Thermodynamics of formation of nitrogen bases and d-ribose from mineral substances in light of the problem of origination of simplest elements of living matter

The paper represents a further development of our hydrate hypothesis of simplest living matter origination (SLMO) from inorganic and simplest organic mineral substances. It is supposed that the sources of SLMO are simplest aliphatic hydrocarbons, niters, and phosphates. Thermodynamic calculations demonstrating a principal possibility for simultaneous syntheses of different nitrogen bases, d-ribose, and desoxy-d-ribose from these source substances are presented. The most probable principal mechanism of SLMO and the principal conditions necessary for realization of the proposed chemism of SLMO in the framework of the proposed mechanism are considered. A principal means for testing the hypothesis is proposed.     

Tetrazoles. 31. Kinetics of the reaction of nitriles with alkylammonium azides. Formation of 5-substituted tetrazoles

5-Substituted tetrazoles are formed by the reaction of nitriles with mono-, di-, and trialkylammonium azides in aprotic dipolar solvents and alcohols. Tetraalkylammonium azides do not react with nitriles. The formation of 5-substituted tetrazoles occurs by a 1,3-dipolar cycloaddition mechanism. Electron-accepting substituents increase the reactivity of nitriles significantly while the structure of the alkylammonium azide and the solvent polarity have no significant effect on the reaction rate.For Communication 30 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1214–1217, September, 1992.     

Acid-Base Properties and Prototropic Tautomerism of Isomeric 1,2,4-Triazin-3- and -5-ones

The acidity and basicity constants of isomeric phenyl(aryl)-1,2,4-triazin-3- and -5-ones in aqueous solution were determined by spectrophotometry: pK _a = 7.3–6.2; pK _BH+= 0.1 to –2.2. 1,2,4-Triazin-3-ones are weaker bases than the corresponding 1,2,4-triazin-5-ones. According to the AM1 calculations, the most thermodynamically favorable tautomer in the gas phase is the oxo form: namely, 2H-tautomers of the neutral bases and 2,4-H,H ⁺-tautomers of the conjugate acids.     

Acylation of Amines with 5-Phenyltetrazol-2-ylacetyl Chloride

The acylation of primary and secondary amines by 5-phenyltetrazol-2-ylacetyl chloride leads to the corresponding tetrazolylacetamides irrespective of the nature of the substituent in the structure of the amine.     

Double exchange in polynuclear mixed-valence clusters. 2. Iron-sulfur proteins [Fe4S4]+ and [Fe4S4]3+

The energy states of tetrameric iron clusters with d⁶-d⁶-d⁶-d⁵ and d⁵-d⁵-d⁵-d⁶ electronic configurations, which form the metal frameworks of the [Fe₄S₄]⁺ and [Fe₄S₄]³⁺ iron-sulfur proteins, are calculated using a general approach. It is revealed that the structural distortions of these systems significantly affect the composition of the magnetic states. The effect of the isotropic Heisenberg exchange is considered. Valencia University, Spain. Bordeaux University, France. Moldova State University. Institute of Chemistry, Academy of Sciences, Moldova Republic. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 5, pp. 816–825, September–October, 1996. Translated by I. Izvekova     

Basicity of 2-phenyl-5-R-1,3,4-oxadiazoles

We have studied the basicity of 2-phenyl-5-R-1,3,4-oxadiazoles (R = H, Me, CH₂Ph, t-Bu, CH₂Cl, CCl₃, CF₃) in aqueous sulfuric acid solutions. These compounds are weak organic bases (pK_BH ⁺ is −1.8 to −5.2). The values of pK_BH ⁺ determined on the H₀ and X acidity function scales agree well with each other. The substituent at the 5 position has a substantial effect on the basicity of the 1,3,4-oxadiazole ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 748–756, May, 2006.     

