Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Nonlinear optical properties of regioregular main‐chain polyesters

We have prepared new polyesters containing quadratic, nonlinear optical (NLO) active chromophores covalently incorporated into the main chain. In these polymers, the sequence of the chromophore units along the main chain is rigorously head to tail. All the polyesters are processable, both in the melt and in solution. For one polyester, a full second‐order NLO characterization has been performed. An out‐of‐resonance d₃₃ coefficient of 21 pm/V at 1368 nm has been measured. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2719–2725, 2007     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Chemical analysis and distribution investigation of trace elements in indium matrix by spark source mass spectrometry

Summary High-purity indium was analysed by spark source mass spectrometry, using electrical and photoplate detection. For the calibration of the differences in elemental sensitivity, a standard sample was prepared in which 10 impurities were determined by graphite furnace atomic absorption spectrometry. In this way accuracies of less than 40% were obtained for relatively homogeneous elements at ppm and sub-ppm level. About 40 elements could be determined with detection limits of 10 to 30 ppb. Two pattern recognition methods, principal component analysis and clustering analysis, were applied to obtain information on trace element distribution, which indicated that a number of elements were strongly spatially correlated in the analysed sample.

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Chemische Analyse und Verteilungsbestimmung von Spurenelementen in Indium-Matrix durch Funkenquellen-Massenspektrometrie

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On leave from: Department of Chemistry, Nanjing Normal University, Nanjing, People's Republic of China     

Coagulation in lipid- and protein-containing systems

The behavior of real disperse systems with organic impurities was examined under conditions of destabilization by inorganic coagulants. A number of physicochemical methods of analysis and a simulation method were used to identify the character and type of the complexes formed and to calculate their stability constants.     

Electro-optic pulse response of ferroelectric liquid crystals

The electro-optic response of ferroelectric smectic C* liquid crystals has been studied. Anomalous switching behaviour of such materials which possess a negative dielectric anisotropy has been reported. These materials show a minimum in response time at a sufficiently high field. We present results showing the dependency of this minimum upon spontaneous polarisation and the effect of AC bias. Calculations based upon the equation of motion of the director around the cone are presented which describe this effect and its dependence on the relative magnitudes of the spontaneous polarization and dielectric anisotropy of the material. Good agreement with the experimental results is found.     

Optical limiters and diffraction elements based on a COANP-fullerene system: Nonlinear optical properties and quantum-chemical simulation

The results of optical study and quantum-chemical simulation of a conjugated organic system, 2-cyclooctylamino-5-nitropyridine (COANP)-fullerene, performed to determine its potential for application as a limiter of visible and near-IR laser radiation and as a material for diffraction elements in systems for reversible recording of optical information, are presented. Complexation between a COANP molecule and fullerene is considered as one of the main mechanisms responsible for the corresponding properties of this system. For the first time, nonlinear optical characteristics of COANP-C₆₀ and COANP-C₇₀ systems are comparatively studied and the intermolecular interaction between a COANP molecule and fullerene is analyzed on the quantum-chemical level.