Stability and solid-state polymerization reactivity of imidazolyl- and benzimidazolyl-substituted diacetylenes: pivotal role of lattice water

International audience1,6-Bis(1-imidazolyl)-2,4-hexadiyne (1) and1,6-bis(1-benzimidazolyl)-2,4-hexadiyne (5) have beenpreparedby a novel method that consists in refluxing excess imidazole and benzimidazole with 2,4-hexadiyne-1,6-diol bis(p-toluenesulfonate),pTS (3). This procedure is a viable alternative to the widely used Hay coupling protocol in case the target diyne possesses substituents capable of deactivating the copper catalyst by complexation. Diyne1crystallizes as a hydrate,1?H2O(2). For this compound, water is essential toachieve a crystalline material, and attempts to obtain crystals without included solvent were unsuccessful. In the structure of2, the organic fragments organize around the water molecule and interact with it through a dense network of hydrogen bonds. The CMC-CMC moieties are not oriented suitably for topochemical polymerization, and when trying to alter the organizationof the crystal by heating so as to induce polymerization, water is lost in an abrupt fashion that leads to instantaneous decomposition into polyaromatic-like species. Similar results were observed when water was removedin vacuo at room temperature. The benzimidazole-containing compound can be crystallized with water molecules (4)orwithout(5). X-ray crystallography shows that the structure of 5is organized by numerous C-H...N, C-H...p,andimidazolyl...imidazolyl p-p interactions. The diacetylene molecules almost have the right arrangement for topochemical polymerization, withpossibly reactingCMC-CMC fragments not beingparallel, a rare situation indiacetylene chemistry. Yet, experiments showthat topochemical polymerizationdoes not occur. Incorporationofwater in the lattice of5leads toa solvate that is topochemically reactive. Unlike2, however, water molecules in 4are not isolated but are organized as ribbons. Spectroscopic characterization of the polymer of4indicates that it is a blue phase polymer, with water coordinated to it. This study shows that it is possible to use water, and more generally solvent molecules, to transform a nonreactive diacetylene into a reactive one, even though this approach is less predictable than the cocrystal approach developed by Fowler, Lauher, and Goroff. The solvate approach is simple to implement, quite versatile because of the large rangeof solvents available, andonedoes not face theproblemof having to remove the host in case one needs to recover the polymer. Previous studies describing a similar approach are scarce

LOS MONAGUILLOS [Material gráfico]

Copia digital. Madrid : Ministerio de Educación, Cultura y Deporte. Subdirección General de Coordinación Bibliotecaria, 201

Dehydration of Alginic Acid Cryogel by TiCl4 vapor : Direct Access to Mesoporous TiO2@C Nanocomposites and Their Performance in Lithium-Ion Batteries

A new strategy for the synthesis of mesoporous TiO2@C nanocomposites through the direct mineralization of seaweed-derived alginic acid cryogel by TiCl4 through a solid/vapor reaction pathway is presented. In this synthesis, alginic acid cryogel can have multiple roles; i) mesoporous template, ii) carbon source, and iii) oxygen source for the TiO2 precursor, TiCl4. The resulting TiO2@alginic acid composite was transformed either into pure mesoporous TiO2 by calcination or into mesoporous TiO2@C nanocomposites by pyrolysis. By comparing with a nonporous TiO2@C composite, the importance of the mesopores on the performance of electrodes for lithium-ion batteries based on mesoporous TiO2@C composite was clearly evidenced. In addition, the carbon matrix in the mesoporous TiO2@C nanocomposite also showed electrochemical activity versus lithium ions, providing twice the capacity of pure mesoporous TiO2 or alginic acid-derived mesoporous carbon (A600). Given the simplicity and environmental friendliness of the process, the mesoporous TiO2@C nanocomposite could satisfy the main prerequisites of green and sustainable chemistry while showing improved electrochemical performance as a negative electrode for lithium-ion batteries

Potential model of a 2D Bunsen flame

The Michelson Sivashinsky equation, which models the non linear dynamics of premixed flames, has been recently extended to describe oblique flames. This approach was extremely successful to describe the behavior on one side of the flame, but some qualitative effects involving the interaction of both sides of the front were left unexplained. We use here a potential flow model, first introduced by Frankel, to study numerically this configuration. Furthermore, this approach allows us to provide a physical explanation of the phenomena occuring in this geometry by means of an electrostatic analogy

