Hydrogen: a good partner for rhodium‐catalyzed hydrosilylation

The influence of hydrogen pressure on the hydrosilylation of ketones catalyzed by [((S)‐SYNPHOS)Rh(nbd)]OTf has been studied. We have notably demonstrated that hydrogen significantly affected the outcome of the reaction while not being consumed as stoichiometric reducing agent. In THF, diethyl ether or toluene, the hydrogen pressure exceedingly accelerated the hydrosilylation reaction and preserved or even improved the enantioselectivity of the process. In CH₂Cl₂, the rhodium catalyst also showed generally higher catalytic activity under hydrogen pressure. Most serendipitously, several ketones were found to give products of absolute opposite configuration upon performing the hydrosilylation under argon atmosphere or under hydrogen pressure. Copyright © 2014 John Wiley & Sons, Ltd.     

A Systematic Account on Aromatic Hydroxylation by a Cytochrome P450 Model Compound I: A Low‐Pressure Mass Spectrometry and Computational Study

Cytochrome P450 enzymes are heme‐containing mono‐oxygenases that mainly react through oxygen‐atom transfer. Specific features of substrate and oxidant that determine the reaction rate constant for oxygen atom transfer are still poorly understood and therefore, we did a systematic gas‐phase study on reactions by iron(IV)‐oxo porphyrin cation radical structures with arenes. We present herein the first results obtained by using Fourier transform‐ion cyclotron resonance mass spectrometry and provide rate constants and product distributions for the assayed reactions. Product distributions and kinetic isotope effect studies implicate a rate‐determining aromatic hydroxylation reaction that correlates with the ionization energy of the substrate and no evidence of aliphatic hydroxylation products is observed. To further understand the details of the reaction mechanism, a computational study on a model complex was performed. These studies confirm the experimental hypothesis of dominant aromatic over aliphatic hydroxylation and show that the lack of an axial ligand affects the aliphatic pathways. Moreover, a two‐parabola valence bond model is used to rationalize the rate constant and identify key properties of the oxidant and substrate that drive the reaction. In particular, the work shows that aromatic hydroxylation rates correlate with the ionization energy of the substrate as well as with the electron affinity of the oxidant.     

From inconsistent results to high speed hydrosilylation

After noting that the presence of dihydrogen, generated in situ from the partial hydrolysis of a silane with residual water, significantly enhances the rate of the rhodium-catalysed hydrosilylation of acetophenone, we developed a high speed hydrosilylation reaction under dihydrogen pressure.     

Comparative measurements of the plasma potential with the ball-pen and emissive probes on the CASTOR tokamak

A novel approach to the direct measurement of the plasma potential in magnetized plasmas, using the so-called “ball-pen probe”, was recently tested in the CASTOR tokamak. Comparison with the standard technique of plasma potential measurement using the emissive probe is reported. It is found that the plasma potential determined by the emissive probe is systematically lower than that measured by the ball-pen probe. The difference is of the of the of kT _e/e. A possible reason of this difference is the space charge occurring in the proximity of the emissive probe.     

Rate‐type Model for electro‐rheological Material Behaviour consistent with Extended Thermodynamics: Application to a steady viscometric flow

Based on extended thermodynamics, a class of rate‐type constitutive equations for electrorheological materials is presented. It is shown unlike many recent works using standard methods of continuum mechanics, that this approach, which consists in postulating expressions which relate the time derivative of the Cauchy stress to the motion, takes well account of the viscoelastic‐plastic effects as well as the coupling between the motion and the electric field. By considering special cases it turns out that the derived nonlinear algebraic model embeds a variety of existing differential models in the literature. The accuracy of the model is illustrated by considering a steady shear flow in which the electric field is applied perpendicularly to the flow direction. Analytical solutions with various parameter variations are obtained and discussed. The model predicts well the behaviour associated with material instabilities observed in viscometric flows for which the existence of the yield stress is required as confirmed by many experiments.     

Fluctuation measurements with emissive probes in tokamaks

A new probe head, composed of two electro-emissive probes and two Langmuir probes has been designed to measure edge fluctuations in the CASTOR tokamak. In this contribution, only one Langmuir and one electron-emissive probe are used to measure the temperature and potential fluctuations and the phase angle between them.     

A novel approach to direct measurement of the plasma potential

A novel probe and approach to the direct measurements of the plasma potential in a strong magnetic field is suggested. The principle of this method is to reduce the electron saturation current to the same magnitude as that of the ion saturation current. In this case, the floating potential of the probe becomes indentical to the plasma potential. This goal is attained by a shield, which screens off an adjustable part of the electron current from the probe collector due to the much smaller gyro-radius of the electrons. First systematic measurements have been perfomred in the CASTOR tokamak.     

Parameter identification of advanced plastic strain rate potentials and impact on plastic anisotropy prediction

In the work presented in this paper, several strain rate potentials are examined in order to analyze their ability to model the initial stress and strain anisotropy of several orthotropic sheet materials. Classical quadratic and more advanced non-quadratic strain rate potentials are investigated in the case of FCC and BCC polycrystals. Different identifications procedures are proposed, which are taking into account the crystallographic texture and/or a set of mechanical test data in the determination of the material parameters.     

Application of strain rate potentials with multiple linear transformations to the description of polycrystal plasticity

This paper reviews a class of anisotropic plastic strain-rate potentials, based on linear transformations of the plastic strain-rate tensor. A new formulation is proposed, which includes former models as particular cases and allows for an arbitrary number of linear transformations, involving an increasing number of anisotropy parameters. The formulation is convex and fully three-dimensional, thus being suitable for computer implementation in finite element codes. The parameter identification procedure uses a micromechanical model to generate evenly distributed reference points in the full space of possible loading modes. Material parameters are determined for several anisotropic, fcc and bcc sheet metals, and the gain in accuracy of the new models is demonstrated. For the considered materials, increasing the number of linear transformations leads to a systematic improvement of the accuracy, up to a number of five linear transformations. The proposed model fits very closely the predictions of the micromechanical model in the whole space of plastic strain-rate directions. The r-values, which are not directly used in the identification procedure, served for the validation of the models and to demonstrate their improved accuracy.     

Redundancy for localized frames

Redundancy is the qualitative property which makes Hilbert space frames so useful in practice. However, developing a meaningful quantitative notion of redundancy for infinite frames has proven elusive. Though quantitative candidates for redundancy exist, the main open problem is whether a frame with redundancy greater than one contains a subframe with redundancy arbitrarily close to one. We will answer this question in the affirmative for ℓ ¹-localized frames. We then specialize our results to Gabor multi-frames with generators in M ¹(R ^d ), and Gabor molecules with envelopes in W(C, l ¹). As a main tool in this work, we show there is a universal function g(x) so that, for every ε =s> 0, every Parseval frame {f _i } _i=1 ^M for an N-dimensional Hilbert space H _N has a subset of fewer than (1+ε)N elements which is a frame for H _N with lower frame bound g(ε/(2M/N − 1)). This work provides the first meaningful quantative notion of redundancy for a large class of infinite frames. In addition, the results give compelling new evidence in support of a general definition of redundancy given in [5].