Aqueous enantioselective organocatalytic Diels-Alder reactions employing hydrazide catalysts. A new scaffold for organic acceleration

[reaction: see text] Cyclic hydrazides function as asymmetric organocatalysts in aqueous Diels-Alder reactions. The hydrazide is employed as the catalytic machinery in a compact camphor-derived framework that imparts facial selectivity to the cycloadditions. Kinetic evidence suggests the reaction involves rapid iminium formation.     

Jack Polynomials in Superspace

This work initiates the study of orthogonal symmetric polynomials in superspace. Here we present two approaches leading to a family of orthogonal polynomials in superspace that generalize the Jack polynomials. The first approach relies on previous work by the authors in which eigenfunctions of the supersymmetric extension of the trigonometric Calogero-Moser-Sutherland Hamiltonian were constructed. Orthogonal eigenfunctions are now obtained by diagonalizing the first nontrivial element of a bosonic tower of commuting conserved charges not containing this Hamiltonian. Quite remarkably, the expansion coefficients of these orthogonal eigenfunctions in the supermonomial basis are stable with respect to the number of variables. The second and more direct approach amounts to symmetrize products of non-symmetric Jack polynomials with monomials in the fermionic variables. This time, the orthogonality is inherited from the orthogonality of the non-symmetric Jack polynomials, and the value of the norm is given explicitly.     

Re-based heterogeneous catalysts for olefin metathesis prepared by surface organometallic chemistry: reactivity and selectivity

Herein we describe the catalytic activity of 1, a well-defined Re alkylidene complex supported silica, in the reaction of olefin metathesis. This system is highly active for terminal and internal olefins with initial rates up to 0.7 mol per mol Re per s. It also catalyses the self-metathesis of methyl oleate (MO) without the need of co-catalysts. The turnover numbers can reach up to 900 for MO, which is unprecedented for a heterogeneous Re-based catalyst. Moreover the use of silica as a support can bring major advantages, such as the possibility to use branched olefins like isobutene, which are usually incompatible with alumina-based supports; therefore, the formation of isoamylene from the cross-metathesis of propene and isobutene can be performed. All these results are in sharp contrast to what has been found for other silica- or alumina-supported rhenium oxide systems, which are either completely inactive (silica system) or typically need co-catalysts when functionalised olefins are used. Finally the initiation step corresponds to a cross-metathesis reaction to give a 3:1 mixture of 3,3-dimethylbutene and trans-4,4-dimethylpent-2-ene, and make this catalyst the first generation of well-defined Re-based heterogeneous catalysts.     

A supramolecular cup-and-ball C60-porphyrin conjugate system

In addition to the ammonium-crown ether recognition, pi-stacking interactions between the C60 sphere and the porphyrin moiety have been evidenced in a supramolecular complex obtained from a porphyrin-crown ether conjugate and a fullerene derivative bearing an ammonium unit.     

On the structure of weight modules

Given any simple Lie superalgebra , we investigate the structure of an arbitrary simple weight -module. We introduce two invariants of simple weight modules: the shadow and the small Weyl group. Generalizing results of Fernando and Futorny we show that any simple module is obtained by parabolic induction from a cuspidal module of a Levi subsuperalgebra. Then we classify the cuspidal Levi subsuperalgebras of all simple classical Lie superalgebras and of the Lie superalgebra W. Most of them are simply Levi subalgebras of , in which case the classification of all finite cuspidal representations has recently been carried out by one of us (Mathieu). Our results reduce the classification of the finite simple weight modules over all classical simple Lie superalgebras to classifying the finite cuspidal modules over certain Lie superalgebras which we list explicitly.

     

Ultrashort microwave pulses generated due to three magnon interactions

Density-functional theory is applied to the interaction site model to study gas-liquid nucleation in a partially immiscible binary system consisting of spherical Lennard-Jones atoms (monomers) and dumbbell molecules of two Lennard-Jones atoms (dimers). Increased interaction anisotropy between the dimer sites and monomers is shown to result in mutual enhancement of nucleation. Critical nuclei with a lamellar structure are observed at high dimer activities.     

