Ultrafiltration of Aqueous Solutions of Bromocresol Purple in the Presence of Dispersed Carbon

Ultrafiltration of solutions of Bromocresol Purple on a UFM-50M membrane in the presence of dispersed carbon was studied. The variation of the flow rate through unit surface area of the membrane and of the dye retention factor with time was traced. The influence exerted on the ultrafiltration by dye adsorption on dispersed carbon and by formation of a dynamic membrane was determined. For the initial stage of filtration, the dependence of the retention factor on the dye concentration in solution was found and accounted for.     

Atom-transfer radical polymerization of poly(ethylene oxide) macromonomers in aqueous media

Soluble comb-shaped and swelling network polymers based on monomethacrylate (M = 2080) and bismethacrylate (M = 4000) poly(ethylene oxide) macromonomers, have been synthesized by the controlled atom-transfer radical polymerization in aqueous media. PEG 2000 methyl ether ethyl-2-bromoisobutyrate and 2-bromoisobutyrate, in combination with CuBr, CuBr₂, and 2,2′-bipyridyl, have been used as initiators. The length of the main chain of comb-shaped polymers, as estimated with multidetector chromatography, is in good agreement with the calculated values in the 15–20 range at M _w /M _n = 1.42–1.89. The polymerization of the methacrylate macromonomer proceeds at a high rate and with a nearly quantitative conversion. The replacement of 10–80 mol % CuBr with CuBr₂ appreciably decelerates polymerization and decreases polydispersity to 1.14–1.21, while the experimental and calculated values of chain lengths remain equal. This finding indicates a higher level of process control. The polymer networks thus prepared manifest Gaussian elastic behavior, as is evident from the relationship between the elastic modulus G and the swelling degree Q that is consistent with the classical prediction G ～ Q ^m , where m = ?1/3. Within the framework of the accepted model of networks of this type, this fact suggests the short length of polymethacrylate chains. In addition, the relationship between the time of attainment of the gelation point and the composition of the initiation system agrees with the atomtransfer controlled polymerization mechanism. The efficiencies of various radical polymerization methods for controlling the network structure are compared.     

Reactions of potassium dibenzo-18-crown-6 pentacyanocobaltate(II) with some lewis bases

ESR has been applied to the interactions of [K(DBC)]₃[Co(CN)₅], in which DBC is dibenzo-18-crown-6, in methanol solution with triphenylphosphine, pyridine, and triethylamine. The ESR spectra are described for the paramagnetic [(NC)₅CoB]^3– adducts, where B is triphenylphosphine or pyridine.Translated from Teoreticheskaya i Éxperimental'naya Khimiya, Vol. 25, No. 2, pp. 234–237, March–April, 1989.     

Transformations of 2-(3-Hydroxy-3-methyl-1-butynyl)adamantan-2-ol >Catalyzed by Acids

Reaction of 2-(3-hydroxy-3-methyl-1-butynyl)adamantan-2-ol with acetonitrile under Ritter reaction conditions is accompanied by isomerization and partial hydration where the water addition to the triple bond occurs nonselectively. As a result of reaction carried out in the presence of 8 equiv of sulfuric acid a mixture was obtained of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]-acetamide, and N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-1-oxo-3-butyl]acetamide in ~10:3:2 ratio. In the presence of 2 equiv of the acid the mixture obtained consisted of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]acetamide, and 1-(1-acetylamino-2-adamantyl)-3-methyl-2-buten-1-one in the same ratio. In Rupe reaction conditions we obtained instead of the expected ,-unsaturated ketones a mixture of 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-1-one and 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-2-one in a 5:3 ratio.     

ON THE OPTICAL SPECTRA OF SOLID FILMS OF RETINYL POLYENES. ISOMERIZATION DURING THE AUTOXIDATION?

