Cyanide reaction with ninhydrin: elucidation of reaction and interference mechanisms.

A new sensitive spectrophotometric method has recently been developed for the trace determination of cyanide with ninhydrin. Cyanide ion was supposed to act as a specific base catalyst. Nevertheless, this paper demonstrates that the reported assay is based on a novel reaction of cyanide with 2,2-dihydroxy-1,3-indanedione, which affords purple or blue colored salts of 2-cyano-1,2,3-trihydroxy-2H indene. Hydrindantin is merely an intermediary of the reaction. The formation of a stable and isolable ninhydrin-cyanide compound has been confirmed by its preparation in crystalline form. Also, it is thoroughly characterized by elemental as well as MS, IR, UV/VIS and 1H NMR analyses. The Ruhemann's sequence of reactions of cyanide with ninhydrin has been reconsidered and an adequate mechanism of the reaction is proposed. As a consequence, the interference of oxidizers as well as copper, silver and mercury ions with the cyanide determination has been elucidated.     

Synthesis of the AI component of the red san jose scale sex pheromone

Conclusions The racemic form of the AI component of the red San Jose scale pheromone and its analog were synthesized on the basis of available citronellol and geraniol derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1143–1146, May, 1989.     

Distance-balanced graphs: Symmetry conditions

A graph X is said to be distance-balanced if for any edge uv of X, the number of vertices closer to u than to v is equal to the number of vertices closer to v than to u. A graph X is said to be strongly distance-balanced if for any edge uv of X and any integer k, the number of vertices at distance k from u and at distance k+1 from v is equal to the number of vertices at distance k+1 from u and at distance k from v. Exploring the connection between symmetry properties of graphs and the metric property of being (strongly) distance-balanced is the main theme of this article. That a vertex-transitive graph is necessarily strongly distance-balanced and thus also distance-balanced is an easy observation. With only a slight relaxation of the transitivity condition, the situation changes drastically: there are infinite families of semisymmetric graphs (that is, graphs which are edge-transitive, but not vertex-transitive) which are distance-balanced, but there are also infinite families of semisymmetric graphs which are not distance-balanced. Results on the distance-balanced property in product graphs prove helpful in obtaining these constructions. Finally, a complete classification of strongly distance-balanced graphs is given for the following infinite families of generalized Petersen graphs: GP(n,2), GP(5k+1,k), GP(3k±3,k), and GP(2k+2,k).     

On Cubic Graphs Admitting an Edge-Transitive Solvable Group

Using covering graph techniques, a structural result about connected cubic simple graphs admitting an edge-transitive solvable group of automorphisms is proved. This implies, among other, that every such graph can be obtained from either the 3-dipole Dip₃ or the complete graph K ₄, by a sequence of elementary-abelian covers. Another consequence of the main structural result is that the action of an arc-transitive solvable group on a connected cubic simple graph is at most 3-arc-transitive. As an application, a new infinite family of semisymmetric cubic graphs, arising as regular elementary abelian covering projections of K _3,3, is constructed.     

Differences in coating mechanism of structurally different aluminosilicates observed through the thermal analysis

Systematic modification of three structurally different minerals (zeolite, mica, and vermiculite) was carried out with the aim of determining the modification mechanism and exposing the hydrophobic surface that can be used as a sorbent for many organic compounds. Mechanism of modification with cationic surfactant depends strongly on the mineral type. In order to identify the influence of aluminosilicates structural differences on the modification process, adsorption experiments with organic matter and water vapor, supplemented with the DTA/TG analysis, were performed. The cation exchange capacity (CEC) value was 1454?>?560?>?28 meq kg^?1 for zeolite (clinoptilolite), vermiculite, and mica (muscovite), respectively. Despite its CEC value, vermiculite adsorbed three times the amount of organic matter than did clinoptilolite due to the porous structure of zeolite, which acted to limit the adsorption only on the external exchangeable cations. If the loading amount is equal to the CEC or the external cation exchange capacity for clinoptilolite (ECEC?≈?10% CEC), the monolayer will form while mineral surface will have hydrophobic character. Only one active center exists at the surface of the clinoptilolite that was identified by DTA curves with a sharp and defined peak around 300 °C and by the mass loss at the TG diagrams. Two significant and equal active centers were observed in vermiculite, one for the exchange of the surface cations and the other for the interlayer cations and H₂O molecules. Muscovite CEC is negligible, and due to the absence of any other functional groups, the modification of this mineral was impossible.     

