Photoconversion of lutetium diphthalocyanine and interpretation of its electronic absorption spectra

When frozen solutions of lutetium diphthalocyanine (LuPC₂) in a mixture of methylene chloride with trichloroethylene are irradiated by UV light, monocations of LuPC₂ form. The photoreaction is slowed and ceases in an early stage apparently due to the reversibility of the photoconversion in this system. The reduced form of LuPC₂ (its monoanions) are completely converted into the neutral form of LuPC₂ during irradiation. When this photoconversion is carried out in a frozen solution, the electronic absorption bands in the spectrum of the LuPC₂ formed are displaced in comparison to the bands of the original substance under the same conditions, posibly due to the difference between the structures of the solvation shells. An interpretation of the electronic absorption spectrum of LuPC₂ in the 300–1600-nm region has been given on the basis of the scheme of the molecular orbitals of sandwich phthalocyanine dimer with one -electronic vacancy.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 5, pp. 614–618, September–October, 1989.We express our thanks to P. N. Moskalev for supplying the preparations of M^IIIPC₂.     

2-Diphenylphosphinoyloxybenzaldehyde 4-Nitrophenyl-, 4-Phenyl-1-phthalazinyl-, and Aroylhydrazones and Thiosemicarbazone

Condensation of aryl- and aroylhydrazines and thiosemicarbazide with 2-diphenylphosphinoyloxybenzaldehyde results in formation of the corresponding hydrazones and thiosemicarbazone. The products give rise to conformational equilibrium between rotational and Z,E isomers, which is strongly displaced toward the E,E',Z' isomer and is determined by the nature of substituent in the hydrazine fragment.     

Asymmetric Baeyer—Villiger oxidation: control of stereoelectronic demand

The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004.     

Catalytic nitrobenzene oxidation of lignins

Alkaline nitrobenzene oxidation of hardwood and softwood lignins in the presence of redox and phase-transfer catalysts was studied. The selectivity of oxidation of lignins increased by 1.7 to 1.9 times. A possible mechanism of catalysis is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 3004–3007, December, 1996.     

The lipids of microalgae II. Lipids of the dry biomass ofMonochrysis lutheri

Institute of the Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 899–900, November–December, 1993.     

Effect of hydrothermal treatment on catalytic properties of superhigh-silica zeolites

The effect of hydrothermal treatment of decationized superhigh-silica zeolite on the mechanism of n-hexane conversion has been studied. It has been established that thermosteam modification sharply decreases the cracking activity and increases the selectivity to aromatization reactions. Zeolite acidity markedly decreases, but its crystal structure does not become amorphous.

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Reaction of chlorine fluosulfate with fluorinated alcohols and some properties of polyfluoroalkyl hypochlorites

Conclusions Stable ,-dihydropolyfluoroalkyl hypochlorites were obtained by reacting ClOSO₂F with fluorinated alcohols, and some of their chemical properties were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2369–2374, October, 1980.     

Effect of the Electrolyte Concentration on the Reversibility of a Nickel Oxide Electrode in a Nickel-Zinc Battery

The degree of charging of a nickel oxide electrode composed of spherical nickel hydroxide in a nickel-zinc battery was studied in anodic oxidation of the electrode in KOH solutions of different concentrations, containing hydroxozincate ions.     

THE QUANTUM EFFICIENCY FOR THE INTERPHOTOCONVERSION OF THE BLUE and PINK FORMS OF PURPLE MEMBRANE

When the cations bound to purple membrane are removed it turns blue, and when this blue membrane is irradiated its color changes to pink. Irradiation of pink membrane leads to the reformation of blue membrane. We have determined that the quantum efficiency for the formation of pink membrane from deionized blue membrane is 1.6 ± 0.6 ± 10 ⁴ at 0^oC, pH 5.0. We also found that the quantum efficiency for the back photoconversion, i.e. the formation of blue membrane from pink membrane, is 8.8 ± 1.6 ± 10^-3 at 0^oC, 55 times greater than that of the forward photoconversion reaction. The extinction coefficients of the pink membrane and blue membrane were determined to be 44 500 ± 670 cm^-1 M^-1 at 491 nm and 54 760 ± 830 cm^-1 M ^-1 at 603 nm, respectively, assuming light-adapted purple membrane is 63 000 cm^-1 M ^-1 at 568 nm. The quantum efficiency for forming pink membrane from blue membrane is much lower than that for forming the photointermediate of the blue membrane's photocycle. Their relationship is similar to that of light-adaptation and photocycle of the dark-adapted purple membrane.