Retardation effects in the rotating string model

A new method to study the retardation effects in mesons is presented. It is based on a generalized rotating string model, in which a nonzero value of the relative time between the quark and the antiquark is allowed. This approach leads to a retardation term in the Hamiltonian which behaves as a perturbation of the nonretarded Hamiltonian and preserves the Regge trajectories for light mesons. The straight-line ansatz is used to describe the string, and the relevance of this approximation is tested. It is shown that the string is actually curved because of retardation, but this bending does not bring a relevant contribution to the energy spectrum of the model.     

Improving the flame retardancy of polyamide 6 by incorporating hexachlorocyclotriphosphazene modified MWNT

A nitrogen‐, phosphorus‐ and chlorine‐containing flame retardant, hexachlorocyclotriphosphazene (HCTP), has been covalently grafted onto the surface of multi‐wall carbon nanotubes (MWNT) to obtain MWNT‐HCTP. Polyamide 6 (PA6)/MWNT composites were then prepared via melt compounding. The flammability of PA6/MWNT composite was characterized by cone calorimetry, limiting oxygen index (LOI) and UL‐94 tests. The results showed that peak heat release rate of samples containing 3 wt% MWNT‐HCTP was only 460 kW/m², which decreased by 35.2% compared with that of a neat PA6 sample. The LOI value was increased from 22.7% to 26.5%, and UL‐94 test performance was also significantly improved by the presence of MWNT‐HCTP. Scanning electron microscope (SEM) and optical microscope analysis showed that modified MWNT had a better dispersion and compatibility in PA6 than unmodified MWNT. The composition of residue chars and volatile products was investigated by SEM/energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermogravimetric‐FTIR, respectively. It was proposed that grafted HCTP was mainly functioned in the condensed phase, where P, N can synergistically promote char formation and Cl element can catch free radicals to terminate the chain reaction during combustion of the PA6 composite. Copyright © 2014 John Wiley & Sons, Ltd.     

Binaural prediction of speech intelligibility in reverberant rooms with multiple noise sources

When speech is in competition with interfering sources in rooms, monaural indicators of intelligibility fail to take account of the listener's abilities to separate target speech from interfering sounds using the binaural system. In order to incorporate these segregation abilities and their susceptibility to reverberation, Lavandier and Culling [J. Acoust. Soc. Am. 127, 387-399 (2010)] proposed a model which combines effects of better-ear listening and binaural unmasking. A computationally efficient version of this model is evaluated here under more realistic conditions that include head shadow, multiple stationary noise sources, and real-room acoustics. Three experiments are presented in which speech reception thresholds were measured in the presence of one to three interferers using real-room listening over headphones, simulated by convolving anechoic stimuli with binaural room impulse-responses measured with dummy-head transducers in five rooms. Without fitting any parameter of the model, there was close correspondence between measured and predicted differences in threshold across all tested conditions. The model's components of better-ear listening and binaural unmasking were validated both in isolation and in combination. The computational efficiency of this prediction method allows the generation of complex "intelligibility maps" from room designs.     

Long-time self-diffusion of charged colloidal particles: electrokinetic and hydrodynamic interaction effects

The authors analyze the long-time self-diffusion of charge-stabilized colloidal macroions in nondilute suspensions using a mode-coupling scheme developed for multicomponent suspensions of interacting Brownian spheres. In this scheme, all ionic species, including counterions and electrolyte ions, are treated on an equal footing as charged hard spheres undergoing overdamped Brownian motion. Hydrodynamic interactions between all ions are accounted for on the far-field level. We show that the influence on the colloidal long-time self-diffusion coefficient arising from the relaxation of the microionic atmosphere surrounding the colloids, the so-called electrolyte friction effect, is usually insignificant in comparison with the friction contributions arising from direct and hydrodynamic interactions between the colloidal particles. This finding is true even for small colloid concentrations unless the mobility difference between colloidal particles and microions is not large. Furthermore, we observe an interesting nonmonotonic density dependence of the colloidal long-time self-diffusion coefficient in suspensions with low amount of added salt. We show that this unusual density dependence is due to colloid-colloid hydrodynamic interactions.