Interaction of cationic 5,10,15,20-tetrakis(4-N-methyl pyridyl) porphyrin with mono-and polynucleotides: A study by picosecond fluorescence spectroscopy

The interaction of water-soluble cationic 5,10,15,20-tetrakis(4-N-methyl pyridyl) porphyrin (H₂TMPyP4) with some mono-and polynucleotides is studied by time-resolved and steady-state fluorescence spectroscopy, as well as by steady-state absorption spectroscopy. The fluorescence decay kinetics are analyzed by reconstructing the decay time distributions, which made it possible to describe in more detail than previously the complexes formed due to the interaction. The main effect of binding of H₂TMPyP4 adenosine 5′-monophosphate and to poly(dA-dT)₂ is shown to be an increase in the fluorescence lifetime from 4.6 ns in the solution to 8.3 and 12.3 ns, respectively. This effect is explained by a less polar (in comparison with water) environment of porphyrin in complexes, which leads to a decrease in the quenching action of the intramolecular charge transfer state between the porphyrin macrocycle and methyl pyridyl groups. In the case of complex formation with guanine-containing nucleotides (guanosine 5′-monophosphate and poly(dG-dC)₂), the effect of decrease in the quenching action of the intramolecular charge transfer state caused by a decrease in the medium polarity is superimposed by a stronger effect of decrease in the fluorescence lifetime of porphyrin as a result of intermolecular electron transfer from guanine to excited porphyrin. A high sensitivity of this intermolecular quenching to the mutual arrangement of the electron donor and the electron acceptor makes it possible to reveal four types of complexes between H₂TMPyP4 and guanosine 5′-monophosphate, which differ in the positions of four broad peaks in the porphyrin fluorescence decay time distribution (0.1, 0.7, 2.4, and 6.1 ns). For the complex with poly(dG-dC)₂, a narrow peak at 2.8 ns prevails in the fluorescence decay time distribution, with the contributions from two additional narrow peaks at 1.0 and 6.2 ns being small.     

Nitroazines. 20. Simple syntheses of nitropyrazolopyridines from aliphatic nitrosynthons and aminopyrazoles

Two variants of a synthesis for nitropyrazolopyridines from aminopyrazoles and two- or three-carbon nitrosynthons are examined.For Communication 19 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1560–1564, November, 1992.     

Condensation of aryl bromides with styrenes,catalyzed by nickel complexes in the presence of zinc

Conclusions Condensation of aryl bromides with styrenes in acetonitrile in the presence of nickel organometallic complex catalysts and metallic zinc occurs regio- and stereoselectively to give E-stilbenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2508–2511, November, 1987.     

α-Aminoazoles in the Synthesis of Heterocycles. Intermediates of Reaction between 3(5)-Aminopyrazoles and Trifluoroacetylacetone

Russian Journal of Organic Chemistry -     

Einige Übergangsmetallkomplexe von Diäthylestern der 1-Cyano-2-Oxo-Propanphosphonsäure (1-CDÄPA) und der Äthoxycarbonylmethanphosphonsäure (CMPD)

Some Transition Metal Complexes of Diethyl Esters of 1-Cyano-2-oxo-propane-phosphonic Acid and Ethoxycarbonylmethane-phosphonic Acid By means of metal exchange cobalt(II), nickel(II), and chromium(III) complexes of diethyl esters of 1-cyano-2-oxo-propane-phosphonic acid (1-CDEPA) and ethoxycarbonylmethanephosphonic acid (CMPD) were obtained from their corresponding potassium salts and halides of transition metals. The stable chelatic structure of these complexes was established by means of i.r. spectra and the configuration on the basis of the electron spectra and their magnetic moments.     

New Synthetic Approaches to Functionally Substituted 4,5-Dihydro-1,2,3-oxadiazole 2-Oxides

A practical procedure has been proposed for the synthesis of functionally substituted 4,5-dihydro-1,2,3-oxadiazole 2-oxides on the basis ofsulfamic acid derivatives.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 121–123.Original Russian Text Copyright © 2005 by Tartakovskii, Ermakov, Strelenko, Vinogradov, Petrov.