Diastereomer configurations from joint experimental-computational analysis

The potential of the approach combining nuclear magnetic resonance (NMR) spectroscopy, relaxed grid search (RGS), molecular dynamics (MD) simulations, and quantum mechanical (QM) calculations for the determination of diastereomer configurations is demonstrated using four diastereomers of a trisubstituted epoxide. Since the change in configuration of the chiral center is expected to change the distribution of conformer populations (including those of side-chain rotamers), changes in NMR parameters [chemical shifts, J couplings, and nuclear Overhauser effects (NOEs)] are expected. The method therefore relies on (1) identification of possible conformations in each diastereomer using relaxed grid search analysis and MD simulations; (2) geometry optimizations of conformers selected from step (1), followed by calculations of their relative energies (populations) using QM methods; (3) calculations of averaged NMR parameters using QM methods; (4) matching calculated and experimental values of NMR parameters of diastereomers. The diastereomer configurations are considered resolved, if three NMR parameters different in nature, chemical shifts, J couplings, and NOEs, are in agreement. A further advantage of this method is that full structural and dynamics characterization of each of the diastereomers is achieved based on the joint analysis of experimental and computational data.     

Refined Enumeration of Permutations Sorted with Two Stacks and a D 8-Symmetry

We study permutations that are sorted by operators of the form S ° α ° S, where S is the usual stack sorting operator introduced by Knuth and α is any D ₈-symmetry obtained by combining the classical reverse, complement, and inverse operations. Such permutations can be characterized by excluded (generalized) patterns. Some conjectures about the enumeration of these permutations, refined with numerous classical statistics, have been proposed by Claesson, Dukes, and Steingrímsson. We prove these conjectures, and enrich one of them with a few more statistics. The proofs mostly rely on generating trees techniques, and on a recent bijection of Giraudo between Baxter and twisted Baxter permutations.     

Quantum vacuum magnetic birefringence

From a series of M?ssbauer measurements performed on a single crystal of FePSe₃, we have observed the effect of electromagnetically induced transparency (EIT) in a second nuclear system, after a first experiment using the mineral siderite FeCO₃. When the condition of nuclear level crossing was fulfilled, an obvious deficit in absorption was observed at the point of level crossing. This reduced absorption cannot be ascribed to saturation effects because of the specific geometry of the measurement. We conclude that the observed deficit in absorption is due to coherence and interference effects.     

Effects of melamine polyphosphate and halloysite nanotubes on the flammability and thermal behavior of polyamide 6

Melamine polyphosphate (MPP) and halloysite nanotubes (HNT) were introduced to polyamide 6 (PA6) by melt blending in order to improve the fire resistance. PA6 composite containing 12% flame retardants with good spinnability was obtained. The flammability of PA6 composite was characterized by limiting oxygen index (LOI), UL‐94 vertical burning and cone calorimeter (CONE) tests. The results indicated that the LOI value could reach 24.0 vol.% and UL‐94 rating could achieve V2 level at the presence of 12% flame retardants. CONE data demonstrated that peak heat release rate was significantly reduced from 554 kW/m² of neat PA6 to 368 kW/m² of the sample containing flame retardants. Thermal analysis indicated that the thermal stability and char formation were improved by the presence of flame retardants. The morphology of residue char was characterized by scanning electron microscopy; and it suggested that a network‐structured protective char layer had been formed. The possible synergism between MPP/HNT and their flame retardant mechanism was also analyzed and discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Predicting a Sharp Decline in Selectivity for Catalytic Esterification of Alcohols from van der Waals Interactions

Controlling the selectivity of catalytic reactions is a critical aspect of improving energy efficiency in the chemical industry; thus, predictive models are of key importance. Herein the performance of a heterogeneous, nanoporous Au catalyst is predicted for the complex catalytic self‐coupling of the series of C₂–C₄ alkyl alcohols, based solely on the known kinetics of the elementary steps of the catalytic cycle for methanol coupling, using scaling methods augmented by density functional theory. Notably, a sharp decrease in selectivity for ester formation with increasing molecular weight to favor the aldehyde due to van der Waals interactions of reaction intermediates with the surface was predicted and subsequently verified quantitatively by experiment. Further, the agreement between theory and experiment clearly demonstrates the efficacy of this approach for building a predictive model of catalytic behavior for a homologous set of reactants using a small set of experimental information.     

Gold(I)/Gold(III) Catalysis that Merges Oxidative Addition and π-Alkene Activation

Heteroarylation of alkenes with aryl iodides was efficiently achieved with a (MeDalphos)AuCl complex through Au^I/Au^III catalysis. The possibility to combine oxidative addition of aryl iodides and π-activation of alkenes at gold is demonstrated for the first time. The reaction is robust and general (>30 examples including internal alkenes, 5-, 6-, and 7-membered rings). It is regioselective and leads exclusively to trans addition products. The (P,N) gold complex is most efficient with electron-rich aryl substrates, which are troublesome with alternative photoredox/oxidative approaches. In addition, it provides a very unusual switch in regioselectivity from 5-exo to 6-endo cyclization between the Z and E isomers of internal alkenols.     

Photochemical grafting of diazonium salts on metals

4-Nitrobenzenediazonium may be photochemically grafted onto gold, copper and iron under visible and UV light. Thin nanometre layers are obtained and characterized by IRRAS, electrochemistry and ellipsometry.     

Mapping the x-ray emission region in a laser-plasma accelerator

The x-ray emission in laser-plasma accelerators can be a powerful tool to understand the physics of relativistic laser-plasma interaction. It is shown here that the mapping of betatron x-ray radiation can be obtained from the x-ray beam profile when an aperture mask is positioned just beyond the end of the emission region. The influence of the plasma density on the position and the longitudinal profile of the x-ray emission is investigated and compared to particle-in-cell simulations. The measurement of the x-ray emission position and length provides insight on the dynamics of the interaction, including the electron self-injection region, possible multiple injection, and the role of the electron beam driven wakefield.