Basicity of Phenyl‐ and Methyl‐Substituted 1,2,4‐Oxadiazoles

The basicity of a series of 3,5‐disubstituted 1,2,4‐oxadiazoles in aqueous H₂SO₄ was examined by means of UV and ¹H‐NMR spectroscopy. The experimental data were analyzed by the modified Yates–McClelland method to yield the following pK values: 3,5‐dimethyl‐1,2,4‐oxadiazole, −1.66±0.06; 3‐methyl‐5‐phenyl‐1,2,4‐oxadiazole, −2.61±0.02; 3‐phenyl‐5‐methyl‐1,2,4‐oxadiazole, −2.95±0.01; 3,5‐diphenyl‐1,2,4‐oxadiazole, −3.55±0.06. A pK value of ca. −3.7 was estimated for the parent unsubstituted 1,2,4‐oxadiazole based on substituents' additivity increments. Possible protonation sites of the compounds were discussed in terms of both experimental data and theoretical calculations (HF/6‐31G**). Generally, protonation is most likely to occur at N(4) of the 1,2,4‐oxadiazole ring. However, concurrent formation of both N(4)‐ and N(2)‐protonated species in comparable amounts is possible in the case of 3‐phenyl‐1,2,4‐oxadiazoles.     

Double exchange in polynuclear mixed-valence clusters. 1. General solution of the electronic problem

The problem of calculating the electronic energy spectra of mixed-valence clusters with one “extra” electron (dⁿ-dⁿ...dⁿ⁺¹) or hole (dⁿ⁺¹-dⁿ⁺¹...dⁿ) delocalized in the paramagnetic cores of transition metals is solved. Unlike the available particular solutions, which are restricted to small numbers of ions and electrons, the solution proposed in this work is general and is suitable for many-electron systems of arbitrary numbers of nuclei and arbitrary symmetries. The new microscopic approach to the double exchange problem is based on the combination of the sequential (“chain”) scheme of spin coupling and angular momentum method. In terms of this approach, an analytical dependence of the matrix elements of the double exchange, Heisenberg exchange, and vibronic interaction on all spin quantum numbers is obtained. The final equations contain only the 6j symbols and are free of the higher-order nj symbols, which obstructed the solution of the double exchange problem in previous works. Valencia University, Spain. Bordeaux University, France. Moldova State University. Institute of Chemistry, Academy of Sciences, Moldova Republic. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 5, pp. 805–815, September–October, 1996. Translated by I. Izvekova     

Phase-locking effects in a system of nonlinear oscillators

Models for the excitation of collective modes in a system of nonlinear classical oscillators, initially out of phase, are discussed. The oscillators may be coupled in a dissipative or conservative manner. The analysis is based on the results of recent studies dealing with the problem of the free excitation of a coherent pulse, analogous to "superradiance" in two-level quantum systems. Several physical examples from the realms of electrodynamics and acoustics are discussed. The processes discussed here may be thought of as chaos-order transitions, provided that "chaos" is understood not as a stochastic nature of an individual oscillator but as the absence of a coherent component in their collective field.     

Electromagnetic waves in thin-film superconducting lines

Conclusions The distinctive features discussed about the propagation of electromagnetic waves in a structure containing a thin-film superconducting line are associated with the fact that the screening properties of the superconducting layer are determined by the distribution of superconducting currents in it. In the quasistatic case under discussion this distribution depends on the nature of the nonuniformity of the magnetic field along the normal to the layer. At specified angles of incidence of a wave the layer is equivalent to an ideal conductor or a diamagnetic; in the intermediate region the screening effect is far smaller. Due to this a thin-film superconducting line possesses some directionality of the leakage of the nonuniform waves when ₁ > ₂. The wave which is emergent at a specified angle which depends on the parameters of the layered structure (₁, ₂,l, _L) possesses the maximum amplitude.When ₁ < ₂, the structure in question does not have a sharply pronounced directionality of the leakage, and at angles of incidence on a thin layer corresponding to total internal reflection it supports the propagation of waves along a line with as small a film thickness as desired. The unscreening effect of a superconducting layer is exhibited here in the fact that the propagation of waves excited in the line occurs at specified angles of incidence onto the layer mainly along its outer surface.Institute of Applied Physics, Academy of Sciences of the USSR. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Vol. 25, No. 5, pp. 527–535, May, 1982.