Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase

A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H₂O₂ is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H₂O₂ is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H₂O₂ is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007     

La5Al3Ni2 – an Intermetallic Phase Observed upon Crystallization of La50Al25Ni25 Metallic Glass

The yet unknown intermetallic phase La₅Al₃Ni₂ was obtained by partially crystallizing amorphous La₅₀Al₂₅Ni₂₅ at 550 K (further heating above 600 K leads to irreversible disappearance of this phase), and its crystal structure was determined from X‐ray powder diffraction data. The crystal structure of the La₅Al₃Ni₂ phase constitutes a new structure type (Cmcm, a = 14.231Å, b = 6.914Å, c = 10.460Å, oC40) and is built from [Al₃Ni₂] chains surrounded by La atoms. In the ternary system La‐Al‐Ni La₅Al₃Ni₂ is located on the section La₅₀Al_50−nNi_n (0 ≤ n ≤ 50) with the binary compounds LaAl and LaNi as end members. Strikingly, also the crystal structures of the end members can be conceived as chain structures with Al and Ni chains surrounded by La, respectively.     

New HPLC-chiral stationary phases for enantiomeric resolution of sulfoxides and selenoxides

Summary Enantiomers of several sulfoxides and some selenoxides can be easily separated by using a new chiral stationary phase (CSP-DACH-DNB) containing the 3,5-dinitrobenzoyl derivative of R,R-(-)1,2-diamino-cyclohexane as selector, covalently bonded to the siliceous matrix. The easy operative conditions and the high enantioselectivity values (α) allow a direct transfer of the analytical separations to a semi-preparative and preparative scale.     

Insights on some chiral smectic phases

Combining layered positional order as smectic order and chirality can generate complex architectures since twist parallel to the layers is not allowed. This paper will review some new experimental results on different phases resulting from the competition between smectic positional order and twist orientational order. It concerns the TGB_A and the NL^*, that is the liquid line phase as well as the SmQ phase. Chiral effects in the isotropic phase will also be discussed.     

Towards the synthesis of MAX-phase functional coatings by pulsed laser deposition

Pulsed laser deposition with a Nd:YAG laser was used to grow thin films from a pre-synthesized Ti₃SiC₂ MAX-phase formulated ablation target on oxidized Si(1 0 0) and MgO(1 0 0) substrates. The depositions were carried out in a substrate temperature range from 300 to 900 K, and the pressure in the deposition chamber ranged from vacuum (10⁻⁵ Pa) to 0.05 Pa Argon background pressure. The properties of the films have been investigated by Rutherford backscattering spectrometry for film thickness and stoichiometric composition and X-ray diffraction for the crystallinity of the films. The silicon content of the films varied with the energy density of the laser beam. To suppress especially the silicon re-sputtering from the substrate, the energy of the incoming particles must be below a threshold of 20 eV. Therefore, the energy density of the laser beam must not be too high. At constant deposition energy density the film thickness depends strongly on the background pressure. The X-ray diffraction measurements show patterns that are typical of amorphous films, i.e. no Ti₃SiC₂ related reflections were found. Only a very weak TiC(2 0 0) reflection was seen, indicating the presence of a small amount of crystalline TiC.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

Preparation and evaluation of nickelmesogen for micropacked gas chromatography

The preparation and mesomorphic properties of a substituted bis(dithiolene)nickel complex derived from 4, 4'-dimethoxybenzil are reported. The phase transition temperatures were based on data obtained by polarized light microscopy and differential scanning calorimetry. The mesogenic phase existed over the temperature range from 77 to 175 degrees C. A novel micropacked column (1.5 or 3 m x 1 mm i.d.) prepared from the slurry of bis[1,2-bis(4-n-undecyloxyphenyl)ethane-1,2-dithiolene] nickel(II) (5%, w/w), coated on Chromosorb W was applied for the separation of dialkyl sulfides. The non-linearity (discontinuity) of Van't Hoff plots suggests that the liquid crystal property existed even in the coated phase. Factors affecting the retention and the sample selectivity on the prepared column were examined by using a flame photometric detector (FPD). The separation might be based on the mechanism of ligand exchange, shape selectivity and polarity interaction besides the vapor pressure. LOD for the determination of dialkyl sulfides was below 1 ng for most of the analytes.