Nonalkaloid Constituents from Stemona japonica

Five new nonalkaloid constituents, a neolignan, japonin A ( 1 ), a macrocyclic lactone, japonin B ( 2 ), a (phenylethyl)benzoquinone, japonin C ( 3 ), a phenanthraquinone, japonin D ( 4 ), as well as a dihydrostilbene, stilbostemin M ( 5 ), were isolated from the roots of Stemona japonica, together with eight known compounds. Their structures were established by spectroscopic analyses.     

Bis[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(perchlorato‐κO)copper(II) bis­[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(methanol‐κO)copper(II) bis­(perchlorate) methanol disolvate

The title compound, [Cu(ClO₄)₂(C₄H₉N₃O₂)₂][Cu(C₄H₉N₃O₂)₂(CH₄O)₂](ClO₄)₂·2CH₃OH, comprises two independent Cu^II species lying on different inversion sites. In the Cu complexes, a distorted octa­hedral geometry arises (from basic square‐planar N₄ coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol mol­ecules in the other (also as Cu—O). Inter­actions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive inter­molecular hydrogen‐bonding network.     

Two salts of 5‐sulfosalicylic acid and 3‐aminopyridine

5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C₅H₇N₂⁺·C₇H₅O₆S⁻·H₂O or 3‐APy·5‐SSA·H₂O, (I), and the anhydrous adduct, C₅H₇N₂⁺·C₇H₅O₆S⁻ or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively.     

Analysis and toxicity of methomyl and ametryn after biodegradation

The controlled biodegradation of ametryn and methomyl has been performed, in accordance with the OECD Zahn-Wellens/EMPA procedure, by use of an enriched mixture of activated sludge collected from three domestic waste-water-treatment plants (WWTP). During the process concentrations of ametryn and methomyl in the water samples were isolated by solid-phase extraction (SPE); recovery rates were 98.9 and 93.2 for methomyl and ametryn, respectively. Liquid chromatography-mass spectrometry (LC-MS) was used to determine final pesticide concentrations and for metabolite identification.The efficiency of aerobic biodegradation of ametryn and methomyl was evaluated by measuring both the decrease in the concentration of the pesticides and global properties such as the chemical oxygen demand (COD). The acute toxicity of ametryn and methomyl was evaluated by use of the ToxAlert100 biological test, which is based on inhibition of the bioluminescence of Vibrio fischeri. There was significant correlation between results from primary and ultimate biodegradation and those from determination of toxicity. Pesticide concentrations were always reduced to below the limit of detection in less than 17 days. High COD removal (90-96%) was achieved in 28 and 18 days for methomyl and ametryn, respectively.     

Crystallization kinetic studies: A means to evaluate time-temperature-transformation curves. Application to metallic glasses

It is shown that the study of the kinetics of crystallization of an amorphous alloy may be used to obtain the correct form of the low temperature part of the time-temperature-transformation (T-T-T) curves. A unified review of the current kinetics of crystallization studies is presented and the general kinetic equation which gives the reaction rate as a function of temperature and crystalline fraction is shown to contain information related to theT-T-T-curves. Finally examples of application to two metallic glasses, Nd₃Fe₇₇B₂₀ and Fe_67.5Co₁₅Nb_1.5B₁₆, obtained by rapid solidification techniques are presented. The comparison between theory and experiment is satisfactory.

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Zusammenfassung Es wird gezeigt, daß die Untersuchung der Kristallisationskinetik von amorphen Legierungen genutzt werden kann, die korrekte Form des Niedertemperaturbereiches der Zeit-Temperatur-Transformation (T-T-T) Kurven zu erhalten. Es wird ein einheitlicher Überblick über die jüngsten Untersuchungen von Kristallisationskinetiken gegeben und an der allgemeinen Gleichung der Reaktionsgeschwindigkeit als eine Funktion von Temperatur und Kristallanteil wird gezeigt, daß sie Informationen bezüglich der T-T-T-Kurven beinhaltet. Letztlich wird eine Anwendung an zwei, durch schnelles Erstarren gewonnenen metallischen Gläsern Nd₃Fe₇₇B₂₀ und Fe_67.5Co₁₅Nb_1.5B₁₆ dargelegt. Zwischen Theorie und Praxis konnte eine ausreichende Übereinstimmung festgestellt werden.

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Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60^th birthday

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This work was supported by the Comision Interdepartamental de Cienca y Tecnologia, CICYT (project No. MAT88-0439) which are acknowledged.     

Structural and dynamical properties of transition metal clusters

Results of molecular dynamics simulation studies of structural and dynamical properties of 12-, 13-, and 14-atom transition metal clusters are presented. The calculations are carried out using a Gupta-like potential expressed in reduced units. The transformation to absolute units involves two size-dependent parameters which effectively convert the potential into a size-dependent one. The minimum energy geometries of the clusters are obtained through the technique of simulated thermal quenching. A melting-like transition is observed as the energy of the clusters is increased. A novel element of the transition is that it may involve a premelting state.     

Thermodynamic studies of complexation and enantiorecognition processes of monoterpenoids by alpha- and beta-cyclodextrin in gas chromatography

Gas-liquid chromatography was applied in thermodynamic investigations of processes of complexation and enantioseparation by alpha- and [-cyclodextrins of chiral monoterpenoids. The distribution constants, stability constants and thermodynamic parameters enthalpy, entropy and free energy of the complexation processes were determined. It has been found that enantioseparation of monoterpenes by alpha- and beta-cyclodextrins is the result of formation of 1:2 stoichiometric complexes. When 1:1 stoichiometric complexes are formed, enantioselectivity is not observed. All investigated processes of complexation are enthalpy-driven regardless of the stoichiometry of the formed complexes. -deltaH, -TdeltaS and -deltaG of complexation process have higher values for bicyclic than for monocyclic monoterpenoids as well as for alpha-CD than for beta-CD. The first or second step of complexation may be responsible for enantioselectivity.     

Electrochemical Synthesis and Characterization of Nickel(II) Complexes with N‐2‐Pyridyl‐sulfonamide Ligands

Heteroleptic nickel(II) complexes [NiL₂L′] of a series of monoanionic and potentially bidentate N‐2‐pyridyl‐sulfonamide ligands [HL] and 2,2′‐bipyridine or 1,10‐Phenanthroline (L′) have been prepared by electrochemical oxidation of a nickel anode in an acetonitrile solution of the ligands. The complexes have been characterized by microanalysis, IR and electronic spectroscopy, magnetic measurements and LSI mass spectrometry. The crystal structure of [Ni(Ms6mepy)₂(bipy)] has been determined by x‐ray diffraction and shows the metal in an octahedral NiN₆ environment. Octahedral structures are also proposed for the other complexes with the N‐2‐pyridyl‐sulfonamide ligands acting as N,N′ or N, O bidentate systems, depending on the position of the methyl substituent on the pyridine ring.