Playing with PtII and ZnII Coordination to Obtain Luminescent Metallomesogens

Blue–green luminescent terpyridine-containing Pt^II and Zn^II complexes are reported. Equipped with lipophilic gallate units, which act as monodentate ancillary coordinating ligands and/or as anions, they display low-temperature mesomorphic properties (lamello-columnar and hexagonal mesophases for Pt^II and Zn^II complexes, respectively). The mesomorphic properties were investigated by polarised optical microscopy, differential scanning calorimetry, thermogravimetric analysis and X-ray scattering of bulk materials and oriented thin films. The model of self-assembly into the lamello-columnar phase of the Pt^II complex has been described in detail. The optical properties of the complexes were investigated in the liquid and condensed liquid crystalline states, highlighting the delicate balance between the role of the metal in determining the type of excited state responsible for the emission, and the role of the ancillary ligand in driving intermolecular interactions for proper mesophase formation.     

Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry

Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd.     

Transport properties of poly(ethylene terephthalate)/Rodrun 3000 blends

The transport properties of incompatible blends of poly(ethylene terephthalate) (PET) and a thermotropic liquid crystalline polymer (TLCP) composed of 40 mol% of PET and 60 mol% of p-hydroxybenzoic acid (Rodrun 3000) have been investigated using dichloromethane as permeant. Films, obtained by a blown film extrusion process, were analyzed and compared with the same samples stored 2 and 15 days at 60°C. With respect to the as-blown films, blends submitted to physical aging show a decrease in permeability by a percentage that increases with the amount of the LC phase present and a larger contribution derived from the polymeric matrix. The decrease of permeability is essentially attributed to a lowering of sorption because diffusional behavior for the different samples is the same.     

Q-switched Ti:Er:LiNbO3 waveguide laser

Q-switched operation of a Ti:Er:LiNbO3 waveguide laser has been achieved with up to 2.4 W pulse peak power (0.18J) at 2kHz repetition frequency with an intracavity Mach–Zehnder-type amplitude modulator. A theoretical model has been developed to describe the laser operation. Good agreement between numerical and experimental results has been achieved. Significant potential for improvement is predicted.     

Magnetic properties of amorphous Bi2DyFe5O12

Amorphous Bi₂DyFe₅O₁₂ films have been prepared by rf sputtering technique. The magnetic properties, structure and effect of annealing have been investigated. The magnetization increases with increasing magnetic field and is not saturated at a high magnetic field of 65 kOe. In the temperature range 20 K<T<200 K the susceptibility can be described by a Curie-Weiss law with a Weiss constant of =–15 K. The effective paramagnetic moment for the iron ion (4.1 _B ) is much smaller than the theoretical moment (5.9 _B ). Above 200 K the slope in ^–1 vsT curve changes. The Weiss constant and effective paramagnetic moment for the iron ion increase. After annealing above 600°C the amorphous samples crystallize to a single garnet phase with the magnetization of 21 emu/g at 1.5 K and 7.2 emu/g at 300 K, which are the same as those of the bulk Bi₂DyFe₅O₁₂ garnet ferrites.     

New silicon-mediated, sequential ring expansions of n-sized 2-cycloalkenones into hydroxyolefinic n + m + p medium-sized lactones: short synthesis of (-)-phoracantholide-J

[reaction: see text] In only four steps from 2-cyclopentenone and 2-cyclohexenone, sequential three- or four-atom and then one- to three-atom ring enlargements produce nine- to 12-membered hydroxyolefinic lactones on a gram scale. 2-Cyclopentenone undergoes this serial 5 + 3 + 2 process to form 10-membered ring natural (-)-phoracantholide-J in six linear steps and 26% overall yield.     

Statistical convergence in topology

We introduce and investigate statistical convergence in topological and uniform spaces and show how this convergence can be applied to selection principles theory, function spaces and hyperspaces.     

Impedance spectroscopy of reactive polymers. 1

Dielectric measurements were utilized to follow the advancement of cure in an epoxy/amine formulation. In contrast to earlier studies, complex impedance was measured during cure and used to calculate ionic resistivity. By using complex impedance were able to separate according to their frequency dependence the contributions to overall polarization from electrode blocking layers, migrating charges, and dipole relaxations. At any stage of cure, there is a unique frequency at which ionic resistivity can be singularly measured. Our approach does not involve trial-and-error frequency search and is conducive to the development of phenomenological models based on equivalent circuits. Excellent agreement was reported between the calculated values of normalized degree of cure obtained by dielectric and calorimetric measurements. © 1994 John Wiley & Sons, Inc.     

δ Lactones from δ-ketoesters-II : Mechanism changes in alkylation reactions and substituent effects on stereoselection

Alkylation of methyl 4-methyl 5-oxo 5-phenyl (m and p-X substituted) pentanoates 1_a-b give cis and trans tetrahydro 5,6-dimethyl 6-phenyl 2H pyran-2-ones. LFER of isomer ratios as function of the X substituent on the phenyl ring is seen in MeLi-Et₂O. The lactone ratios of reactions in THF with MeMgCl are not affected by the X phenyl substituent, while a more complex situation is showed by reactions of MeMgl in Et₂O and benzene. Changes in the cis: trans-ratios with variations in reactant and solvent are discussed in terms of equilibrium between folded and unfolded conformations in transition states.     

Wijsman topology on function spaces

LetC(X,Y) be the space of continuous functions from a metric space (X,d) to a metric space (Y, e).C(X, Y) can be thought as subset of the hyperspaceCL(X×Y) of closed and nonempty subsets ofX×Y by identifying each element ofC(X,Y) with its graph. We considerC(X,Y) with the topology inherited from the Wijsman topology induced onCL(X×Y) by the box metric ofd ande. We study the relationships between the Wijsman topology and the compact-open topology onC(X,Y) and also conditions under which the Wijsman topology coincide with the Fell topology. Sufficient conditions under which the compactopen topology onC(X,Y) is weaker than the Wijsman topology are given (IfY is totally bounded, then for every metric spaceX the compactopen topology onC(X,Y) is weaker than the Wijsman topology and the same is true forX locally connected andY rim-totally bounded). We prove that a metric spaceX is boundedly compact iff the Wijsman topology onC(X, ?) is weaker than the compact-open topology. We show that ifX is a σ-compact complete metric space andY a compact metric space, then the Wijsman topology onC(X,Y) is Polish.