The mechanism of the alkylation of isoxazolidin-3-one

In solvents of different polarities, the lactam-lactim tautomeric equilibrium of isoxazoli-din-3-one is strongly displaced in the direction of the lactam. The lactim form cannot be detected. It has been concluded that there is no connection between the dual chemical behavior of isoxazolidin-3-one and its potassium salt in the alkylation reaction with the equilibrium isomerization of these compounds. It has been shown that the mechanism of alkylation is connected with the structure of the lactam anion. Evidence is given in favor of a mesomeric structure of the anion with the main charge on the nitrogen at which substitution chiefly takes place.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–901, July, 1973.     

1-Ethylthio-2R-isoindoles. An example of nonsynchronous addition in the diels-alder reaction

The previously unknown 1-ethylthio-2R-isoindoles have been obtained by modifying the corresponding isoindol-1-ones. The reaction of these isoindoles with N-arylmaleimide derivatives has been investigated. A rare case of nonsynchronous addition in the Diels-Alder reaction has been found.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1200–1205, September, 1984.     

Diastereospecific ring cleavage of bornane-2,3-dione in the Bucherer-Bergs reaction

A novel regio- and diastereospecific ring cleavage of bornane-2,3-dione (camphor quinone) under Bucherer-Bergs reaction conditions has been investigated. The simplicity of this transformation provides a novel and straightforward synthetic pathway to enantiopure derivatives of cyclopentane carboxylic acid as well as functionalized hydantoins in just two steps, starting from inexpensive and easily available camphor.     

Synthesis, fluorescent properties and aggregation of 2,3-dihydroisoindolenylcalix[4]arenes

New derivatives of calix[4]arenes, containing two isoindole fragments in distal positions of the macrocycle upper rim were synthesized. According to NMR and molecular modeling data, the obtained calixarenes exist in “flattened cone” conformation with inclination angles of benzene rings to the macrocycle plane equal to 133–140° and 92–100°. Fluorometric studies showed the presence of self-aggregation of isoindolenylcalixarenes in acetone solutions starting from micromolar concentrations.     

Some insights in superdiffusive transport

In a wide range of systems, the relaxation in response to an initial pulse has been experimentally found to follow a nonlinear relationship for the mean squared displacement, of the kind 〈x²(t)〉∝t^α$〈x^2(t)〉\propto t^{\alpha }$, where α$\alpha$ may be greater or smaller than 1. Such phenomena have been described under the generic term of anomalous diffusion. “Lévy flights” stochastic processes lead to superdiffusive behaviour (1<α<2)$(1<\alpha <2)$ and have been recently proposed to model—among the others—the subsurface contaminant spread in highly heterogeneous media under the effects of water flow. In this paper, within the continuous-time random walk (CTRW) approach to anomalous diffusion, we compare the analytical solution of the approximated fractional diffusion equation (FDE) with the Monte Carlo one, obtained by simulating the superdiffusive behaviour of an ensemble of particle in a medium. We show that the two are neatly different as the process approaches the standard diffusive behaviour. We argue that this is due to a truncation in the Fourier space expansion introduced by the FDE approach. We propose a second-order correction to this expansion and numerically solve the CTRW model under this hypothesis: the accuracy of the results thus obtained is validated through Monte Carlo simulation over all the superdiffusive range. The same kind of discrepancy is shown to occur also in the derivation of the fractional moments of the distribution: analogous corrections are proposed and validated through the Monte Carlo approach.     

Metalla‐Assembled Electron‐Rich Tweezers: Redox‐Controlled Guest Release Through Supramolecular Dimerization

Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1,3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway.     

Effect of charge density waves on the tunnel spectra of the Bi2Sr2CaCu2O8+δ superconductor

The differential tunnel conductance G _S of the junction between a normal metal and a superconductor with a charge density wave (CDW) is calculated as a function of the voltage V across the junction. The results are averaged over the spread of superconducting and CDW energy gaps in the nanoscale-inhomogeneous superconductor. It is shown that, if both order parameters are nonzero, a dip-hump structure is formed beyond the superconducting gap of G _S (V). If the phase of the CDW order parameter is not equal to π/2, a dip-hump structure will appear solely or mainly for one sign of the bias polarity. The results agree with the experimental data for Bi₂Sr₂CaCu₂O_8+δ and other high-temperature oxides     

Interaction of nickel hydroxocarbonate,ammonium paramolybdate,and ammonium metatungstate under mechanical activation

The interaction of nickel hydroxocarbonate, ammonium paramolybdate, and ammonium metatungstate (Ni: Mo: W = 3: 1: 1) is reported. Under mechanical activation conditions, nickel hydroxocarbonate particles undergo comminution and ammonium paramolybdate and ammonium metatungstate particles soften and aggregate. It is demonstrated by DTA, X-ray diffraction, and IR spectroscopy that heat treatment of the mechanically activated mixture at 400–450°C yields the salts NiMoO₄ and NiWO₄.     

Principal energy characteristics of a linear jet engine

Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 2, pp. 118–120, March–April, 1990.