Porous polycrystals built up by uniformly and axisymmetrically oriented needles: homogenization of elastic propertiesPolycristaux poreux constitués d'aiguilles orientées de façon uniforme ou axisymétrique : homogénéisation des propriétés élastiques

Porous polycrystal-type microstructures built up of needle-like platelets or sheets are characteristic for a number of biological and man-made materials. Herein, we consider (i) uniform, (ii) axisymmetrical orientation distribution of linear elastic, isotropic as well as anisotropic needles. Axisymmetrical needle orientation requires derivation of the Hill tensor for arbitrarily oriented ellipsoidal inclusions with one axis tending towards infinity, embedded in a transversely isotropic matrix; therefore, Laws' integral expression of the Hill tensor is evaluated employing the theory of rational functions. For a porosity lower 0.4, the elastic properties of the polycrystal with uniformly oriented needles are quasi-identical to those of a polycrystal with solid spheres. However, as opposed to the sphere-based model, the needle-based model does not predict a percolation threshold. As regards axisymmetrical orientation distribution of needles, two effects are remarkable: Firstly, the sharper the cone of orientations the higher the anisotropy of the polycrystal. Secondly, for a given cone, the anisotropy increases with the porosity. Estimates for the polycrystal stiffness are hardly influenced by the anisotropy of the bone mineral needles. Our results also confirm the very high degree of orientation randomness of crystals building up mineral foams in bone tissues. To cite this article: A. Fritsch et al., C. R. Mecanique 334 (2006).     

In situ study on molecular diffusion phenomena in nanoporous catalytic solids

As an omnipresent phenomenon in nature, diffusion is among the rate-determining processes in many technological processes. This is in particular true for catalytic conversion in nanoporous materials. We provide a critical review of the possibilities of exploring diffusion phenomena over microscopic dimensions in such media by direct experimental observation. By monitoring the probability distribution of molecular displacements as a function of time, the pulsed field gradient technique of NMR (PFG NMR) records the rate of molecular re-distribution. By varying the observation time, PFG NMR is thus able to trace even hierarchies of transport resistances as occurring, e.g., in catalyst particles in the form of binder-compacted assemblages of zeolite crystallites. Alternatively, and complementary to this information, interference microscopy (IFM) and IR microscopy (IRM) are able to follow the evolution of intracrystalline concentration profiles during uptake and release. This allows, in particular, an accurate quantification of the transport resistances on the surface of the individual crystallites and of the probability that reactant molecules from the gas phase, upon colliding with the external surface, are able to penetrate through such "surface barriers" into the crystal bulk phase. Being able to distinguish between different molecular species, IRM is able to record the evolution of intracrystalline concentration profiles even during multi-component adsorption and catalytic reactions (169 references).     

Liquid densities of THF and excess volumes for the mixture with water in a wide temperature and pressure range

In this paper densities for THF (tetrahydrofuran) and THF + water mixtures measured with the help of the Anton Paar DMA HPM vibrating tube densimeter are reported. The pure component densities of tetrahydrofuran measured in the temperature range from 278 to 437 K and pressures up to 130 MPa were correlated with the TRIDEN-System. Additionally densities of the binary mixture tetrahydrofuran + water were measured for 6 different concentrations in a temperature range from 288 to 338 K and up to 130 MPa. Excess volumes (vE)$(v^E)$ of the mixture were determined using the own correlation of the tetrahydrofuran densities and the equation of state (EoS) for water by Wagner and Pruß. Redlich–Kister polynomials were used to fit the vE-data$v^E\text{-data}$. Additionally in this work it was checked if the vibrating tube densimeter allows the determination of the miscibility gap for the system THF–water as a function of temperature and pressure.     

Rheology and structure formation in diluted mixed particle-surfactant systems

In the present work, we focus on the bulk rheology of mixtures consisting of surfactant modified silica nanoparticles in water. Depending on the ratio of surfactant and nanoparticle concentrations, significant modifications in the measured rheology are evidenced. A domain where the dispersions behave like viscoelastic media is observed. Outside this domain, the dispersions exhibit viscous properties. The changes in the bulk rheology characteristics are discussed in terms of interaction effects between the surfactant and the particles. The results obtained are seen in the context of diluted emulsions' properties and characteristics.     

Synthesis and characterization of an aliphatic monoimide-bridged polysilsesquioxane by the sol–gel route

Based on differential scanning calorimetry data, it was shown that the reaction of (3-triethoxysilylpropyl)succinic anhydride and (3-amino)propyltriethoxysilane at 110 °C resulted in the formation of polyamic acid, whereas the thermal treatment at 220 °C led to the generation of an aliphatic monoimide-bridged polysilsesquioxane as proved by FT-IR. X-ray powder diffraction studies showed a prominent reflection at 2θ = 6.66° (d = 1.32 nm) revealing that a crystalline area is formed. ²⁹Si CP-MAS-NMR and ¹³C CP-TOSS-MAS-NMR measurements proved that no cleavage of the Si–C bond occurred, and a highly condensed material was obtained.     

