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.     

Simulating the Kinematic Dynamo Forced by Heteroclinic Convective Velocity Fields

We report on the integration of the kinematic dynamo problem in a spherical domain forced by velocity fields that are convective fluid flows resulting from a bifurcation analysis of the spherical Bénard problem. We derive a code based on generalized spherical harmonics that ensures a divergence-free magnetic field. We determine the growth or decay of a magnetic field in the kinematic dynamo equation for various physically relevant velocity fields which are stationary as well as time-periodic and chaotic. Velocity signals that are produced by heteroclinic cycles are used as an input to an energy-saturated kinematic dynamo equation that limits the growth of the linearly unstable modes. Preliminary calculations indicate the possibility of reversals of the magnetic field for this case of forcing. Received 8 October 1996 and accepted 28 April 1997     

Resistance of composite flywheel rim to radial tensile stresses from centrifugal forces based on results of pure bending of a rim segment

A method is proposed for evaluating the resistance of a flywheel rim to radial stresses in free rotation. The method is based on loading a rim segment in pure bending and calculating the limiting moment and the corresponding limiting angular velocity. Applicability of the method is substantiated theoretically by investigating the similarity of the radial stress diagrams in rotation and pure bending. The method is verified experimentally for the strained state of a rim segment in pure bending.Translated from Mekhanika Kompozitnykh Materialov, Vol. 29, No. 4, pp. 521–526, July–August, 1993.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

Hamiltonian circle actions on symplectic manifolds and the signature

Let M be a symplectic manifold with a Hamiltonian circle action with isolated fixed points. We prove that σ (M) = b₀(M) − b₂(M) + b₄(M) − b₆(M) + … where σ (M) is the signature of M and b_i(M) is the ith Betti number of M.     

Isomorphism of the Baumslag-Solitar groups

Necessary and sufficient conditions for the isomorphism of two groups, each defined by a single relation of the type a^–1b^ma=bⁿ, are obtained.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 43, No. 12, pp. 1684–1686, December, 1991.     

Strings at nonzero temperature

String theory at nonzero temperature is reviewed. A bosonic string at nonzero temperature is studied and the calculation of its free energy in both the one-loop approximation and the case of arbitrary genus (multiloop analysis) is discussed. A string at nonzero temperature is compared with a string compacted on a one-dimensional torus. The properties of modular invariance and dual symmetry are discussed at both the one-loop and multiloop levels. The thermodynamics of superstrings, including also superstrings compactified on a torus, is also studied. Possible cosmological applications are briefly considered. It is shown that many features of string thermodynamics (in particular, the existence of the Hagedorn temperature and dual symmetry) also occur in the theory of noncritical strings.Translated from Izvestiya Vysshykh Uchebnykh Zavedenii, Fizika, No. 12, pp. 3–49, December, 1991.