Structure of aconifine

The structure of the new alkaloid aconifine, which has been isolated from the tubers and epigeal part ofAconitum karakolicum Rapcs. has been established on the basis of the results of chemical transformations and spectral characteristics. Some features of the selective acetylation of aconitine and aconine have been elucidated. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 665–672, September–October, 1980.     

A CNDO/2 calculation of a rearrangement in cyclopentadienylsilane

The ground state geometry of cyclopentadienylsilane and the transition state geometry for SiH₃ group migration have been calculated by the CNDO technique, a semi-empirical version of the LCAO MO SCF approach.     

Liquid-liquid extraction in the absence of usual organic solvents: Application of two-phase aqueous systems based on a water-soluble polymer

Summary Capabilities of liquid-liquid extraction systems without organic solvents have been examined. Ternary poly(ethylene glycol)-inorganic salt-water systems have been proposed for extraction of complexes of metals with water-soluble organic reagents and inorganic ligands.Phase diagrams for such two-phase systems have been studied. The distribution of some inorganic ions and organic reagents in PEG 2000-ammonium sulphate systems has been examined at different pH values of the salt-phase. It is shown that the distribution coefficients are lower than unit for all the cations studied while reagents, containing aromatic rings, are extracted into the PEG-phase with distribution coefficients higher than one hundred. Conditions are reported which provide effective extraction of iron(III) in presence of several water-soluble photometric reagents. Extraction in the PEG 2000-ammonium sulphate-water system in presence of ammonium thiocyanate and sulphuric acid has been studied. Copper, zinc, cobalt, iron(III), indium, molybdenum(V) are extracted into the PEG-phase with high distribution coefficients.

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Flüssig-flüssig-Extraktion ohne übliche organische Lösungsmittel: Anwendung wäriger Zweiphasen-Systeme mit einem wasserlöslichen Polymerisat

Zusammenfassung Die Eignung von Flüssig-flüssig-Extraktions-Systemen ohne organisches Lösungsmittel wurde geprüft. Ternäre Systeme aus Polyethylenglykol-anorganischem Salz-Wasser wurden für die Extraktion von Metallkomplexen mit wasserlöslichen organischen Reagenzien und anorganischen Liganden vorgeschlagen.Die Phasendiagramme solcher Zwei-Phasen-Systeme wurden untersucht. Die Verteilung einiger anorganischer Ionen und organischer Reagenzien in Polyethylenglykol (PEG) 2000-Ammoniumsulfat-Systemen wurde bei verschiedenem pH der Salzphase geprüft. Dabei ergab sich, daß die Verteilungskoeffizienten für alle untersuchten Kationen geringer sind als eins, während Reagenzien, die einen aromatischen Ring enthalten, in die PEG-Phase mit Verteilungskoeffizienten über 100 extrahiert werden. Versuchsbedingungen für die wirkungsvolle Extraktion von Fe(III) in Gegenwart verschiedener wasserlöslicher photometrischer Reagenzien wurden angegeben. Die Extraktion mit PEG 2000-Ammoniumsulfat-Wasser in Gegenwart von Ammoniumrhodanid und Schwefelsäure wurde untersucht. Kupfer, Zink, Kobalt, Eisen (III), Indium und Molybdän werden mit hohem Verteilungskoeffizienten in die PEG-Phase extrahiert.

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The paper has been presented at the Fifth European Conference on Analytical Chemistry (Euroanalysis V), Cracow, August 26–31, 1984.     

Trennung,Identifizierung und Bestimmung von Bactericiden auf der Basis von halogenierten Aromaten mittels Gas-Chromatographie

The separation of a mixture of 22 bactericides has been achieved by gas chromatography on columns with silicone rubber W-982 as stationary phase with temperatures between 100° and 300°C. The unchanged compounds as well as their silylation products have been used. The latter are more conveniently used especially for the quantitative determination. To be able to calculate the retention indices after Kovats gas chromatography has been performed isothermally at 180°C for the more volatile compounds and at 250°C for all other bactericides.The retention indices obtained under these conditions are tabulated together with the limits of detection.     

Anomalies of the partition coefficient and properties of crystals in the region of low concentrations of an isomorphous admixture. 1. Unusual decomposition of solid solutions of the NaCl—CdCl2 system

Solid solutions NaCl—CdCl₂ were studied in an interval of CdCl₂ concentrations of 0.05—3 mol.% by Raman spectroscopy. The molecular form Na₂CdCl₄ decomposes: Na₂CdCl₄ 2Na⁺ + Cd²⁺ + 2Cl₂ ^– + 2e^–; 2Na + 2e^– 2Na⁰. Free sodium atoms form color centers of crystal (F centers) in the region of jumpwise changing the partition coefficient of CdCl₂ in NaCl (K jump).     

