Captured and cross-linked palladium nanoparticles

Polystyrene-poly(ethylene glycol) resin-captured cross-linked palladium nanopaticles were prepared via a straightforward route, and their heterogeneous behavior was truly confirmed by various tests. They were applied to aqueous Suzuki cross-coupling reactions with various aryl bromides and recycled up to six times without loss of activity.     

Fe(0)-mediated synthesis of tri- and tetra-substituted olefins from carbonyls: an environmentally friendly alternative to Cr(II)

Fe(0) was investigated as a cost-effective, environmentally friendly alternative to Cr(II) for the olefination of carbonyls by activated polyhalides. In many instances, Fe(0) was equivalent or superior to Cr(II). Notably, Fe(0), but not Cr(II), proved compatible with a wide range of functionality, inter alia, unprotected phenol, aryl nitro, carboxylic acid, and alkyl nitrile. A surprising reversal of stereoselectivity for aldehydes versus ketones was observed using both metals. The resultant alpha-halo-alpha,beta-unsaturated or alpha,beta-unsaturated carboxylic acids, esters, and nitriles are common structural elements in numerous compounds of interest as well as key intermediates in the preparation of other functionality.     

Compression-induced stiffness in the buckling of a one fiber composite

We study the buckling of a one fiber composite whose matrix stiffness is slightly dependent on the compressive force. We show that the equilibrium curves of the system exhibit a limit load when the induced stiffness parameter gets bigger than a threshold. This limit load increases when the stiffness parameter is increasing and it is related to a possible localized path in the post-buckling domain. Such a change in the maximum load may be very desirable from a structural stand point.     

Morphology of MgO smoke crystallites upon etching in wet environment

The etching of MgO smoke in wet conditions – an archetype for aqueous dissolution of oxide crystals – is explored on the basis of transmission electron microscope (TEM) analyses. In pure water with neutral pH, in acid solutions and in moist air, the MgO cubic crystallites show first (1 1 0) truncations of the 〈1 1 0〉 edges and then (1 1 1) cuts at the corners. Criteria are given to characterize (1 1 0) and (1 1 1) cuts on the TEM images. It is shown that (1 1 0) truncations appear independently of the formation of the (1 1 1) cuts and are associated with a stationary state. The picture is fully consistent with the previous suggestion of a “constrained Wulff profile” [9] which explains the formation of (1 1 0) cuts by excluding (1 1 1) facets.     

Tracy–Widom at High Temperature

We investigate the marginal distribution of the bottom eigenvalues of the stochastic Airy operator when the inverse temperature \(\beta \) tends to \(0\) . We prove that the minimal eigenvalue, whose fluctuations are governed by the Tracy–Widom \(\beta \) law, converges weakly, when properly centered and scaled, to the Gumbel distribution. More generally we obtain the convergence in law of the marginal distribution of any eigenvalue with given index \(k\) . Those convergences are obtained after a careful analysis of the explosion times process of the Riccati diffusion associated to the stochastic Airy operator. We show that the empirical measure of the explosion times converges weakly to a Poisson point process using estimates proved in Dumaz and Virág (Ann Inst H Poincaré Probab Statist 49(4):915–933, 2013). We further compute the empirical eigenvalue density of the stochastic Airy ensemble on the macroscopic scale when \(\beta \rightarrow 0\) . As an application, we investigate the maximal eigenvalues statistics of \(\beta _N\) -ensembles when the repulsion parameter \(\beta _N\rightarrow 0\) when \(N\rightarrow +\infty \) . We study the double scaling limit \(N\rightarrow +\infty , \beta _N \rightarrow 0\) and argue with heuristic and numerical arguments that the statistics of the marginal distributions can be deduced following the ideas of Edelman and Sutton (J Stat Phys 127(6):1121–1165, 2007) and Ramírez et al. (J Am Math Soc 24:919–944, 2011) from our later study of the stochastic Airy operator.     

How Can a Hydrophobic MOF be Water‐Unstable? Insight into the Hydration Mechanism of IRMOFs

We report an ab initio molecular dynamics study of the hydration process in a model IRMOF material. At low water content (one molecule per unit cell), water physisorption is observed on the zinc cation but the free?bound equilibrium strongly favors the free state. This is consistent with the hydrophobic nature of the host matrix and its type‐V isotherm observed in a classical Monte Carlo simulation. At higher loading, a water cluster can be formed at the Zn₄O site and this is shown to stabilize the water‐bound state. This structure rapidly transforms into a linker‐displaced state, where water has fully displaced one arm of a linker and which corresponds to the loss of the material’s fully ordered structure. Thus an overall hydrophobic MOF material can also become water unstable, a feature that has not been fully understood until now.     

