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.     

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 imaging and pulsed Doppler sonography of poststenotic jets: Correlation between signal void and flow velocity distribution

To correlate the appearance of poststenotic jets on gradient echo images with features of localized Doppler spectra of the jets, we studied an in vitro model of steady flow-through stenoses of 86, 96, and 99% area reduction. As fluids, water and a 40% glycerol solution in water were used. MRI was performed with a 1.5 T whole body imager and gradient echo images were obtained in planes parallel to the direction of flow. Doppler spectra were acquired separately from the MR measurements at 1 cm intervals for a distance of 10 cm downstream from the stenosis. Poststenotic signal void was observed for water and for the 40% glycerol solution only if the mean velocity within the stenosis exceeded a limit of 50–60 cm/sec. On the MR images, the jets could be divided into two segments: A proximal jet segment of uniform width equal to the diameter of the stenosis, followed by a distal jet segment which was characterized by broadening and then dissipating signal void. Except for the 99% stenosis, a high signal intensity core was present within the proximal jet segment. In the proximal jet segment, the Doppler measurements showed a low temporal fluctuation of the maximal flow velocity and only little flow opposite to the main flow direction. In the distal jet segment, the velocity fluctuation and the intensity of reverse flow increased sharply. The high signal intensity core of the jet was associated with a poststenotic zone of constant maximal flow velocity. The results demonstrate a close relationship between characteristic features of poststenotic jets in MRI and pulsed Doppler sonography.     

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.     

Optical diagnostics of dispersing He plasma

An experimental study has been made of the characteristics of radiation from a dispersing helium plasma. From measurements of the space-time dependence of the line intensities of the helium 2³P — n³D series we obtained the distribution of the populations of the n³D levels for n=3–10. The study has shown that over a wide range of conditions the high-lying levels (n=5–10) are in equilibrium with electrons while a substantial deviation from equilibrium is observed for levels n=3, 4. From the energy distribution of the populations of the upper levels we determined the space-time dependence of the electron temperature, which reflects the process of effective electron cooling during dispersal of the plasma. The gas temperature was estimated from the populations of helium singlet and triplet levels with n=5. The time distribution of the electron density in the plasma was found from the Stark broadening of the spectral lines.Deceased.V. D. Kuznetsov Siberian Physicotechnical Institute, Tomsk State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 15–19, November, 1992.     

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.     

The exactly resolved nonlattice model of random media based on Markov walks with a stable law for jumps

A random-medium model which is a correlated distribution of points (particles) randomly positioned in the 3-dimensional space is considered. The construction of the medium starts from a noncorrelated (Poisson) distribution of parent particles, each of them initiates a finite Markov chain of its descendants. The complete collection of correlation functions of all orders within the scope of the model have been obtained. The use of the 3-dimensional stable law (Lévy law) as a transition probability allows us to present the correlation function in an explicit form. Proceedings of the XVII Seminar on Stability Problems for Stochastic Models, Kazan, Russian, 1995, Part II.