Aziridinylketones and their cyclic anils. 12

We have measured the PMR spectra of 5, 7-diaryl-1, 4-diazabicyclo[4. ].O]hept-4-enes. We have studied the structure of the 5-(4-nitrophenyl)-7-phenyl derivative by x-ray diffraction. We show that the six-membered heterocycle has the half-chair form. The 6-H and 7-H protons of the aziridine ring are trans, while the 7-aryl is exo relative to the six-membered ring. Introduction of substituents into the aromatic ring has practically no effect on the geometry of the bicycle.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1117–1124, August, 1994.For Communication 11, see [1].     

Redispersion of Highly Disperse Powder of Titanium Dioxide in Aqueous Medium

Based on an analysis of interparticle interaction in highly disperse powders, a parameter is suggested allowing one to evaluate the tendency of dispersed particles to the formation of aggregates, the aggregation coefficient. It was shown that the particles of metal oxide powders with radius smaller than 10 m are present in their aggregated state. It was found that redispersion of highly disperse titanium dioxide powder in the aqueous medium is incomplete. The incomplete redispersion may be caused by the roughness of particles and/or the formation of the regions of entrapped air that are not destroyed by capillary pressure.     

Intermolecular interactions of polymethacrylic acid with nonylphenoxypoly(ethoxy)ethanol in water solutions

On the basis of concentration pH dependences of binary solutions of anionic polyelectrolyte, polymethacrylic acid, and nonionic surfactant, nonylphenoxypoly(ethoxy)ethanol the role of hydrophobic interaction in the development of associative and aggregative processes was shown. It is established that the criterion of evaluation of the preferred contribution of hydrophobic interaction is the inflection point on the dependence of pH difference of the individual solutions of nonylphenoxypoly(ethoxy)ethanol and binary solutions of polymethacrylic acid and nonylphenoxypoly(ehoxy)ethanol on the logarithm of ratio of their concentrations.     

Raman scattering in A3B2C9 ferroelectric crystals

Raman spectra of some A₃B₂C₉ ferroelectric crystals (here A=Cs, Rb; B=Sb, Bi; C=Br) have been obtained, and a number of high-frequency bands have been assigned. The Rb₃Bi₂Br₉ and Rb₃Sb₂Br₉ crystals are shown to differ in structure from Cs₂Bi₂Br₉. The qualitative changes in the spectra in the 77–300 K temperature interval can be associated not only with structural phase transitions, but with the effect of the anharmonic Fermi resonance between one-and two-phonon excitations as well. Fiz. Tverd. Tela (St. Petersburg) 39, 1452–1455 (August 1997)     

Redispergation of TiO2 particles in aqueous solutions

The colloidal stability of TiO2 dispersions in aqueous solutions was studied. Aqueous solutions of ATLAS G-3300 (1.57 x 10(-3) mol/l), TRITON X-100 (5 x 10(-5) mol/l), and PMAA (4 x 10(-6) and 5.81 x 10(-3) mol/l) have been used as medium for redispergation of TiO2 particles. Stability of dispersions was investigated at different pH values by two different methods. By using analytical centrifuge the sedimentation velocity of TiO2 particles was directly measured and by means of light scattering the particle size of dispersed particles has been monitored. Combination of these two methods allowed determination of the aggregation degree of TiO2 particles as well as structure of the aggregates formed in aqueous phase. It has been found that redispergation process does not provide complete separation of virgin TiO2 particles. Even in the case of stable dispersions some aggregates were found, which consisted of 2-4 virgin TiO2 particles. With increasing colloidal stability of dispersions aggregates appear to be spherically shaped. In the system where TRITON X-100 was used, formation of secondary aggregates by fusion of primary ones was observed.     

Theory of profiles of hydrogen stretching infrared bands of hydrogen-bonded solids. Multi-Fermi resonance effects and strong coupling between the high-frequency hydrogen stretching vibration and low-frequency phonons

A theory is developed to describe the profiles of hydrogen stretching infrared bands of hydrogen-bonded solids taking into account the anharmonic coupling between the high-frequency stretching vibration, ν(XH), and low-frequency lattice phonons, Ω_i, as well as multi-Fermi resonances between states involving the ν(XH) stretching and overtones or combinations of some internal modes. The theory has been constructed in the framework of the extended molecular exciton Davydov approach. Model calculations show that the strong couplings between the high frequency ν(XH) and low-lattice vibration frequencies, Ω_i, generate the broadness of the ν(XH) band but the multi-Fermi resonances between the ν(XH) state and overtones or combinations of internal modes generate the complicated substructure band which is observed experimentally.     

Effect of anharmonicity and vibrations resonance interaction in the vibrational spectra of H-bonded crystals

On the basis of the absorption coefficient calculation it is shown that strong optical and mechanical anharmonicity of the OH group vibrations and the interaction between the main tone and the overtone of the other vibration of the same OH group and the same symmetry (Fermi-resonance) leads to the formation of two-phonon bound states (biphonons) seen in spectra as “additional” sharp bands. The IR and Raman bands half-width and shape of the main tone and the bound state is measured as a function of temperature and a possible theoretical treatment is proposed. The anharmonicity parameters and low-frequency vibrations responsible for the temperature behavour of the main tone and the biphonons are determined.