Crystal and molecular structures of 1,8-diacetyl-3-methyl-DL-allantoin

DL-Allantoin (I) has been isolated from an alcoholic extract of a marine spongeAxinellidae gen. sp., and derivatives of it have been obtained: 1, 8-diacetyl-DL-allantoin (II) and 1,8-diacetyl-3-methyl-DL-allantoin (III). The crystal and molecular structures of (III) have been established by X-ray structural analysis.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 422–426, May–June, 1988.     

Rethinking ramoplanin: the role of substrate binding in inhibition of peptidoglycan biosynthesis

Ramoplanin is a cyclicdepsipeptide antibiotic that inhibits peptidoglycan biosynthesis. It was proposed in 1990 to block the MurG step of peptidoglycan synthesis by binding to the substrate of MurG, Lipid I. The proposed mechanism of MurG inhibition has become widely accepted even though it was never directly tested. In this paper, we disprove the accepted mechanism for how ramoplanin functions, and we present an alternative mechanism. This work has implications for the design of ramoplanin derivatives and may influence how other proposed substrate binding antibiotics are studied.     

Electron Transfer through Monolayers of Mixed Long-chain Aliphatic Acids and Alcohols

Properties of monolayers of cetyl, stearyl, and eicosyl alcohols and stearic and behenic acids and their mixtures are studied, along with the kinetics of a redox reaction of hemin adsorbed on these monolayers. Three-dimensional computer models of corresponding monolayers are constructed and compared with their electrochemical behavior. Properties of monolayers of cetyl alcohol in acid and alkaline solutions and stearyl alcohol in acid solutions correspond to package of molecules in a stretched conformation oriented normally to the electrode surface; for the other one-component systems, the monolayer structure is less regular. The hemin redox reaction rate has no correlation whatsoever with the monolayer thickness and is defined by the length of the electron transfer path (over a chain of covalent bonds and through van der Waals contacts between molecules). The stronger the deviation of the conformation of molecules from the stretched one, the shorter the effective path of the electron transfer. In mixed films of stearic acid and cetyl alcohol (1 : 6), it is sometimes possible to keep molecules of stearic acid in a stretched conformation, thus inhibiting the electron transfer along the hydrocarbon chain of this molecule to a maximum extent. The other mixed systems, while making the conformation more stretched, fail to provide for a completely regular structure.     

Sc(OTf)3-catalyzed efficient synthesis of beta,beta-bis(indolyl) ketones by the double indolylation of acetic acid 2-methylene-3-oxobutyl ester

In the presence of 5 mol% Sc(OTf)3, double indolylation of acetic acid 2-methylene-3-oxo-butyl ester with differently substituted indoles readily afforded beta,beta-bis(indolyl) ketones. The reaction may proceed via a Sc(OTf)3-catalyzed SN2'-type substitution and subsequent conjugate addition.     

Structural Relationships between the Hemiporphyrazine Macrocyclic Ligand and its Metal Complexes. II.: Planar Neutral Ligand,C26H16N8, and Four Isomorphous Metal Complexes, [M(C26H16N8)(H2O)], M=Mn(II), Co(II), Cu(II), Zn(II)

Crystal and molecular structures of the planar neutral ligand, C₂₆H₁₆N₈, and the four isomorphous five-coordinated metal complexes, [M(C₂₆H₁₆N₈)(H₂O)], M = Mn(II), Co(II), Cu(II), Zn(II), have been determined from three-dimensional X-ray diffraction data. The free ligand hpH₂, C₂₆H₁₆N₈, belongs to the P 2₁/c space group with Z=2, a=4.142(3), b=23.736(6), c=10.338(3) Ä, β=94.66(6)°. The metal complexes monohydrate Mhp-H₂O all belong to the orthorhombic Pcab space group with Z=8. The dimensions are roughly 8.8×19.3×23.7 ų. In each structure, the macrocyclic ligand has an almost planar conformation which differs from the saddle shaped ligand hydrate (hpH₂·H₂O) and the nickel complex [Nihp]⁵. The distances from the center of the macrocyclic ring to the nitrogen atom of the free ligand are 1.907(6) and 2.245(6)Å. The coordination geometry in these four complexes is square pyramidal with a water molecule as an axial ligand. The bond distances of M(II)-O(H₂O), M(II)-N1 (imine), M(II)-N3 (pyridine) are: 2.19(1), 2.00(2), 2.27(2)Å respectively for the manganese complex; 2.08(1), 1.97(1), 2.23(1)Å for the cobalt complex; 2.33(1), 1.92(3), 2.18(1)Å for the copper complex; 2.110(5), 1.964(6), 2.252(6)Å for the zinc complex. The variation of metal-ligand distances can be correlated to the metal d orbital occupancy. A comparison with similar ligands will be presented.