Abstract— The UV spectra of solid amorphous films of all-trans retinyl polyenes. i. e. retinyl acetate, retinyl palmitate, axerophtene and retinal, on supports are investigated. It is shown that in the absence of oxygen the spectra of the films do not change at room temperature; in the presence of O₂ the fast oxidation of the polyenes occurs which in the case of retinol esters and axerophtene is accompanied by the shift of the absorption maxima to the shorter wavelengths. Consequently, the interpretation of blue shift of UV spectra of retinyl polyene films given by Hotchandani and Leblanc (1976) is incorrect. The formation of the only compound is shown to occur during the first stage of the oxidation of retinyl acetate and retinyl palmitate films. Proceeding from IR spectra of oxidized films the compound is assigned to the corresponding 11-cis isomer.     

Two-body interatomic interaction and properties of the alloy Cu3Au

Calculations are made of the ordering energyV (R) and the Fourier transform v() of it for the disordered Cu₃Au alloy in the Fermi sphere approximation using the pseudopotential method in the second order of perturbation theory. These characteristics are used to calculate some properties of the alloy, in particular, the short- and long-range order and the temperature of the order-disorder transition.Translated from Izvestiya Vysshikh Zavedenii, Fizika, No. 10, pp. 84–88, October, 1980.     

Optical “memory” centers on an adsorption silicon surface

The charging of an illuminated silicon surface discovered by Abkevich [1] is of considerable interest for a number of practical applications (for example, semiconductor photography [2] and gas analysis). The present paper gives the results of investigations aimed at establishing the possibility of controlling the optical charge memory on the silicon surface by adsorption methods.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 92–96, January, 1981.We thank V. F. Kiselev for discussing the work and for helpful comments.     

Photoinjection phenomena in a silicon-silcon dioxide system

Silicon-silicon dioxide structures obtained by thermal, anodic, and chemical oxidation of silicon are studied by the photocharge and photoinjection current methods. It is shown that the extent of the fluctuation state tails" near the edges of the SiO₂ forbidden zone is small (0.2 eV). The threshold for negative photocharging of anodic oxide traps is found to decrease with increase in oxide thickness, a fact related to the existence of a nonstoichiometric transition layer between the silicon and silicon dioxide. The effect of hydration and dehydration on negative optical charge of oxide traps is studied, and it is shown that the basis of electron traps is formed by the most hydrated and deformed SiO₄H_n tetrahedra. The possibility of creating electron and hole traps in the oxide layer by doping with metal ions from a solution is demonstrated. It is found that the corresponding defects are also adsorption centers for water molecules by a coordination mechanism.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 3–7, July, 1981.In conclusion, the authors thank V. F. Kiselev for his interest in the study and valuable remarks.     

Synthesis of bipyridine and terpyridine based ruthenium metallosynthons for grafting of multiple pyrene auxiliaries

The synthesis of novel ruthenium(II) bipyridine or terpyridine complexes bearing an increasing number of pyrene or toluyl moieties is described. The ruthenium complexes are constructed in a first step with ligands bearing the required bromine functions, followed in a second step by stepwise grafting of 1-ethynylpyrene or 4-ethynyltoluene promoted by Pd(0). A complex bearing a protected triethylsilylacetylene function was also prepared. In situ deprotection of this function with K₂CO₃ and cross-coupling with 1-bromopyrene afforded a soluble complex in which two pyrene moieties are linearly linked via ethynyl spacers to one of the bipyridine ligands. These highly coloured complexes exhibit well defined absorption and emission properties in solution at both rt and 77 K.     

(-)-(R)- and (+)-(S)-Carvone in the Synthesis of Optically Active Acetylenic Alcohols,Ethers, and Dichlorosilyl Derivatives

Reaction of butyllithium with acetylene and 1-hexyne gave the corresponding lithium acetylides which reacted with (-)-(R)- and (+)-(S-carvone in a stereospecific fashion to give lithium (1-ethynyl- or 1-hexynyl)-5-isopropenyl-2-methyl-2-cyclohexenolates. Hydrolysis of the latter gave individual optically active tertiary terpene alcohols having both acetylenic and p-menthene fragment. Their treatment with methyl iodide in the presence of hexamethylphosphoric triamide afforded the corresponding methyl ethers. The reaction of 3-ethynyl-5-isopropenyl-3-methoxy-2-methylcyclohexene with butyllithium and trichloro(vinyl)silane yielded optically active dichlorosilyl-containing acetylenic compounds.