New reaction of glycidols with oxalyl chloride and phosgene—an approach to cyclic esters

2,3-Epoxy alcohols (glycidols) react with carboxylic acid dichlorides to form cyclic esters of 3-chloro-1,2-diols. The reaction proceeds with complete retention of the configuration of the C(2) atom of the initial glycidol and with predominant (but not complete) inversion of the configuration of the C(3) atom in the final heterocycle. Translated fromIzvestiya Akademii Nuak. Seriya Khimicheskaya, No. 11, pp. 2110–2114, November, 1999.     

Purcell effect in one-dimensional photonic quasicrystals

The change in probability of spontaneous emission for emitter placed in one-dimensional photonic quasicrystal (optical Fibonacci lattice) was examined. When the dipole is placed in Fibonacci lattice two different scenarios can be expected: enhancing (if frequency and direction of the dipole emission correspond to optical eigenmode of structure, and position corresponds to maximum value of modes electric field profile) or suppression (in case of photonic band gap) of spontaneous emission rate. Fact that both effects are expressed in quasicrystals less than in the Bragg reflectors and in the microcavities was demonstrated.     

Mechanism reduction of chemical reaction based on sensitivity analysis: development and testing of some new procedure

This paper proposes a procedure for simplifying the mathematical model of a chemical reaction by reducing the number of steps and species in the reaction scheme. This procedure is based on the sensitivity analysis of the model functional to the change in the model parameters. The application of this procedure makes it possible to accelerate and improve the construction of mathematical models for chemical reactions, as this does not require the calculation of sensitivity coefficients at various time points or sensitivity matrix analysis. This scheme was predicted the same behavior of the main reaction components as the detailed reaction scheme but includes much fewer steps. The efficiency of using this procedure was demonstrated by comparative results of modeling of formaldehyde oxidation and hydrogen oxidation in terms of detailed and reduced schemes. The sensitivity analysis was performed by Sobol’s method.     

Field cycling by fast NMR probe transfer: Design and application in field-dependent CIDNP experiments

A novel field-cycling unit with fast digital positioning of a high-resolution nuclear magnetic resonance probe in a spatially varying magnetic field is described and used to measure CIDNP spectra of the amino acid-dye (histidine-bipyridyl) photoreaction system in the range between 0 and 7 T. The pattern of nuclear polarization varies with the magnetic field. In particular, strong polarization with an emission/absorption pattern (multiplet effect) is found at low field for two histidine ringprotons with scalar coupling below 3 Hz visible only because of the high resolution made possible by the new field-cycling setup. Also for the CH₂ protons in the β-position a multiplet effect is observed having a pattern changing with magnetic field. By analysis of the spin nutation the non-Boltzmann population differences of the nuclear levels have been determined.     

Tamm Plasmons in Structures with Quasiperiodic Metal Gratings

JETP Letters - A theoretical study of structures with Tamm plasmons, where metal strips forming a one-dimensional periodic structure with a quasiperiodic unit cell on the surface of a structure are...     

Quantization of an electromagnetic field in two-dimensional photonic structures based on the scattering matrix formalism (<Emphasis Type="Italic">S</Emphasis>-quantization)

We have analyzed the parameters of the Franck–Condon and Herzberg–Teller interactions, which form the fine-structure spectra of diphenylbutadiene substituted derivatives with the general formula X–Ph–(C=C)2–Ph–Y (where X, Y = H, NO₂, N(CH₃)₂, and NH₂ are the substituents in different combinations) in solutions of n-paraffins at 4.2 K. The influence of substituents on the vibronic parameters of characteristic bands that describe the states (vibrations, types of deformations upon excitation) of the phenyl rings and diphenylbutadiene polyene bridge has been considered. Data on the influence of the H, NO₂, N(CH₃)₂, or NH₂ terminal fragment on the parameters of the intra- and intermolecular interactions of diphenylbutadiene substituted derivatives have been presented.     

Quantization of electromagnetic field and analysis of Purcell effect based on formalism of scattering matrix

We have developed a rigorous self-consistent approach for the quantization of electromagnetic field in inhomogeneous structures. The approach is based on utilization of the scattering matrix of the system. Instead of the use of standard periodic Born-Karman boundary conditions, we use the quantization condition implying equating eigenvalues of the scattering matrix (S-matrix) of the system to unity (S-quantization). In the trivial case of uniform medium boundary condition for S-quantization is nothing but periodic boundary condition. S-quantization allows calculating modification of the spontaneous emission rate for arbitrary inhomogeneous structure and direction of the emitted radiation. S-quantization solves the long-standing problem coupled to normalization of the quasi-stationary electromagnetic modes. Examples of application of S-quantization for the calculation of spontaneous emission rate for the cases of Bragg reflector and microcavity are demonstrated.     

Shear and elongational flow behavior of acrylic thickener solutions. Part II: effect of gel content

We have investigated the effect of crosslink density on shear and elongational flow properties of alkali-swellable acrylic thickener solutions using a mixing series of the two commercial thickeners Sterocoll FD and Sterocoll D as model system. Linear viscoelastic moduli show a smooth transition from weakly elastic to gel-like behavior. Steady shear data are very well described by a single mode Giesekus model at all mixing ratios. Extensional flow behavior has been characterized using the CaBER technique. Corresponding decay of filament diameter is also well fitted by the Giesekus model, except for the highest crosslink densities, when filament deformation is highly non-uniform, but the non-linearity parameter α, which is independent of the mixing ratio, is two orders of magnitude higher in shear compared to elongational flow. Shear relaxation times increase by orders of magnitude, but the characteristic elongational relaxation time decreases weakly, as gel content increases. Accordingly, variation of gel content is a valuable tool to adjust the low shear viscosity in a wide range while keeping extensional flow resistance essentially constant.