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.     

Hamiltonization of theories with degenerate coordinates

We consider a class of Lagrangian theories where part of the coordinates does not have any time derivatives in the Lagrange function (we call such coordinates degenerate). We advocate that it is reasonable to reconsider the conventional definition of singularity based on the usual Hessian and, moreover, to simplify the conventional hamiltonization procedure. In particular, in such a procedure, it is not necessary to complete the degenerate coordinates with the corresponding conjugate momenta.     

Aminomethylation of 1-R-Tetrazoles

The reaction of tetrazole and a series of its 1-substituted derivatives with formaldehyde and alkylamines under mild conditions results in aminomethylation of the heterocyclic ring at the carbon atom with the formation of the corresponding Mannich bases. It was found that strong acids (HCl and CF₃COOH) have an activating action during the process. An ylide mechanism of the reaction was proposed from the data obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 66–71, January, 1991.     

Method of fictitious regions for one class of fourth-order quasilinear elliptical equations

We investigate the application of the fictitious region method to fourth-order quasilinear elliptical equations with Dirichlet and Neumann conditions. Convergence bounds are established for two versions of the fictitious region method.Translated from Vychislitel'naya i Prikladnaya Matematika, No. 56, pp. 21–29, 1985     

Chaotic oscillations and noise transformations in a simple dissipative system with delayed feedback

We analyze the statistical behavior of signals in nonlinear circuits with delayed feedback in the presence of external Markovian noise. For the special class of circuits with intense phase mixing we develop an approach for the computation of the probability distributions and multitime correlation functions based on the random phase approximation. Both Gaussian and Kubo-Andersen models of external noise statistics are analyzed and the existence of the stationary (asymptotic) random process in the long-time limit is shown. We demonstrate that a nonlinear system with chaotic behavior becomes a noise amplifier with specific statistical transformation properties.     

Reaction of furan compounds with hydrogen peroxide in the presence of vanadium catalysts

The reactions of furan and a number of its derivatives (furfural, furan-2-carboxylic acid, 2-furfuryl alcohol, and others), in systems containing H₂O₂ and vanadium compounds, proceed through a mechanism of radical hydoxylation of the furan ring with the formation of 5-hydroxy-2(5H)-furanone and maleic acid. The total yield and ratio of the synthesized compounds depend on the reaction conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1462–1467, November, 1991.     

Method of homogeneous solutions under non-smooth loads

We consider a two-dimensional problem concerned with static deformation of an elastic halfstrip under the action of a self-equilibrated load at its end. A method is proposed for regularization of series over homogeneous solutions in the case of non-smooth prescribed loads. An example is given of a load for which divergence obtains for a series over homogeneous solutions for the stress field at the end of the halfstrip.Translated from Teoreticheskaya i Prikladnaya Mekhanika, No. 19, pp. 111–116, 1988.     

Fluorescent spectroscopy of 3-aminophthalimide molecules cooled in an ultrasonic jet

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 50, No. 3, pp. 385–391, March, 1989.