Chemistry of 1,1,2,2-tetracyanoethane

Conclusions 1-(N,N-Dimethylhydrazino)-4-methyl-2,2,3,3-tetracyanocyclopentane is isomerized reverslbly in solution, with inversion of the configuration of the tetrahedral carbon atom in position 1.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1075–1079, May, 1989.     

Chemistry of 1,1,2,2-tetracyanoethane. 14. Structure of 3-(N′,N′-dimethyl-N-acetylhydrazino)-5-methyl-1,1,2,2-tetracyanocyclopentane in solution and the crystal and the reasons for the selective addition of nucleophiles to a specific cyano group

For communication 13, see [1].     

19F-detected dual-optimized inverted 1JCC 1,n-ADEQUATE

Modification of the recently reported ¹⁹F-detected 1,1-ADEQUATE experiment that incorporates dual-optimization to selectively invert a wide range of ¹J_CC correlations in a 1,n-ADEQUATE experiment is reported. Parameters for the dual-optimization segment of the pulse sequence were modified to accommodate the increased size of ¹J_CC homonuclear coupling constants of poly- and perfluorinated molecules relative to protonated molecules to allow broadband inversion of the ¹J_CC correlations. The observation and utility of isotope shifts are reported for the first time for 1,1- and 1,n-ADEQUATE correlations.     

Using LR-HSQMBC to observe long-range H–N correlations

The recently reported LR-HSQMBC experiment has been optimized for ¹H–¹⁵N long-range heteronuclear couplings. Several previously unreported four-bond correlations, consistent with the predicted by DFT calculations (0.2–0.3 Hz ⁴J_NH couplings), have been observed for strychnine using 2 Hz optimization of the LR-HSQMBC experiment. This experiment offers an advantage over accordion-optimized experiments such as IMPEACH and CIGAR for the observation of long-range ¹H–¹⁵N correlations in that the experiment is refocused and employs a CLIP pulse sequence element to bring the long-range correlations into phase, allowing broadband X-decoupling to be employed during acquisition.     

Change in the structure of a polymer solution in a longitudinal hydrodynamic field

There are two qualitatively different conditions for the stretching of liquid fibers formed by moderately concentrated polymer solutions [1]. If the longitudinal gradient of the drawing rate is rather small the structure of the solution remains unchanged. If this gradient exceeds a certain critical value, some of the solvent is expressed from the solution in and the liquid filament is converted into a slightly swollen fiber. The solvent released settles as droplets on the filament surface. This effect is of very great importance for a number of industrial processes pertaining to the production of filaments and films from polymer solutions. In addition, as was reported in [1], the drawing of a liquid filament, accomapnied by orientational formation of the solid phase, can serve as a most simple imitation of the formation of silk and gossamer filaments in nature.This paper presents a qualitative theory for this phenomenon, based on investigation of the thermodynamic stability of a polymer solution in a longitudinal hydrodynamic field.In conclusion the author thanks S. Ya. Frenkel for kindly providing information about the experiments conducted in his laboratory.     

Effect of particles suspended in a fluid flow on the decay of isotropic turbulence

Dynamic equations have been obtained for the two-point double correlations of the fluctuation velocities of a fluid and the particles suspended in it at low volume concentrations of the solid phase. In the case of uniform isotropic turbulence these equations can be considerably simplified. The final period of decay of isotropic turbulence has been studied in detail. At this stage in the case of high-inertia particles the inhomogeneous-fluid turbulence is similar to the turbulence of a homogeneous fluid (without particles) in the sense that the presence of the particles affects only the fluctuation energy but leaves unchanged the spatial scales of turbulence and the spatial energy spectrum function. The suspended particles lead to exponential damping of the turbulent pulsations.Little theoretical information is available on the hydrodynamics of a suspension of fine particles in a turbulent liquid or gas. Research has been mainly confined to the behavior of the individual particles in a given turbulence field [1]. The problem of the turbulent motion of the mixture as a whole has been examined by Barenblatt [2], who derived the equations of motion of the mixture, using Kolmogorov's hypothesis to close them. Hinze [3] has also attempted to derive equations for turbulent pulsations of the mixture. However, as Murray showed [4], Hinze' s equations contradict Newton' s third law.The effect of suspended particles on the turbulence of a two-phase flow is governed by the noncorrespondence of the local velocities of the particles and the medium. The forces of resistance to the motion of the particles relative to the fluid lead to additional dissipation of fluctuation energy and decay of turbulence [2]. On the other hand, if the averaged velocities of particles and medium do not correspond, the suspended particles may also have a destabilizing effect [5, 6], causing energy transfer from the averaged to the pulsating motion. Below we shall consider the case where the averaged velocities of the two phases coincide, i.e., we shall deal only with the first of the two above-mentioned effects.The authors thank G.I. Barenblatt for his useful advice.     

Properties of the particle pseudogas in a vertical fluid-particle flow

The rheological equations of state of the dispersed medium are obtained for one-dimensional flows of monodisperse systems in which the acceleration of the external body force field and the average interphase slip velocity are collinear, on the basis of an analysis of the pseudoturbulence properties. Ekaterinburg. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No.2, pp. 53–65, March–April, 1994.     

Stratification of a neutrally buoyant suspension in a circular tube

Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 2, pp. 124–131, March–April, 1991.     

Cover Picture: Turning Spiroketals Inside Out: A Rearrangement Triggered by an Enol Ether Epoxidation (ChemistryOpen 5/2015)

Invited for this month''s cover picture is the group of Professor Mark Peczuh at the University of Connecticut. The cover picture compares the rearrangement of a small molecule to the process of turning a stuffed animal inside out. The recycled, inside-out stuffed animals are both artistic and philosophically provocative. They capture the essence of the rearrangement reaction because the compounds themselves turn inside out over the course of the reaction, extending the diversity of products that can arise from simple starting materials. Small molecules often have functional groups with latent reactivity; under the appropriate conditions, those groups can react with other compounds (e.g., reagents) and also with other groups in the same molecule in an intramolecular reaction. The research team found that the epoxidation of some highly functionalized spiroketal compounds promoted rearrangements of their structures that turned them inside out. Some of the features of the products led them to use X-ray crystallography or a combination of computer-assisted structure elucidation, computation, and a new version of the 1,1-ADEQUATE NMR experiment to determine their structures. For more details, see the Communication on p. 577 ff.     

Viscosity of the liquid phase in a dispersion

The motion of a dispersion (continuous medium and particles) may be described [1] via the equations ot conservation of matter and momentum for the two phases separately. Here it is necessary to know how the viscosity, pressure in the solid, and other quantities vary with the parameters of the motion. This difficulty occurs even for the very simple model where the internal stresses in the dispersed phase are taken as zero, as there is then an uncertainty as to the viscosity of the medium, which is not a material constant and is dependent on the concentration. There is also uncertainty as to the forces of interaction between the phases. There are numerous empirical relationships for these forces, and also a theoretical one [2]. Here an analogous method is applied to derive an expression for the viscosity of the liquid. This viscosity applies to a liquid filtering through a porous medium in the particular case where the concentration is such as to produce close packing of the solid particles. The result corresponds to standard formulas in the case of low concentrations.