Fast atom bombardment mass spectrometry of new polydentate schiff bases. 2. The case of mono- and bisaldimines containing pyridine groups

The mass spectrometric behaviour of seven polydentate Schiff bases derived from the condensation of formyl or diformyl precursors (2,3-dihydroxy- or 2,5-dihydroxy-benzaldehyde, 3-metoxy- or 3-ethoxy-salicylaldehyde, 3-formyl-salicyclic acid, 4-methoxy- or 4-chloro-2,6-diformylphenol) with 2-aminomethylpyridine have been investigated by fast atom bombardment mass spectrometry and metastable ion studies.     

Proximity effects in mass spectrometry. Electron impact ionization-induced cyclization of 1,2-bis(1,4-dithiafulven-6-yl)benzenes

The electron impact ionization mass spectra of o-, m- and p-bis(1,4-dithiafulven-6-yl)benzenes were studied by means of accurate mass measurements, metastable analysis and collision-induced dissociation. Differences observed in the spectra of the ortho isomers are due to a cyclization reaction leading to molecular ions with the same structure as those generated from certain cyclic compounds, as confirmed by comparison of linked scans at constant B/E of metastable and collisionally activated molecular ions. Parallels of this cyclization of molecular ions with their electrochemical or acid-induced isomerization are also discussed.     

DTA and X-ray diffraction investigations of laser-irradiated CeO2 powders

The TG and DTA curves and diffractograms of powdered CeO₂ samples irradiated with a CO₂ laser beam with powers of 0.41–1.39 kW/cm² are presented. The laser treatment induced structural changes and probably generation of a metastable phase. X-ray diffraction coupled with thermal analysis was used to establish the structural modifications in the irradiated samples after heating.     

A thermoanalytical study of the formation and activation of novel copper-carbon catalysts

Simultaneous DSC-TG and DTA-TG were used to investigate the calatytic effect of the metal on the thermal decomposition of a cellulose matrix containing small copper particles. The techniques were also used to demonstrate the effect of the metal particles on the subsequent activation of the carbon matrix, a process which develops the pore structure necessary to expose the metal particles to the gas phase. Temperature programmed desorption was used to study the initial mass loss found on activation. To quantify the catalytic effect of the copper particles on the activation process an estimate was made of the activation energy of the catalysed and uncatalysed reactions. The work gives valuable information on the processes involved in the preparation of a new range of metal-carbon catalysts. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

Pressure-induced dislocation amorphization of crystals

In terms of the isotropic elastic crystal model, it is shown that the formation of planar layers consisting of edge dislocation pileups is advantageous in energy if the shear modulus of the crystal is far lower than the bulk modulus. As pressure rises, the dislocation radius decreases, which can destroy the crystal structure.     

The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

Pretransitional electro-optic response of 6CB liquid crystal in the isotropic phase

In this work, the electro-optic response of a 6CB liquid crystal layer is studied using a sensitive differential technique. The layer is held at a temperature just above the nematic to isotropic phase transition. Transverse magnetic (p) polarized light incident on the cell is coupled to guided modes in the liquid crystal layer using prism coupling. The modes manifest themselves as sharp dips in the reflectivity as the angle of incidence is scanned. When a low frequency sinusoidal voltage is applied to the cell, the resonant mode shapes and excitation angles are altered at a frequency which is twice that of the applied field, resulting in a modulation of the reflectivity for a given angle of incidence. By synchronous observation of the modulated signal, a differential signal is recorded. Comparing the data with modelling generated from multilayer optics theory, two effects are then quantified. The first of these is an induced birefringence, varying quadratically with applied voltage, which is well understood and can be expressed in terms of Landau-de Gennes theory. The second is a field induced perturbation in the imaginary part of the optical permittivity, δε_i, which implies a modification of the light scattering properties of the liquid crystal. The measurement of the latter effect is, as far as we know, a novel one, being only made possible by the remarkable sensitivity of the synchronous differential technique.     

Electrochemical characterization of composite membranes based on crown-ethers intercalated into montmorillonite

Oxyethylene macrocyclic compounds (crown-ethers) act as ligands of intracrystalline cations of certain layered silicates as montmorillonites. Stable intercalation materials are formed which are used to prepare organic-inorganic membranes by encapsulating these intercalation compounds with a poly-butadiene thin coating. Electrochemical Impedance Spectroscopy (EIS) is used to study the resulting composite membranes in contact with aqueous electrolytes. From the impedance plots, the ionic resistance of the membranes is obtained. The thickness of the polybutadiene coating is an important factor determining the ability of ions to pass across the membrane. Marked differences in the ionic resistance are observed as a function of the nature of the interlayer macrocyclic compound. For non-intercalated montmorillonite membranes, the ionic resistance is strongly reduced, whereas for some crown-ether intercalated materials such as 18-crown-6 and dibenzo 24-crown-8, iono-selective membranes are obtained. Concerning the nature of the electrolyte, cations exhibiting greater hydration energies show higher difficulties to pass through the membrane and, consequently, the ionic resistance increases.