X-ray diffraction study of 'side-on fixed' homopolysiloxanes from nematic to smectic C phases

The X-ray patterns for the nematic phase in a series of side-on fixed polysiloxanes show different kinds of diffuse elements which imply complex short range ordering. A systematic structural study of the evolution of the patterns versus two molecular parameters, namely the spacer length and the length of the terminal aliphatic tails, suggests the possible occurrence of a smectic C phase for certain values of these parameters. Taking into account these tendencies, new synthesis led to a nematic-smectic C polymorphism observed for the first time in side-on fixed polysiloxanes.     

Nonparametric decision-making models for large samples

Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 79–83, September, 1995.     

On exact order estimates of N-widths of classes of functions analytic in a simply connected domain

In the spaces E _q(Ω), 1 < q < ∞, introduced by Smirnov, we obtain exact order estimates of projective and spectral n-widths of the classes W ^r E _p(Ω) and W ^r E _p(Ω)Ф in the case where p and q are not equal. We also indicate extremal subspaces and operators for the approximative values under consideration.     

A case for sharing

Unlike in other branches of science and technology, computer programs and algorithms are generally not fully disclosed. This leads to duplication of effort, and prevents building new knowledge rapidly on existing knowledge. To remedy this, effective patents on computer programs and algorithms should be granted. The community of authors and inventors, along with expert advice from patent attorneys, have to arrive at effective and equitable definitions of obviousness and novelty, so that the boundaries of protection on one side, and free progress on the other, can be defined. The same reasons exist for patenting and disclosing computer software knowledge as for chemistry, electrical and mechanical inventions. Patenting has protected inventors and assured progress for many decades successfully in these fields.     

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 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.     

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.