Alkaloids ofThalictrum isopyroides

Summary 6,7-Dimethoxy-2-methyl-1,2-dihydroisoquinolin-1-one and the new aporphine base 9-hydroxy-1,2,3,10-tetramethoxyaporphine, which has been called thalisopynine, have been isolated fromThalictrum for the first time.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnyk Soedinenii, No. 4, pp. 472–474, July–August, 1978.     

(PPh3Me)2[{MoCl4(NO)}2 (μ-S2N2)]; Synthese,IR-Spektrum und Kristallstruktur

(PPh₃Me)₂[{MoCl₄(NO)}₂(μ-S₂ N₂)]; Synthesis, I.R. Spectrum, and Crystal Structure The title compound is prepared by the reaction of (PPh₃Me)₂[MoCl₃(NO)₂]₂ with trithiazyl chloride in CH₂Cl₂ solution. It forms yellow, only slightly moisture sensitive crystals, which are characterized by their IR spectrum as well as by an X-ray structure determination. (PPh₃Me)₂[{MoCl₄(NO)}₂ (μ-S₂N₂)] crystallizes triclinic in the space group P1 with one formula unit in the unit cell (5952 independent, observed reflexions, R = 0.045). The lattice dimensions are at 20°C: a = 1021, b = 1143, c = 1243, pm; α = 64,15°, β = 68.24°, γ = 80.85°. The compound consists of PPh₃Me⊕ cations and anions [{MoCl₄(NO)}₂(μ-S₂N₂)]²?, in which the molybdenum atoms are bridged by the N-atoms of the planar S₂N₂ ring. In the trans-positions of these N-atoms the linear nitrosyl groups are coordinated via Mo ? N ? O .     

Absorption and fluorescence spectroscopy of rhodamine 6G in titanium dioxide nanocomposites

A comparison has been made between the spectroscopic properties of the laser dye rhodamine 6G (R6G) in mesostructured titanium dioxide (TiO(2)) and in ethanol. Steady-state excitation and emission techniques have been used to probe the dye-matrix interactions. We show that the TiO(2)-nanocomposite studied is a good host for R6G, as it allows high dye concentrations, while keeping dye molecules isolated, and preventing aggregation. Our findings have important implications in the context of solid state dye-lasers and microphotonic device applications.     

Molecular characteristics of the inhibition of human neutrophil elastase by nonsteroidal antiinflammatory drugs

Nonsteroidal antiinflammatory drugs(NSAIDs) are known as clinically effective agents for treatment of inflammatory diseases. Inhibition of cyclooxygenase has been thought to be a major facet of the pharmacological mechanism of NSAIDs. However, it is difficult to ascribe the antiinflammatory effects of NSAIDs solely to the inhibition of prostaglandin synthesis. Human neutrophil elastase (HNElastase; HNE, EC 3.4.21.37) has been known as a causative factor in inflammatory diseases. To investigate the specific relationship between HNElastase inhibition and specificity of molecular structure of several NSAIDs, HNElastase was purified by Ultrogel AcA54 gel filtration, CM-Sephadex ion exchange, and HPLC (with TSK 250 column) chromatography. HNElastase was inhibited by aspirin and salicylate in a competitive manner and by naproxen, ketoprofen, phenylbutazone, and oxyphenbutazone in a partial competative manner, but not by ibuprofen and tolmetin. HNElastase-phenylbutazone-complex showed strong Raman shifts at 200, 440, 1124, 1194, 1384, 1506, and 1768 cm(-1). The Raman bands 1194, 1384, and 1768 cm(-1) may represent evidences of the conformational change at -N=N-phi radical, pyrazol ring, and -C=O radical of the elastase-drug complex, respectively. Phenylbutazone might be bound to HNElastase by ionic and hydrophobic interaction, and masked the active site. Inhibition of HNElastase could be another mechanism of action of NSAIDs besides cyclooxygenase inhibition in the treatment of inflammatory diseases. Different inhibition characteristics of HNE-lastase by NSAIDs such as aspirin, phenylbutazone-like drugs and ineffective drugs could be important points for drawing the criteria for appropriate drugs in clinical application.     

Free-electron attachment to coronene and corannulene in the gas phase

Electron attachment to the polyaromatic hydrocarbons coronene and corannulene is studied in the electron energy range of about 0-14 eV using a high-resolution crossed electron-neutral beam setup. The major anions observed are the parent anions peaking at about 0 eV with cross sections of 3.8 x 10(-20) and 1 x 10(-19) m(2), respectively. The only fragment anions formed in coronene and corannulene are the dehydrogenated coronene and corannulene anions. Other anions observed in the negative mass spectra at about 0 eV can be ascribed to impurities of the sample. High-level quantum-mechanical studies are carried out for the determination of electron affinities, hydrogen binding energies, and structures of both molecules. The behavior of coronene and corannulene upon electron attachment is compared with that of other polyaromatic hydrocarbons studied previously.     

