Photolysis of hexamethyldisilane at 206 nm

The photolysis of Me₆Si₂ at 206 nm results in two main decomposition processes: simple Si---Si bond breaking with a quantum yield of Φ = 0.21 ± 0.03, and Me₃SiH elimination with the concomitant formation of Me₂SiCH₂ with Φ = 0.18 ± 0.01. There is also a minor decomposition channel with a very small quantum yield, Φ = (5.6 ± 0.2) × 10⁻³, which results in the formation of Me₄Si and Me₂Si. The main fate of the excited Me₆Si₂ molecule produced during photolysis is stabilization by collisional deactivation. The end products observed indicate that the reaction pathways followed by the main intermediates, Me₃Si and Me₂SiCH₂, are the same as those found in the photolysis of Me₄Si (Ahmed et al., J. Photochem. Photobiol. A: Chem. 86 (1995) 33).     

Acylation of n-phenyl-2-(indol-3-yl)succinimides

Treatment of N-phenyl-2-(1-R-indol-3-yl)succinimides with acetyl perchlorate leads to acylation of the benzene ring of the indole substituent.L. M. Litvinenko Institute of Physico-Organic and Carbon Chemistry, Ukrainian Academy of Sciences, Donetsk 340114. A. N. Kosygin State Textile Academy, Moscow 117918, GSP-1. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 85–88, January, 1997.     

Pulsed photothermal phase-shift spectroscopy for weak absorption measurement

A novel photothermal phase-shift spectroscopy configuration based on the retro-reflected beam interference has been developed and its operational principle is described. The weak absorption measurement ability of this technique is experimentally proven with a water/ethanol solution of standard Pyronine G dye and the limit of detection is found to be 1.8 x 10(-6) absorbance. Potential applications of the technique are discussed.     

Catalytic Properties of Acid Solutions and the Structure of Acid–Base Complexes with Strong Hydrogen Bonds

The catalytic action of acid solutions involves an equilibrium step in the formation of a reactive complex of reactant molecules with catalyst entities. The relative concentrations of these complexes are determined by using thermodynamic parameters (acidity functions and activities of catalyst components). Data on the structure of complexes with strong H-bonds can be obtained from the vibrational spectra of these species. These data are required for establishing the mechanisms of catalytic reactions and for predicting the catalytic properties of acid solutions containing these complexes.     

A Study of Amorphous Precursors for PbZrO3-PbTiO3 Based Ceramic Materials

Amorphous precursors for PbZrO₃ and PbTiO₃ ceramics were prepared from lead acetate and the transition metaln-propoxide inn-propanol orn-butoxide inn-butanol and hydrolysed with an excess of water. According to GLC and TGA/EGA analyses, the type of alkoxide group influences distinctly the structure of heterometallic precursors, i.e., oxo or acetate bridging, and the amounts of hydroxyl and organic groups bound to the metal network. The local environments of metal atoms in the amorphous precursors were also studied by EXAFS. The analysis reveals that in Pb−Zr precursors alkoxide groups modify the coordination spheres of the zirconium atoms. Conversely, local environments of both lead and titanium atoms within the analysed range of 3.4 A depend weakly on the type of alkoxide used.     

Synthesis of the first stable carborane containing simple enol

A carborane-containing stable simple enol — 1-2-isopropyl-o-carboran-I-yl)-1-phenyl2-mesityl-2-lrydroxyctlrylcne — has been synthesized. This enol does not isomerize to the starting ketone or keto-enol mixture even after prolonged heating in benzene in the presence of CF₃COOH.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1561–1563, June, 1996.     

1,2,2-Trimethyldisilane-1,1,2-triol: intermediate formation and conversion to condensation products

1,2,2-Trimethyldisilane-1,1,2-triol (1) is formed as an unstable intermediate upon hydrolysis of oligo(trimethyldisilanylsesquiazane). In the absence of trapping agents it undergoes rapid condensation to give ether-soluble poly(trimethyldisilanyloxane) which contains silanol groups. Treatment of the hydrolysis products with chlorotrimethylsilane in the presence of triethylamine affords trimethylsiloxy derivatives, (Me₃SiO)₂MeSiSiMe₂(OSiMe₃),5,6, and [Si₂Me₃O _x (OSiMe₃) _y ] _n . The isolation of these products indicates that disilanetriol1 readily undergoes condensation to form hydroxylcontaining six-membered rings and polysiloxanes. The condensation of compound1 in the presence of Me₃SiOH has been studied. The ratio between the isomeric cyclosiloxanes5 and6 has been determined both by¹H NMR spectroscopy and by a chemical method (chlorinolysis). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1788–1792, October, 1993.     

Resolution of a paradox in the electrophoresis of DNA in agarose gels

A paradox was observed in a previous study of the electrophoresis of linear DNA fragments in agarose gels (D. L. Holmes and N. C. Stellwagen, Electrophoresis 1990, 11, 5-15). The pore size of the agarose matrix was more accurately determined if the root-mean-square radius of gyration was used to measure DNA macromolecular size. However, the Ogston equations were obeyed and other gel parameters such as the apparent fiber radius and fiber volume appeared to be better described if the geometric mean radius was used to measure DNA size. This paradox can be resolved if relative mobilities (with respect to the smallest DNA molecule in the data set) are used to construct the Ferguson plots, instead of absolute mobilities. Using relative mobilities and the root-mean-square radius of gyration, the Ogston equations are obeyed and the pore size of the matrix is consistent with values determined by other methods.     

Fluorimetric determination of anionic surfactants by extraction as safranine-T ion-pairs

A simple and rapid method is proposed for the spectrofluorimetric determination of anionic surfactants. It is based on formation of an ion-pair at pH 2 with safranine-T and its subsequent extraction into chloroform. Fluorescence intensity is increased by a factor of about 5 with respect to that of the reagent. The calibration graph is linear in the concentration range 0.015–0.40 mg l^?1 dodecyl sulfate; the relative standard deviation is 5.6% at 0.22 ml l^?1 surfactant. The method is applied to determine anionic surfactants in city waste-waters, giving recoveries close to 100%.