Kinetic Model of the Decomposition of Sodium Hydroxymethanesulfinate in Aqueous Solution

A kinetic model of the decomposition of sodium hydroxymethanesulfinate (rongalite) in aqueous solution at an initial value of pH 7.9 was considered. This multistep reaction was found to include oxidation decomposition in a solution surface layer and bulk reactions both with and without the participation of oxygen. To evaluate the parameters of this model, it was modified over three time intervals. The adequacy of this model to experimental data supported the hypothesis on the catalytic effect of active sulfur in the decomposition of rongalite.     

Structural equilibrium (S=0) ⇄ (S=1)and inversion of the configuration of the seven-membered saturated metal-containing ring in four-coordinate pyrazolealdiminate metal chelates of nickel(II) based on tetradentate ligands

¹H and¹³C NMR, x-ray structural analysis, and magnetic moment measurements have shown that in 5-thio(seleno)pyrazolealdiminate complexes of nickel(II) based on tetradentate ligands containing the fragment, with n=2, flattening of the chelate unit takes place in solution and in the solid state. A similar structure in which the diamine metal-containing ring has the twist-chair conformation is observed for the crystals of the complexes with n=4. For the complexes with n=4 in solution at a temperature below –50°C, rapid (on the NMR time scale) interconversion of the flattened (P) (S=0) and pseudotetrahedral (T) (S=1) structures is observed, not accompanied by inversion of the tetrahedral configuration of the metal atom. At temperatures above –50°C, in addition to the low-barrier reactions (T) (P), conversion of the seven-membered saturated metal-containing ring and inversion of the tetrahedral configuration of the Ni atom with activation barriers of 48–51 kJ/mole are observed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 327–335, February, 1990.     

Phototropism: a "simple" physiological response modulated by multiple interacting photosensory-response pathways

Phototropism is the process by which plants reorient growth of various organs, most notably stems, in response to lateral differences in light quantity and/or quality. The ubiquitous nature of the phototropic response in the plant kingdom implies that it provides some adaptive evolutionary advantage. Upon visual inspection it is tempting to surmise that phototropic curvatures result from a relatively simple growth response to a directional stimulus. However, detailed photophysiological, and more recently genetic and molecular, studies have demonstrated that phototropism is in fact regulated by complex interactions among several photosensory systems. At least two receptors, phototropin and a presently unidentified receptor, appear to mediate the primary photoreception of directional blue light cues in dark-grown plants. PhyB may also function as a primary receptor to detect lateral increases in far-red light in neighbor-avoidance responses of light-grown plants. Phytochromes (phyA and phyB at a minimum) also appear to function as secondary receptors to regulate adaptation processes that ultimately modulate the magnitude of curvature induced by primary photoperception. As a result of the interactions of these multiple photosensory systems plants are able to maximize the adaptive advantage of the phototropic response in ever changing light environments.     

The kinetics of radical polymerization—XXVII. Investigation of the radical reactivity of 3,3′- and 4,4′-disubstituted azobenzenes in the polymerization of vinylacetate

A study was made on the inhibition by some 3,3′- and 4,4′-disubstituted azobenzenes of the polymerization of vinylacetate initiated by azoisobutyronitrile at 50°. The inhibitory effects of these substances can be attributed to their ability to engage in radical addition giving a less reactive hydrazyl type radical. The mechanism of the inhibition has been established by ESR and kinetic (stoichiometric) measurements. The value of k₅/k₂ (characteristic of the reactivity of an inhibitor) was determined for 9 substituents. The radical reactivity of the aromatic azo group was decreased by electron donor substituents and increased by electron acceptors. The substituent effect can be well interpreted by the Hammett equation; the value of the reaction constant was ? = +0.53.     

Fluorinated dioxolanes. 3. Nucleophilic reactions of perfluoro-4-methyl-1,3-dioxolanes

Conclusions Perfluoro-2,4-dimethyl-2-fluorocarbonyl-1,3-dioxolane reacts with sodium carbonate to give perfluoro-2-methylene-2-methyl-1,3-dioxolane. Under the reaction conditions, the latter dimerizes to perfluoro-2-(2,4-dimethyl-1,3-dioxolan-2-ylmethylene)-4-methyl-1,3-dioxolane, and on treatment with CsF is converted into perfluoromethyl-(1,3-dioxolany-2-yl)ketone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 938–942, April, 1989.     

Composition of lipids of the grain of opaque-2 maize

It has been established that the change in the composition of the total lipids and the fall in the fatty acid content depend on the initial maize genotype. A decrease in the amount of unsaponifiable substances in the grain of mutants is accompanied by qualitative changes in the composition regardless of the nature of the genotype.Scientific-Research Institute of Biology Dnepropetrovsk State university. Translated from Khimiya Prirodnykh Soedinenii. No. 3. pp. 360–363. May–June, 1988.     

The mass spectra of 1,1,1-trichloro-2,4-pentanedione and its Al(III), Cr(III), Fe(III), Mn(II), Co(II) and Cu(II) complexes

The compounds 1,1,1-trichloro-2,4-pentanedione, Cu(II)tca₂, Co(II)tca₂, Mn(II)tca₂, Al(III)tca₃, Cr(III)tca₃ and Fe(III)tca₃ (tca?1,1,1-trichloro-2,4-pentanedionato, [CCl₃COCHCOCH₃]^?) have been prepared and their mass spectra have been obtained. The mass spectral results have been compared with findings for comparable fluorinated and nonhalogenated compounds. Comparisons are made in terms of internal redox reactions and hard and soft acid base theory. Rearrangement of chloride from ligand to metal accompanied by the elimination of CO or other neutral even electron fragments emerges as an important reaction for the ions of these compounds. While the internal redox reactions characteristic of all previous β-diketonate complex mass spectra still occur, their importance appears reduced to some degree by the facility of the chlorine rearrangement.     

Chemistry of heteroanalogs of isoflavones

Condensation of 2-pyridylacetonitrile with polyphenols gave the corresponding -(2-pyridyl)-acetophenones, which were converted to the pyridine analogs of natural isoflavones and to 3-pyridylchromones with methyl, trifluoromethyl, and ethoxycarbonyl groups in the 2 position. The antimicrobial activity of 3-pyridylchromones and their reaction with alkylating and acylating agents and phosphorus pentasulfide were investigated.See [1] for communication V.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1180–1185, September, 1977.     

Chemische Vitamin D<Subscript>3</Subscript>-Bestimmung in Lebertran

The different aspects of Vitamin D₃ determination and the data reported in the literature are discussed. The spectrophotometric determination of Vitamin D₃ in cod-liver oil is carried out after the alkaline saponification, extraction of unsaponified parts, precipitation of accompanying sterols and the column- and thin-layer chromatographic purification and separation of vitamin D₃ on 40 cm plates from other vitamins. The dyestuff α-naphtholbenzein is suited well as standard substance for the better location and identification of vitamin D₃ zone on the thin-layer plate. The results obtained from the chemical method were checked through the simultaneous biological determination.