Comparison of an analytic horn equation approach and a boundary element method for the calculation of sound fields in the human ear canal

The sound field inside a model human ear canal has been computed, to show both longitudinal variations along the canal length and transverse variations through cross-sectional slices. Two methods of computation were used. A modified horn equation approach parametrizes the sound field with a single coordinate, the position along a curved center axis-this approach can accommodate the curvature and varying cross-sectional area of the ear canal but cannot compute transverse variations of the sound field. A boundary element method (BEM) was also implemented to compute the full three-dimensional sound field. Over 2000 triangular mesh elements were used to represent the ear canal geometry. For a plane piston source at the entrance plane, the pressure along the curved center axis predicted by the two methods is in good agreement, for frequencies up to 15 kHz, for four different ear canals. The BEM approach, though, reveals spatial variations of sound pressure within each canal cross section. These variations are small below 4 kHz, but increase with frequency, reaching 1.5 dB at 8 kHz and 4.5 dB at 15 kHz. For source configurations that are more realistic than a simple piston, large transverse variations in sound pressure are anticipated in the vicinity of the source.     

Monte carlo estimates of domain-deformation sensitivities

It is shown that, when a Monte Carlo algorithm is used for estimation of any physical quantity A, a simple and fast additional procedure can be implemented that simultaneously estimates the sensitivity of A to any problem parameter. The proposed approach is general and systematic in the sense that: (i) it includes domain-deformation sensitivities, i.e., cases where a change in the parameter modifies the domain over which the sampled random variables are defined and (ii) a simple generic procedure is presented to address all remaining free choices in terms of variance minimization.     

Phosphine-mediated [4 + 2] annulation of bis(enones): a Lewis base catalyzed "mock Diels-Alder" reaction

Lewis-base-catalyzed cycloisomerization of bis(enones) to decalins has been demonstrated as an alternative to the traditional Lewis acid catalyzed Diels-Alder cycloaddition. In this process, a trialkylphosphine mediates both bond formation steps in two distinct catalytic cycles. The single-pot operation generates two carbon-carbon bonds and up to five contiguous stereocenters in one step, starting from achiral, aliphatic substrates; eight examples are provided. [reaction: see text]     

Effect of handset proximity on hearing aid feedback

The increased sensitivity of hearing aids to feedback as a telephone handset is brought near has been studied experimentally and numerically. For the measurements, three different hearing aids were modified so that the open-loop transfer function could be measured. They were mounted in the pinna of a mannikin and the change in open-loop transfer function determined as a function of handset proximity. Increases of over 20 dB were observed, most of this change occurring within the first 10 mm of separation between pinna and handset. Numerical calculations performed using a boundary element technique were in good agreement with the measurements.     

A note on triangular derivations of

For a field of characteristic zero, and for each integer , we construct a triangular derivation of whose ring of constants, though finitely generated over , cannot be generated by fewer than elements.

     

Synthesis and complete assignment of the 1H and 13C NMR signals of new acetamido and aminoflavonoid derivatives

The complete ¹H and ¹³C NMR assignment of 9 acetamidochalcones, 18 acetamidoflavones, 18 aminoflavones, 9 acetamidoflavonols and 9 aminoflavonols has been performed using one‐ and two‐dimensional NMR techniques including COSY, HMQC and HMBC experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Palladium(0) pre‐catalysts with heteroditopic NHC–amine ligands by transmetallation from their silver(I) complexes

The synthesis of an air‐stable series of Pd⁰ complexes with dissymmetric bidentate N‐heterocyclic carbene–amine ligands has been performed. The key step is an unprecedented carbene transfer from Ag^I to obtain electron‐rich zero‐valent palladium precatalysts. The coordination behavior of the ligands was determined with X‐ray crystallography. Surprising results were obtained in the catalysis of transfer semi‐hydrogenation, where the addition of base appeared not to be necessary to obtain the desired product stereoselectively. Copyright © 2009 John Wiley & Sons, Ltd.     

An experimental and kinetic modeling study on the oxidation of 1,3-dioxolane

The modern catalytic or enzymatic advances allow the production of novel biofuel. Among them, 1,3-dioxolane can be produced from formaldehyde and ethylene glycol, both can be obtained from biomass. In this study, the oxidation of 1,3-dioxolane is studied at stoichiometric conditions. The ignition delay times of 1,3-dioxolane/O₂/inert mixtures were measured in a shock tube and in a rapid compression machine at pressures of 20 to 40 bar and temperatures ranging from 630 to 1300 K. The pressure profiles recorded in the rapid compression machine show a first stage of ignition enlightening the influence of the low temperature chemistry of combustion. Furthermore, mole fraction profiles of the stable intermediates produced during the oxidation of 1,3-dioxolane were measured in a jet-stirred reactor at 10 bar. Following these observations, a detailed kinetic model was developed with reaction rate coefficients and thermochemical data calculated by theoretical calculations or estimated by analogies to suitable molecules. In order to get an insight into the most important reaction pathways brute force sensitivity analysis and reaction pathway analysis were performed with the proposed model and discussed. It became clear that in the fuel-in-air case for the alkylhydroperoxide of 1,3-dioxolane the ring opening beta-scission pathway is favored against the further alkane-like second addition to molecular oxygen, which leads to a limited negative temperature coefficient.     

Homoleptic Zincate‐Promoted Room‐Temperature Halogen–Metal Exchange of Bromopyridines

Homoleptic lithium tri‐ and tetraalkyl zincates were reacted with a set of bromopyridines. Efficient and chemoselective bromine–metal exchanges were realized at room temperature with a substoichiometric amount of nBu₄ZnLi₂?TMEDA reagent (1/3 equiv; TMEDA=N,N,N′,N′‐tetramethylethylenediamine). This reactivity contrasted with that of tBu₄ZnLi₂?TMEDA, which was inefficient below one equivalent. DFT calculations allowed us to rationalize the formation of N???Li stabilized polypyridyl zincates in the reaction. The one‐pot difunctionalization of dibromopyridines was also realized using the reagent stoichiometrically. The direct creation of C? Zn bonds in bromopyridines enabled us to perform efficient Negishi‐type cross‐couplings.