Ultrasound synthesis of diaryl ethers

Russian Chemical Bulletin - 2,2-Bis[4-(4-nitroaryl)phenyl]hexafluoropropanes appropriate for the synthesis of monomers were prepared by the reaction of 2,2-bis[4-hydroxyphenyl)hexafluoropropane...     

Kinetic features of ammonium persulfate decomposition in aqueous medium

Russian Chemical Bulletin - Decomposition of ammonium persulfate in an aqueous medium (353–368 K) is limited by decomposition of persulfate ions with a rate constant logk 2 =...     

Diphenyl[(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadienylidene)-methyl]phosphonate in reactions with o-phenylenediamine

Russian Journal of General Chemistry -     

Metals in surface water of Ukraine: the migration forms,features of distribution between the abiotic components of aquatic ecosystems,and potential bioavailability

We have generalized the results of long-term studies of coexisting forms of a series of metals (Al, Fe, Mn, Zn, Cu, Cr, Pb, Mo, Cd, and V) in surface water bodies of Ukraine, differing in the hydrological regime and the water chemical composition (rivers, reservoirs, lakes, and ponds). The studied metals content has ranged widely, the concentrations of aluminum, iron, and manganese being typically the highest, and the concentration of molybdenum, vanadium, and cadmium being typically the lowest. The ratio between the suspended and the dissolved forms of the metals has been established. Iron and aluminum migrate mostly as part of the suspended matter, whereas the other metals mainly migrate in the dissolved state. The dissolved manganese form predominates in the water bodies under anaerobic conditions. Copper and molybdenum are present almost always in the dissolved state, regardless of the water body type. The data on the relative content of the labile metal fraction (potentially toxic to aquatic organisms) are reported. The relatively low content of this fraction has been found to be majorly owing to the metal ions complexing with natural organic ligands. The humic compounds, the most widespread group of natural organic compounds, play the primary role in the complexation. Even metals with variable oxidation state (Cr, Mo, and V) are found mainly in the form of anionic complexes with the humic substances. Carbohydrates are also involved in the metals binding in the highly bioproductive water bodies, thus increasing the mass fraction of the neutral complexes during the summer and autumn periods. The molecular weight distribution of anionic metal complexes has been discussed; the substantial part of the metals constitutes the compounds with the molecular weight of below 5.0 kDa.     

Synthesis and photochemical properties of 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-9<Emphasis Type="Italic">H</Emphasis>-carbazole derivatives

Method of synthesis has been developed for a series of 3,6-di-tert-butyl-9H-carbazole derivatives and their photochemical properties have been investigated. The dependence of the Steglich esterification reaction on the nature of the catalyst was studied. The synthesized compounds show fluorescent emission in the range 400–600 nm with a high quantum yield.     

Lead,cadmium, and arsenic in commercial algae of the Sea of Japan

The concentrations of toxic elements (arsenic, cadmium, lead) in commercial algae Saccharina japonica and Ahnfeltia tobuchiensis from different habitats of the Sea of Japan have been determined. Bioaccumulation of heavy metals has been analyzed with respect to the habitat and growth conditions. The lead content of Sascharina japonica from all habitats and arsenic content of the same alga species from the Ol’ga Bay, Kievka Bay, and Tatar Strait have been found to exceed maximum permissible levels. Increased lead concentrations have been detected in Ahnfeltia tobuchiensis. Samples of Ahnfeltia tobuchiensis collected from the bottom layer contain more toxic elements than those from the upper layer.     

Reaction of 1-germatranol hydrate with carboxylic acids

Reaction of 1-germatranol hydrate with carboxylic acids RCOOH (R = ClCH₂, PhCH=CH, Ph, 2-FC₆H₄, 3-BrC₆H₄, 3-HOC₆H₄, 3-EtOC₆H₄) in protic (CH₃OH, iso-C₅H₁₁OH) and aprotic polar solvent (CH₃CN) is studied. 1-Acyloxygermatranes RC(O)OGe(OCH{in2}CH{in2}){in3}N are formed in yields from 11 to ~100 % depending on the nature of the acid, solvent, duration of the process and the method of its completion. The reaction is the most effective in acetonitrile. Its topochemical completion (heating of the reaction residue in a vacuum) increases the yield of 1-acyloxygermatranes.     

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.