Co4(OH)2(C10H16O4)3 metal-organic framework: slow magnetic relaxation in the ordered phase of magnetic chains

Reported here are the synthesis and structural and topological analysis as well as a magnetic investigation of the new Co(4)(OH)(2)(C(10)H(16)O(4))(3) metal-organic framework. The structural analysis reveals a one-dimensional inorganic subnetwork based on complex chains of cobalt(II) ions in two different oxygen environments. Long alkane dioic acid molecules bridge these inorganic chains together to afford large distances and poor magnetic media between dense spin chains. The thermal dependence of the χT product provides evidence for uncompensated antiferromagnetic interactions within the cobaltous chains. In zero-field, dynamic magnetic susceptibility measurements show slow magnetic relaxation below 5.4 K while both neutron diffraction and heat capacity measurements give evidence of long-range order (LRO) below this temperature. The slow dynamics may originate from the motion of broad domain walls and is characterized by an Arrhenius law with a single energy barrier Δ(τ)/k(B) = 67(1) K for the [10-5000 Hz] frequency range. Moreover, in nonzero dc fields the ac susceptibility signal splits into a low-temperature frequency-dependent peak and a high-temperature frequency-independent peak which strongly shifts to higher temperature upon increasing the bias dc field. Heat capacity measurements have been carried out for various applied field values, and the recorded C(P)(T) data are used for the calculation of the thermal variations of both the adiabatic temperature change ΔT(ad) and magnetic entropy change ΔS(m). The deduced data show a modest magnetocaloric effect at low temperature. Its maximum moves up to higher temperature upon increasing the field variation, in relation with the field-sensibility of the intrachain magnetic correlation length.     

Analysis and reconstruction of a pulsed jet in crossflow by multi-plane snapshot POD

In this work, snapshot proper orthogonal decomposition (POD) is used to study a pulsed jet in crossflow where the velocity fields are extracted from stereoscopic particle image velocimetry (SPIV) results. The studied pulsed jet is characterized by a frequency f = 1 Hz, a Reynolds number Re _j  = 500 (based on the mean jet velocity ${\overline{U}_{j}}$  = 1.67 cm/s and a mean velocity ratio of R = 1). Pulsed jet and continuous jet are compared via mean velocity field trajectory and Q criterion. POD results of instantaneous, phase-averaged and fluctuating velocity fields are presented and compared in this paper. Snapshot POD applied on one plane allows us to distinguish an organization of the first spatial eigenmodes. A distinction between “natural modes” and “pulsed modes” is achieved with the results obtained by the pulsed and unforced jet. Secondly, the correlation tensor is established with four parallel planes (multi-plane snapshot POD) for the evaluation of volume spatial modes. These resulting modes are interpolated and the volume velocity field is reconstructed with a minimal number of modes for all the times of the pulsation period. These reconstructions are compared to orthogonal measurements to the transverse jet in order to validate the obtained three-dimensional velocity fields. Finally, this POD approach for the 3D flow field reconstruction from experimental data issued from planes parallel to the flow seems capable to extract relevant information from a complex three-dimensional flow and can be an alternative to tomo-PIV for large volume of measurement.     

Vibrational study of the superprotonic phase transition in the mixed crystal Rb2(HSeO4)(H2PO4)

Raman spectra (10–1200 cm⁻¹) of polycrystalline samples of Rb₂(HSeO₄)(H₂PO₄) were studied at temperatures ranging from 300 to 423 K. An assignment of most of the observed bands is proposed. The first‐order phase transition previously detected at 382 K was characterized as: This superionic‐protonic transition is believed to be governed by librations of the HSe/PO₄²⁻ ion and the A OH (A = Se, P) stretching mode. It corresponds to the weakening of  Se(P) O H˙˙˙ H O Se(P) hydrogen bonds and to the melting of the proton sublattice into a quasi‐liquid state in which the protons and the HSe/PO₄²⁻ ions contribute to the unusually high conductivity. The activation energy that was determined from the plot Δν_1/2 versus temperature for the ν (A OH) band has the same order of magnitude as that determined from conductivity measurements. Copyright © 2006 John Wiley & Sons, Ltd.