Dehydrogenation of ammonia borane aided by hydrophobic ionic liquids

The beneficial effect on the dehydrogenation of ammonia borane due to mixing with hydrophobic ionic liquids (ILs) is investigated by means of detailed combined TG–DTA and IR measurements. Desorption of several mixtures of ammonia borane with hydrophobic ILs having bis(trifluoromethanesulfonyl)-imide or trifluorosulfonyl-imide anions was studied in both isothermal and non-isothermal conditions. The addition of hydrophobic liquids lowers the dehydrogenation temperatures and allows the observation of the decomposition process without any induction time even at temperatures below 90 °C. The IR data of the products of the decomposition confirm that ILs do not react with AB but provide an highly polar medium which promotes the decomposition reaction. Furthermore, the proposed method to enhance hydrogen release from ammonia borane provides the possibility of working in air avoiding any protective atmosphere.     

Flexural-torsional bifurcations of a cantilever beam under potential and circulatory forces I: Non-linear model and stability analysis

The stability of a cantilever elastic beam with rectangular cross-section under the action of a follower tangential force and a bending conservative couple at the free end is analyzed. The beam is herein modeled as a non-linear Cosserat rod model. Non-linear, partial integro-differential equations of motion are derived expanded up to cubic terms in the transversal displacement and torsional angle of the beam. The linear stability of the trivial equilibrium is studied, revealing the existence of buckling, flutter and double-zero critical points. Interaction between conservative and non-conservative loads with respect to the stability problem is discussed. The critical spectral properties are derived and the corresponding critical eigenspace is evaluated.     

Dependence of CO oxidation on Pt nanoparticle shape: a shape‐selective approach to the synthesis of PEMFC catalysts

In real catalyst systems, it is difficult to establish a correlation between catalytic properties and the shape (crystal planes, corners and steps) of the active catalytic particles. In this paper we present a clear shape dependence of the catalytic properties of a Vulcan‐supported fuel cell catalyst having 4 nm cubo‐octahedral platinum(0) nanocrystallites with (111) and (100) surfaces stabilized by sodium polyacrylate. The electrode materials were characterized by CO‐stripping cyclic voltammetry and transmission electron microscopy (TEM), showing that no agglomeration had occurred among the nanoparticles on the catalyst surfaces. Copyright © 2007 John Wiley & Sons, Ltd.     

Can simple enones be useful partners for the catalytic stereoselective alkylation of indoles?

A new catalytic system for the first example of enantioselective Friedel-Crafts-type (FC) addition of indoles to simple enones is described. The use of an equimolar amount of chiral [Al(salen)Cl] and 2,6-lutidine (10 mol %) was found to be effective in promoting the conjugate addition of indoles to (E)-arylcrotyl ketones, furnishing the corresponding beta-indolyl ketones in excellent yield and high enantioselectivity (ee up to 89%). The role of the base was investigated through spectroscopic as well as computational analyses, which suggested that in situ formation of a new chiral (base.[Al(salen)]) complex was operating under our reaction conditions. In particular, a stable cationic [Al(salen)] hexacoordinate trans complex with the additive base and the enone is suggested as being responsible for the stereocontrolled reaction. Finally, detailed monitoring of the reaction course was carried out showing that a conventional FC pathway induced by [Al(salen)Cl] acting as a Lewis acid is operating.     

Stability boundaries, percolation threshold, and two-phase coexistence for polydisperse fluids of adhesive colloidal particles

We study the polydisperse Baxter model of sticky hard spheres (SHS) in the modified mean spherical approximation (mMSA). This closure is known to be the zero-order approximation C0 of the Percus-Yevick closure in a density expansion. The simplicity of the closure allows a full analytical study of the model. In particular we study stability boundaries, the percolation threshold, and the gas-liquid coexistence curves. Various possible subcases of the model are treated in details. Although the detailed behavior depends upon the particularly chosen case, we find that, in general, polydispersity inhibits instabilities, increases the extent of the nonpercolating phase, and diminishes the size of the gas-liquid coexistence region. We also consider the first-order improvement of the mMSA (C0) closure (C1) and compare the percolation and gas-liquid boundaries for the one-component system with recent Monte Carlo simulations. Our results provide a qualitative understanding of the effect of polydispersity on SHS models and are expected to shed new light on the applicability of SHS models for colloidal mixtures.     

New furoquinoline alkaloid and flavanone glycoside derivatives from the leaves of Oricia suaveolens and Oricia renieri (Rutaceae)

Fractionation of the methanol extract of the leaves of Oricia renieri and Oricia suaveolens (Rutaceae) led to the isolation of 13 compounds including the hitherto unknown furoquinoline alkaloid named 6,7-methylenedioxy-5-hydroxy-8-methoxy-dictamnine (1) and a flavanone glycoside named 5-hydroxy-4′-methoxy-7-O-[α-l-rhamnopyranosyl(1?→5″)-β-d-apiofuranosyl]-flavanoside (2), together with 11 known compounds (3–13). The structures of the compounds were determined by comprehensive analyses of their 1D and 2D NMR, mass spectral data and comparison. All compounds isolated were examined for their activity against human carcinoma cell lines. The alkaloids 1, 5, 12, 13 and the phenolic 2, 8, 11 tested compounds exhibited non-selective moderate cytotoxic activity with IC₅₀ 8.7–15.9 μM whereas compounds 3, 4, 6, 7, 9 and 10 showed low activity.