Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition-metal carbonyl complexes

Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.     

Novel optical techniques for the analysis of polymer surfaces and thin films

Summary We report on novel optical techniques, based on evanescent waves, for the characterization of polymer surfaces and thin films. We first describe photo-ablation studies with polysilane films investigated by surface plasmon microscopy, a technique which is particularly well-suited for ultrathin samples. Thicker films that are homogeneous enough to carry optical waveguide modes can be characterized with high lateral resolution by the recently developed waveguide microscopy. We demonstrate this for a thin film of a solid polyelectrolyte. Finally, we report on surface plasmon field-enhanced Raman-spectroscopic and -imaging investigations of ultrathin Langmuir-Blodgett-Kuhn-layers of cadmium arachidate.W. Hickel is now with HOECHST AG, Angewandte Physik, W-6230 Frankfurt 80     

Existence of solutions for the time-dependent thermistor equations

The equations describing the behaviour of temperature/flow microsensorsemploy-ing polysilicon thermistors form a degenerate nonlinearparabolic system. One special feature is that different equationsof this system are to be satisfied on different domains. Bymeans of supersolutions and subsolutions, the maximum principle,and fixed point arguments, the authors show the existence ofsolutions to the equations.     

Bound states and resonances ofN-particle discrete Schrödinger operator

The existence of bound states and resonances of the Hamiltonian of a system ofN different quantum lattice particles with nonvanishingN-particle short-range interaction is proved. The dependence of the bound states and the resonances on the coupling constant and the quasimomentum is studied.Samarkand State University. Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 91, No. 1, pp. 51–65, April, 1992.     

Magnetic resonance findings in sarcoidosis of the thorax.

Fifteen patients with sarcoidosis underwent thoracic MRI examinations. The T2 signal intensity of lymphadenopathy varied, with no characteristic pattern noted. Three of four patients with bright lymph nodes on T2 images had stage I sarcoidosis, but low intensity nodes were also seen in stage I patients. Coronal images were complementary to axial images and better depicted subcarinal adenopathy. MRI does not distinguish the lymphadenopathy of sarcoidosis from other entities, but is useful for defining the anatomic extent of disease and differentiating pulmonary artery enlargement from adenopathy.     

On the retrograde condensation of one or two liquids

This contribution discusses the phenomena of retrograde condensation of one or two liquids. It w1 be shown that both phenomena can be well understood. Also the relation of retrograde condensation of one liquid phase with the condensation behavior of natural gas will be discussed. Similarly that of two liquid phases with multiple phase behavior occurring in low temperature reservoir fluids will be pointed out.     

Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate.     

A generalised model and calculation of the hyperfine interaction constant for anomalous muonium in the crystalline lattice of silicon

A new microscopic model of anomalous muonium for the elemental semiconductors is proposed. The relevant configuration consisting of both a diamagrentic molecule Si−Mu and an unpaired orbital e⁻ is contained into a semivacancy of the real lattice. By using the unrestricted Hartree-Fock computational method the principal properties of the system are established. A dynamical version of the model together with a question on the formation of such system are discussed.