary approximation but the amount of literature on the subject is sparse, mainly due to the difficulties involved in the measurement of dynamic flows in channels with an oscillating reed. In this paper, a numerical technique based on the lattice Boltzmann method and a finite difference scheme is proposed in order to investigate the characteristics of fully coupled fluid-structure interaction in single-reed mouthpieces with different channel configurations. Results obtained for a stationary simulation with a static reed agree very well with those predicted by the literature based on the quasistationary approximation. However, simulations carried out for a dynamic regime with an oscillating reed show that the phenomenon associated with flow detachment and reattachment diverges considerably from the theoretical assumptions. Furthermore, in the case of long reed channels, the results obtained for the vena contracta factor are in significant disagreement with those predicted by theory. For short channels, the assumption of constant vena contracta was found to be valid for only 40% of the duty cycle.     

Effect of viscous dissipation on the mixed convection heat transfer from an exponentially stretching surface

The mixed convection flow and heat transfer from an exponentially stretching vertical surface in a quiescent fluid is analyzed using similarity solution technique. Wall temperature and stretching velocity are assumed to have specific exponential function forms. The influence of buoyancy along with viscous dissipation on the convective transport in the boundary layer region is analyzed in both aiding and opposing flow situations. The flow is governed by the mixed convection parameter Gr/Re². The velocity and temperature inside the boundary layer are observed to be influenced by the parameters like Prandtl number Pr, Gebhart number Gb. Significant changes are observed in non-dimensional skin friction and heat transfer coefficients due to viscous dissipation in the medium. The flow and temperature distributions inside the boundary layer are analyzed and the results for non-dimensional skin friction and heat transfer coefficients are discussed through computer generated plots.