Synthesis of room-temperature ionic liquids with the weakly coordinating [Al(ORF)4]- anion (RF=C(H)(CF3)2) and the determination of their principal physical properties

A large series of ionic liquids (ILs) based on the weakly coordinating alkoxyaluminate [Al(hfip)(4)](-) (hfip: hexafluoroisopropoxy) with classical as well as functionalized cations were prepared, and their principal physical properties determined. Melting points are between 0 ([C(4)MMIM][Al(hfip)(4)]) and 69 °C ([C(3)MPip][Al(hfip)(4)]); three qualify as room-temperature ILs (RTILs). Crystal structures for six ILs were determined; their structural parameters and anion-cation contacts are compared here with known ILs, with a special focus on their influence on physical properties. Moreover, the biodegradability of the compounds was investigated by using the closed-bottle and the manometric respirometry test. Temperature-dependent viscosities and conductivities were measured between 0 and 80 °C, and described by either the Vogel-Fulcher-Tammann (VFT) or the Arrhenius equations. Moreover, conductivities and viscosities were investigated in the context of the molecular volume, V(m). Physical property-V(m) correlations were carried out for various temperatures, and the temperature dependence of the molecular volume was analyzed by using crystal structure data and DFT calculations. The IL ionicity was investigated by Walden plots; according to this analysis, [Al(hfip)(4)](-) ILs may be classified as "very good to good ILs"; while [C(2)MIM][Al(hfip)(4)] is a better IL than [C(2)MIM][NTf(2)]. The dielectric constants of ten [Al(hfip)(4)](-) ILs were determined, and are unexpectedly high (ε(r)=11.5 to 16.8). This could be rationalized by considering additional calculated dipole moments of the structures frozen in the solid state by DFT. The determination of hydrogen gas solubility in [Al(hfip)(4)](-) RTILs by high-pressure NMR spectroscopy revealed very high hydrogen solubilities at 25 °C and 1 atm. These results indicate the significant potential of this class of ILs in manifold applications.     

Guanidinium Alkynesulfonates with Single‐Layer Stacking Motif: Interlayer Hydrogen Bonding Between Sulfonate Anions Changes the Orientation of the Organosulfonate R Group from “Alternate Side” to “Same Side”

Hydrolyses of HC?CSO₃SiMe₃ ( 1 ) and CH₃C?CSO₃SiMe₃ ( 2 ) lead to the formation of acetylenic sulfonic acids HC?CSO₃H?2.33 H₂O ( 3 ) and CH₃C?CSO₃H?1.88 H₂O ( 4 ). These acids were reacted with guanidinium carbonate to yield [⁺C(NH₂)₃][HC?CSO₃^?] ( 5 ) and [⁺C(NH₂)₃][CH₃C?CSO₃^?] ( 6 ). Compounds 1 – 6 were characterized by spectroscopic methods, and the X‐ray crystal structures of the guanidinium salts were determined. The X‐ray results of 5 show that the guanidinium cations and organosulfonate anions associate into 1D ribbons through ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) dimer interactions, whereas association of these ions in 6 is achieved through ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) and ${{\rm R}{{1\hfill \atop 2\hfill}}}$ (6) interactions. The ribbons in 5 associate into 2D sheets through ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) dimer interactions and ${{\rm R}{{3\hfill \atop 6\hfill}}}$ (12) rings, whereas those in 6 are connected through ${{\rm R}{{1\hfill \atop 2\hfill}}}$ (6) and ${{\rm R}{{2\hfill \atop 2\hfill}}}$ (8) dimer interactions and ${{\rm R}{{4\hfill \atop 6\hfill}}}$ (14) rings. Compound 6 exhibits a single‐layer stacking motif similar to that found in guanidinium alkane‐ and arenesulfonates, that is, the alkynyl groups alternate orientation from one ribbon to the next. The stacking motif in 5 is also single‐layer, but due to interlayer hydrogen bonding between sulfonate anions, the alkynyl groups of each sheet all point to the same side of the sheet.     

Indoline-3-carboxylic acid derived organocatalysts for the anti-Mannich reaction

Mannich type reactions of a preformed aldimine with various carbonyl compounds were investigated with a series of functionalised indoline derivatives as catalysts: indoline‐3‐carboxylic acid, the diphenylcarbinol analogue and O‐protected silyl ether analogues. All compounds were readily prepared in enantiopure form by using an enzymatic kinetic resolution as a key step (E?100). The alcohol and ether catalysts failed to induce complete chirality transfer but did afford the Mannich bases in good yields and high diastereomeric ratios, whereas the acid catalyst gave the products in a highly diastereo‐ and enantioselective manner. The absolute configuration of the products was determined by a syn–anti isomerisation protocol, initiated by the sterically demanding base 1,8‐diazabicyclo[5.4.0]undec‐7‐ene.     

Synthesis of the core structure of the lipoteichoic acid of Streptococcus pneumoniae

Streptococcus pneumoniae LTA is a highly complex glycophospholipid that consists of nine carbohydrate residues: three glucose, two galactosamine and two 2‐acetamino‐4‐amino‐2,4,6‐trideoxygalactose (AATDgal) residues that are each differently linked, one ribitol and one diacylated glycerol (DAG) residue. Suitable building blocks for the glucose and the AATDgal residues were designed and their synthesis is described in this paper. These building blocks permitted the successful synthesis of the core structure Glcβ(1‐3)AATDgalβ(1‐3)Glcα(1‐O)DAG in a suitably protected form for further chain extension ( 1 b , 1 c ) and as unprotected glycolipid ( 1 a ) that was employed in biological studies. These studies revealed that 1 a as well as 1 lead to interleukin‐8 release, however not via TLR2 or TLR4 as receptor.