Ordering Starlike Trees by the Totality of Their Spectral Moments

The k-th spectral moment M_k(G) of the adjacency matrix of a graph G represents the number of closed walks of length k in G. We study here the partial order ? of graphs, defined by G ? H if M_k(G) ≤ M_k(H) for all k ≥?0, and are interested in the question when is ? a linear order within a specified set of graphs? Our main result is that ? is a linear order on each set of starlike trees with constant number of vertices. Recall that a connected graph G is a starlike tree if it has a vertex u such that the components of G ? u are paths, called the branches of G. It turns out that the ? ordering of starlike trees with constant number of vertices coincides with the shortlex order of sorted sequence of their branch lengths.

     

Proton exit channels in bovine cytochrome c oxidase

Cytochrome c oxidase (CcO) is the terminal transmembrane enzyme of the respiratory electron transport chain in aerobic cells. It catalyzes the reduction of oxygen to water and utilizes the free energy of the reduction reaction for proton pumping, a process which results in a membrane electrochemical proton gradient. Although the structure of the enzyme has been solved for several organisms, the molecular mechanism of proton pumping and proton exit pathways remain unknown. In our previous work, the continuum electrostatic calculations were employed to evaluate the electrostatic potential, energies, and protonation state of bovine cytochrome c oxidase for different redox states of the enzyme. A possible mechanism of oxygen reduction and proton pumping via His291 was proposed. In this paper, using electrostatic calculations, we examine the proton exit pathways in the enzyme. By monitoring the changes of the protonation states, proton affinities, and energies of electrostatic interactions between the titratable groups in different redox states of CcO, we identified the clusters of strongly interacting residues. Using these data, we detected four possible proton exit points on the periplasmic side of the membrane (Lys171B/Asp173B, His24B/Asp25B, Asp51, and Asp300). We then were able to trace the proton exit pathways and to evaluate the energy profiles along the paths. On the basis of energetic considerations and the conservation of the residues in a protein sequence, the most likely exit pathway is one via the Lys171B/Asp173B site. The obtained results are fully consistent with our His291 model of proton pumping, and provide a rationale for the absence of proton leaking in CcO between the pumping strokes.     

Unions of dihedral groups

By the following simple formula (1) $$\forall x \exists y (x = xyy, y = xyx)$$ We characterize semigroups from the title. Considering a local property of their ?-classes we get bands and Boolean groups as extreme cases of semigroups with that property. We also provide a construction showing that ?-classes can be sufficiently complicated (at least as Abelian groups are). Then we permute right-hand sides of identities in (1) getting Boolean semigroups (x³=x) and so-called anti-inverse semigroups. Finally we show that Boolean semigroups are a proper subclass of the intersection of anti-inverse semigroups and unions of dihedral groups.     

Cationic polyelectrolytes. V. On macromolecular chain conformational state during amination reactions of CMPS

The macromolecular chain conformational state during the amination of chloromethylated polystyrene (CMPS) with two aliphatic amines, namely methyl(2-hydroxyethyl)amine (MHEA) and N,N-dimethyl(2-hydroxypropyl)amine (DM2HPA), has been studied. Viscosimetric and light scattering measurements were performed during reactions in binary solvent mixtures. The observed kinetic deviations have been related with the conformational transformations of the macromolecular chain.     

Investigation of ionic thermocurrents in SrCl2-K crystals

Ionic thermocurrents in SrCl₂-K crystals have been investigated for the first time. Two maxima of thermally stimulated depolarization currents have been detected at T=112°K and T=210–240°K. The low-temperature maximum with a reorientation energy =0.25 eV and a frequency factor _o=7.1·10⁹ Hz is due to relaxation of impurity-vacancy dipoles. Its intensity grows linearly with the concentration of the dopand. The high-temperature maximum is due to the space charge. Its activation energy =0.46 eV coincides with the migration energy of anion vacancies associated with the potassium ions.Translated from Izvestiya Vysshikh Zavedenii, Fizika, No. 9, pp. 80–83, September, 1982.