Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.     

Gas-phase vibrational spectroscopy and ab initio study of organophosphorus compounds: discrimination between species and conformers

Gas phase vibrational spectra of dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), and triethyl phosphate (TEP) have been measured using FTIR spectroscopy. For DMMP, TMP, and TEP, most of the infrared active vibrational modes have been observed in the 50-5000 cm (-1) spectral range, allowing an unambiguous discrimination between the three molecules. The vibrational analysis of the spectra was performed by comparing with MP2 and B3LYP harmonic and anharmonic force field ab initio calculations. The extension to anharmonic calculations provides the best agreement for the mid-infrared and the near-infrared spectra, but they do not improve the harmonic frequency predictions in the far-infrared domain. This part of the vibrational spectra associated with collective and nonlocalized vibrational modes presents the largest frequency differences between the two lowest energy conformers of DMMP and TMP. These two conformers were taken into account in the vibrational assignment of the spectra. Their experimental evidence was obtained by deconvoluting vibrational bands in the mid-infrared and in the far-infrared regions, respectively. For TEP, the conformational landscape appears very complicated at ambient temperature, and a further analysis at low temperature is required to explain the vibrational features of each conformer.     

Numerical analysis of steady turbulent triple jet flow with temperature difference

The numerical predictions confirm a new classification of flow patterns of triple jet interaction. The addition of side jets increase the rate of decrease of the centreline velocity for the flow of type A and decreases in the other cases. The effect of various types of flow on the rate of decrease of the velocity, the turbulent kinetic energy and the temperature in the combined region are detailed. Several correlations are proposed.     

Efficient multicomponent synthesis of 2-aminopyridines catalysed by basic mesoporous materials

Research on Chemical Intermediates - An efficient and green procedure for the synthesis of 2-aminopyridines derivatives via four-component reaction of acetophenone, malononitrile, triethoxymethane...     

Synthesis and characterization of nanoheterostructures based on oligothiophene functionalized Ru nanoparticles

Monodisperse ruthenium nanoparticles functionalized by electroactive oligothiophenes have been prepared and characterized. Using TEM, UV-visible and FTIR we established that the organization of these nanoparticles into nanospheres can be directly controlled via modulation of the pi-pi interaction between the organic components adsorbed on the surface. This finding also shows that the self-assembled nanoheterostructures may be switched from monodisperse nanoparticles to ordered nanospheres by tuning the pH.     

Nanocrystalline iron oxide synthesised within Hierarchical Porous Silica prepared by nanoemulsion templating

PIC (Phase Inversion Composition) O-W nanoemulsions was used as a template for the synthesis of Hierarchical Porous Silica (HPS), and the oil phase of the nanoemulsion was used as a nanoreactor for the preparation of magnetic gamma-Fe(2)O(3) nanoparticles, confined within the silica matrix.     

Zeolite-Polymer Composite Materials as Water Scavenger

The influence of the charge compensating cation nature (Na⁺, Mg²⁺) on the water adsorption properties of LTA-type zeolites used as filler in composite materials (zeolite/polymers) was investigated. Large scale cation exchanges were performed on zeolite powder at 80 °C for 2 h using 1 M magnesium chloride (MgCl₂) aqueous solutions. XRF, ICP, and EDX analyses indicate a successful cationic exchange process without the modification of the zeolite structure as shown by XRD and solid-state NMR analyses. Composite materials (granulates and molded parts) were manufactured using to extrusion and injection processes. In the case of MgA zeolite, nitrogen adsorption–desorption experiments allowed us to measure a microporous volume, unlike NaA zeolite, which is non-porous to nitrogen probe molecule. SEM and EDX analyses highlighted the homogeneous distribution of zeolite crystals into the polymer matrix. Water adsorption capacities confirmed that the trends observed in the zeolite powder samples are preserved after dragging zeolites into composite formulations. Granulates and molded parts composite samples containing the magnesium exchanged zeolite showed an increase of their water adsorption capacity up to +27% in comparison to composite samples containing the non-exchanged zeolite. The MgA composite is more promising for water decontamination applications due to its higher water adsorption properties than the NaA composite.     

Antioxidant compounds from Algerian Convolvulus tricolor (Convolvulaceae) seed husks

Seed husk extracts of Convolvulus tricolor L. (Convolvulaceae) afforded six compounds, identified for the first time from this plant: isorhamnetin 3-O-beta-D-galactopyranoside (1), isorhamnetin 3-O-beta-D-(6"-acetyl)-galactopyranoside (2), isorhamnetin 3-O-robinobioside (3), 3,4-di-O-caffeoylquinic acid (4), gentisic acid 5-O-glucoside (5), and scopoletin (6). Separation of compounds was carried out by CC and CPC. Structural elucidations were performed by HPLC-UV-DAD, HPLC-ESI/MS (negative mode) and NMR.