Synthesis,spatial structure and spectral properties of pyrylo‐4 (thio) squaraines variously substituted in cyclobutene moiety

Synthetic routes have been developed to a number of (thio) squaraine dyes containing the residues of CH‐acids at the central cyclobutene ring. The electronic and spatial structure as well as the chemical conversions and optical behaviour of the compounds obtained have been studied both theoretically and by X‐ray diffraction analysis, ¹H NMR and electronic spectroscopy. As shown, the electronic nature and sterical characteristics of the central ring substituents give rise to some general conformational features and crystal packing regularities and also govern the spectral position of the first π–π^* absorption band. The structure–property relationships established in the study provide guidance for the purposeful design of deeply coloured (thio) squaraines. Copyright © 2015 John Wiley & Sons, Ltd.     

Nd3+:Y3Al5O12 laser ceramics: Influence of the size of yttrium oxide particles on sintering

The influence of the size of Y₂O₃ powder particles on the structure formation and densification of Nd³⁺:Y₃Al₅O₁₂ laser ceramics has been studied. It is shown that the use of 50- and 100-nm yttrium oxide particles makes it possible to synthesize single-phase yttrium aluminum garnet at temperatures of 1200 and 1500°C, respectively, whereas in the case of 5000-nm yttrium oxide particles 2-h exposure at a temperature of 1500°C yields only 80 wt % of the Nd³⁺:Y₃Al₅O₁₂ phase. Bulk swelling of pressed samples during sintering of 2.94Y₂O₃-0.06Nd₂O₃-5Al₂O₃ powders with the size ratio of the initial particles R(Al₂O₃/Y₂O₃) ～ 5 is observed. The application of different-sized powders (R ～ 2.5) provides quantitative ratios between phases in the 3Y₂O₃-5Al₂O₃ system at which shrinkage in a temperature range of 20–1500°C is dominant. Laser ceramics 0–2 at % Nd³⁺:Y₃Al₅O₁₂ have been obtained by the solid-phase sintering of oxide powders (R ～ 2.5). The slope efficiency for 1 at % Nd³⁺:Y₃Al₅O₁₂ laser ceramics is found to be 33%.

     

Invited Lecture. Helical twisting in cholesteric mesophases: Molecular structure and microscopic description

Recent studies of cholesteric systems are briefly reviewed, with special attention paid to the relationship between the molecular structure of the optically active molecules and the helical twisting features. Microscopic models are presented which provide an account of specific intermolecular interactions, conformational equilibria, etc. Mechanisms of dopant-induced helix distortions are discussed based on N.M.R. studies. The use of cholesteric systems as solvents for selective reflection spectroscopy is considered.     

Generation of unipolar pulses in nonlinear media

Methods recently proposed for generating unipolar pulses in nonlinear media in terahertz and optical electromagnetic ranges are reviewed. Such pulses have nonzero “electric area” (time integral of the field strength over the entire duration of a pulse) and, correspondingly, a significant component of the field with zero frequency, thus exhibiting quasistatic properties. Effective generation of unipolar pulses would allow, e.g., transferring mechanical momentum to charged particles and, thereby, controlling the motion of wave packets of matter, which can be useful for compact accelerators of charged particles and for other applications.     

Pyrylocyanines. 34.* pyrylocarbocyanines of asymmetrical structure with bridge groups in the chromophore

Asymmetrical carbocyanines with bridge groups in the chromophore, containing pyrylium, benzothiazolium, and pyridinium residues, were produced. The electronic and steric influence of the bridge groups on the spectral properties of the dyes was analyzed. The structure of the compounds obtained was confirmed by the data of electron spectroscopy and PMR spectroscopy.     

Application of the method of energy moments to an analysis of the rotational and centrifugal constants of the H2O molecule

A method is described to compute the centrifugal constants from the first and second order energy moments. Presented as an illustration is a computation of the centrifugal constants of the H₂O molecule for the 000 vibrational state; conditions proposed in [2] were imposed on the parameters of the unitary transformation; the centrifugal constants obtained under such conditions reproduce the spectrum to 0.1 cm^–1 accuracy.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 80–84, August, 1973.     

Tuning of the photonic band gaps and the reflection spectra of a one-dimensional photonic crystal based on silicon and a liquid crystal

The reflection spectra and the photonic band gaps of a one-dimensional composite photonic crystal are calculated for different filling factors (the ratio of the thickness of a silicon layer to the lattice constant A). A change in the refractive index of the filler in a photonic crystal leads to the shift of both edges for certain side photonic bands. It is shown that, with a change in the refractive index from 1.49 to 1.69, the shift of the edges (the tuning effect) can reach the value A/λ = 0.04 for the main photonic band and 0.08 for a side band. An additional criterion for designing a photonic crystal is the estimation of the sharpness of the edges of photonic bands in the reflection spectra.     

Self-assembly and vortices formed by microparticles in weak electrolytes

We carried out experimental studies of the self-assembly of metallic micron-size particles in poorly conducting liquid subject to a constant electric field. Depending on the experimental conditions, the particles self-assemble into long chains directed along the electric field lines and form vortices and other structures. The vortices perform Brownian-type random motion due to self-induced chaotic hydrodynamic flows. We measured the diffusivity constant of the vortices and the conductivity and mechanical stiffness of the chains.     

Direct astatination of a tumour-binding protein, human epidermal growth factor, using nido-carborane as a prosthetic group

We have investigated a method for direct astatine labeling of proteins. Binding sites for astatine were created by coupling of a nido-carborane derivative to a protein, the human epidermal growth factor (hEGF), using two different conjugation methods - by glutaraldehyde cross-linking or by introduction of sulfohydryl groups by Traut's reagent with subsequent linking of ANC-1 with m-maleimidobenzoyl-N-hydroxysulfosuccinimide ester. The conjugates were astatinated using the Chloramine-T method in high yield. The best labeling was obtained by the glutaraldehyde conjugate with an average yield of 68±9%. In vitro stability tests indicated that the glutaraldehyde conjugated label was as stable as hEGF labeled with astatobenzoate.