Temperature effect on the microstructure and viscoelastic properties of aqueous micellar systems of sodium <Emphasis Type="Italic">N</Emphasis>-methyl-<Emphasis Type="Italic">N</Emphasis>-oleyl taurate

The quantitative characteristics of the temperature effect on the rheological properties of aqueous solutions of the anionic surfactant sodium methyl oleyl taurate (SMOT) are presented. An increase in the intensity of thermal motion of surfactant molecules on heating from 25 to 45 °С was shown to decrease the average contour length of SMOT micelles from 2 μm to 700 nm. The decrease in the length of cylindrical micelles is probably one of the main reasons for a substantial decrease in the viscosity of micellar solutions of the surfactant with temperature.     

Enthalpies of the Diels–Alder reactions of a series of dienes with tetracyanoethylene and 4-phenyl-1,2,4-triazoline-3,5-dione

Russian Chemical Bulletin - The enthalpies of the Diels–Alder reactions of twenty dienes with two active dienophiles, tetracyanoethylene and 4-phenyl-1,2,4-triazoline-3,5-dione, are compared,...     

Advances in the synthesis of 7-(3-cyclopentyloxy-4-methoxyphenyl)-hexahydro-3<Emphasis Type="Italic">H</Emphasis>-pyrrolizin-3-one (Pyrromilast)–a promising agent for treatment of chronic obstructive pulmonary disease

The review summarizes the known approaches to diastereo- and enantioselective synthesis of 7-(3-cyclopentyloxy-4-methoxyphenyl)hexahydro-3H-pyrrolizin-3-one (Pyrromilast), a highly active inhibitor of subtype 4B phosphodiesterase and a promising agent for treatment of chronic obstructive pulmonary disease.     

Acetylenic derivatives of betulonic acid amide as a new type of compounds possessing spasmolytic activity

Efficient and versatile synthetic procedures towards novel derivatives of betulonic acid via Mannich reaction, Sonogashira cross-coupling, and copper(i)-catalyzed 1,3-dipolar cyclo-additions were developed. Introduction of secondary amines (Mannich reaction) into betulonic acid amides led to derivatives possessing marked spasmolytic activity, which is not characteristic of the triterpene fragment.     

Quantum chemistry of many-electron systems: high-priority aspects

The review generalizes the studies devoted to the development of a new quantum chemistry method representing an alternative to the Hartree–Fock approximation. Based on the hypothesis of prohibition of equipotential surfaces, which clarifies the physical sense of the Pauli exclusion principle, and taking account of the condition for antisymmetrical wave function of the triplet state (3S) of He atom, the Hartree–Fock approximation is inappropriate for a priori determination of the nodal surfaces of many-electron wave functions (MWFs) for the test systems traditionally used in quantum chemistry, namely, excited triplet state of H₂ molecule and the ground electronic states of Li atom and LiH molecule. The nodal surfaces of the wave functions corresponding to the minimum basis set of Slater orbitals in the Hartree–Fock approximation are constructed and analyzed. An alternative to the Hartree–Fock approximation is provided by the MWF quantum chemical method being developed by the authors. In the MWF method, the nodal surfaces for H₂(³Σ _u ^v ) and Li(²S) are specified a priori. Some aspects of geometric interpretation of the Pauli exclusion principle are discussed. Unlike the MWF method, the Hartree–Fock approximation is unsuitable for taking account of the dependence of the MWF nodal surfaces on the nuclear charges and on correlation effects related to the motion of electrons with antiparallel spins because such nodal surfaces are predefined by the mathematical properties of Slater determinants rather than by physically clear and more practically valuable algebraic products of electrostatic potential differences.     

Calculation of possible stabilization of glycosyl carbocations in furanosides by different theoretical methods

The paper deals with the comparison of different theoretical methods for the calculation of stabilization energies of glycosyl cations from fucofuranoside glycosyl donors containing different protecting groups at atom O(3). The experimental and calculated data on stereoselectivity of glycosylation were compared. The formation of the stabilized glycosyl cations is considered as one of the possible steps of glycosylation reaction, which exerts influence on the stereoselectivity of the process and makes it possible to obtain difficultly accessible 1,2-cis-glycosides. Semi-empirical and ab initio methods without allowance for the electron correlation underestimate the stabilization energy values. The allowance for the electron correlation in the MP2 approximation, as well as the calculations by density functional theory, allowed us to obtain the data corresponding to the experimentally observed stereoselectivity.     

Quantum chemical studies of azoles 4. A novel elimination–addition mechanism of tetrazole and 1,2,4-triazole electrophilic substitution

Thermodynamic parameters of the addition–elimination and elimination–addition electrophilic substitution reactions of 1H-tetrazole and 1,2,4-1H-triazole obtained from DFT B3LYP/ 6-31G(d,p) quantum chemical calculations with proton as model electrophile are compared. According to calculations, the elimination–addition reactions can proceed without preliminary formation of N-protonated azolium salts.