Alginic acid-derived mesoporous carbonaceous materials (Starbon®) as negative electrodes for lithium ion batteries : Importance of porosity and electronic conductivity

Alginic acid-derived mesoporous carbonaceous materials (Starbon® A800 series) were investigated as negative electrodes for lithium ion batteries. To this extent, a set of mesoporous carbons with different pore volume and electronic conductivity was tested. The best electrochemical performance was obtained for A800 with High Pore Volume (A800HPV), which displays both the highest pore volume (0.9 cm3 g−1) and the highest electronic conductivity (84 S m−1) of the tested materials. When compared to a commercial mesoporous carbon, A800HPV was found to exhibit both better long-term stability, and a markedly improved rate capability. The presence of a hierarchical interconnected pore network in A800HPV, accounting for a high electrolyte accessibility, could lay at the origin of the good electrochemical performance. Overall, the electronic conductivity and the mesopore size appear to be the most important parameters, much more than the specific surface area. Finally, A800HPV electrodes display similar electrochemical performance when formulated with or without added conductive additive, which could make for a simpler and more eco-friendly electrode processing

Sustainable polysaccharide-derived mesoporous carbons (Starbon®) as additives in lithium-ion batteries negative electrodes

For the first time, polysaccharide-derived mesoporous carbonaceous materials (Starbon®) are used as carbon additives in Li-ion battery negative electrodes. A set of samples with pore volumes ranging from ≈0 to 0.91 cm3 g-1 was prepared to evidence the role of porosity in such sustainable carbon additives. Both pore volume and pore diameter have been found crucial parameters for improving the electrodes performance e.g. reversible capacity. Mesoporous carbons with large pore volumes and pore diameters provide efficient pathways for both lithium ions and electrons as proven by the improved electrochemical performances of Li4Ti5O12 (LTO) and TiO2 based electrodes compared to conventional carbon additives. The mesopores provide easy access for the electrolyte to the active material surface, and the fibrous morphology favors the connection of active materials particles. These results suggest that polysaccharide-derived mesoporous carbonaceous materials are promising, sustainable carbon additives for Li-ion batteries

Non-linear model equation for three-dimensional Bunsen flames

The non linear description of laminar premixed flames has been very successful, because of the existence of model equations describing the dynamics of these flames. The Michelson Sivashinsky equation is the most well known of these equations, and has been used in different geometries, including three-dimensional quasi-planar and spherical flames. Another interesting model, usually known as the Frankel equation,which could in principle take into account large deviations of the flame front, has been used for the moment only for two-dimensional expanding and Bunsen flames. We report here for the first time numerical solutions of this equation for three-dimensional flames

Nouveaux precurseurs chimiques de ceramiques. Syntheses, caracterisations et traitements thermiques

SIGLEINIST T 71441 / INIST-CNRS - Institut de l'Information Scientifique et TechniqueFRFranc

Applications of bacterial cellulose as precursor of carbon and composites with metal oxide, metal sulfide and metal nanoparticles: A review of recent advances

International audienceA review. This mini review is limited to recent studies (last 5-​10 years) on two major issues, concerning: the prodn. and phys.​/chem. modification of bacterial cellulose (BC)​, and its transformation into carbon and integrated synthesis of metal oxides (TiO2, ZnO, Fe3O4, etc.)​, metal sulfide (ZnS, CdS, etc.) and metal nanoparticles (Au, Ag, Pt, Pd, etc.) within bacterial cellulose nanoribbons network. We believe that the crossover of these two domains could be of considerable interest in the view of improving the performance of materials prepd. with bacterial cellulose. The diversity of these nanomaterials allows targeting of many different properties​/applications: electrochem. devices, catalysis and photocatalysis, sensors, etc. After an introduction to the most important chem. and phys. characteristics of BC, prodn. parameters, and its phys. and chem. modifications, we review the use of BC as a precursor of inorg. materials like carbon and composites with metal or inorg. nanoparticles