Selective liquid adsorption and structural properties of montmorillonite and its hexadecylpyridinium derivatives

Summary An X-ray diffraction method was used to study the structures of montmorillonites, the surfaces of which were covered to a systematically increasing extent with hexadecylpyridinium (HDP) cations. It was found that, depending on the degree of cover of the surface, the HDP cations form a mono- or bimolecular layer in the interlayer space. A detailed investigation was made of the selective sorption of binary mixtures on montmorillonite and on HDP-montmorillonites with different surface coverages. The adsorption excess isotherms were determined, as were the adsorption capacities from analysis of the isotherms, and also the equivalent specific surface areas.It was established that from benzene-n-heptane mixtures the benzene is adsorbed only on the external surface of montmorillonite, while in the case of organocomplexes it causes moderate disaggregation.From benzene, alcohols with different numbers of carbon atoms are also preferentially adsorbed on the internal surfaces of montmorillonite; with the rise in the number of carbon atoms, the extent of interlamellar adsorption decreases. In the case of HDP-montmorillonites in methanol-benzene mixtures, the adsorption capacity exhibits a monotonous increase with the degree of organopbility in the range under consideration. In the event of optimum organophility the disaggregation of the organocomplex is complete, and the equivalent specific surface area is 764-778 m² · g^–1. The swelling of the organocomplex, which can be characterized by X-ray diffraction measurement, is in close correlation with the interlamellar liquid adsorption. The results show modification of the surface of montmorillonite with HDP cations fundamentally determines the nature and extent of the selective liquid adsorption.

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Zusammenfassung Die Struktur von mit Hexadecyl-pyridinium(HDP)-Kationen im systematisch gesteigerten Maße bedeckten Montmorilloniten wurde mit der Röntgendiffraktions-Methode untersucht. Es wurde festgestellt, daß die HDP-Kationen, von der Bedeckung der Oberfläche abhängend, im Schichtzwischenraum eine mono- bzw. bimolekulare Schicht bilden. Die selektive Sorption binärer Gemische wurde an Montmorilloniten und an HDP-Montmorilloniten verschiedener Bedeckung eingehend untersucht. Es wurden die Adsorptionsisothermen von Flüssigkeitsgemischen und aus deren Analyse die Adsorptionskapazitäten und die äquivalenten spezifischen Oberflächen bestimmt.Es wurde festgestellt, daß aus Benzol-n-Heptan-Gemischen das Benzol nur an der äußeren Montmorillonite-Oberfläche adsorbiert wird, während es bei Organokomplexen eine mäßige Desaggregation verursacht. Die Adsorption von Alkoholen verschiedener Kohlenstoffzahl aus Benzol erscheint auch an inneren Montmorillonit-Oberflächen bevorzugt; mit zunehmender Kohlenstoffzahl nimmt das Ausmaß der interlamellaren Adsorption ab. Bei HDP-Montmorilloniten zeigt die Adsorptionskapazität aus Methanol-Benzol-Gemischen mit zunehmender Organophilität im untersuchten Gebiet eine monotone Steigerung. Im Falle optimaler Organophilität ist die Desaggregation vollständig, die äquivalente spezifische Oberfläche beträgt 764-778 m²/g. Die durch Röntgenn-diffraktionsmessung charakterisierbare Quellung des Organokomplexes steht mit der interlamellaren Flüssig-keitsadsorption in engern Zusammenhang. Unsere Ergebnisse zeigen, daß Charakter und Ausmaß der selektiven Flüssigkeitsadsorption durch die Modifizierung der Montmorillonit-Oberfläche mit HDP-Kationen grundlegend verändert wird.

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With 14 figures and 4 tables     

Synthesis of racemic and optically active Δ1- and Δ6-3,4-cis-tetrahydrocannabinols1

Three syntheses of the hitherto unknown (±)-Δ⁶-3,4-cis-THC 4a and the first total synthesis of optically active Δ¹- and Δ⁶-cis-THC's are described. These syntheses utilize a stereospecific intramolecular epoxide opening by phenolate anion; an acid catalyzed equilibration of Δ¹- and Δ⁶-cis-THC acetates; and a kinetically controlled dehydration. The use of HPLC, GLC and NMR for the separation and identification of closely related THC's is discussed.     

Chemistry of thienopyridines. VII. Mechanistic studies on the synthesis of thieno[2,3-c] pyridine by thermolytic cyclization

A study was made of the formation of thieno[2,3-c]pyridine (1) from hydrogen sulfide and 4-vinylpyridine in a flow system at 630°. 2-(4-Pyridyl)ethanethiol and bis-2-(4-pyridyl)ethyl sulfide were found to be likely intermediates. Based on these studies, there was devised a two-step practical preparative method for I (optimum overall yield 58%) which consists of preliminary conversion of 4-vinylpyridine to benzyl 2-(4-pyridyl)ethyl sulfide and subsequent thermolysis (at 605°) of this substance.     

Translational energy disposal in molecular collisions: The transfer of momentum constraint

A Franck—Condon type argument, which requires the least transfer of momenta to the nuclei during a collision is outlined and applied to the analysis of translational energy disposal and its dependence on the initial translational energy. Using the maximal entropy procedure of information theory we are able to proceed directly from the assumed (model) constraint to the product state distribution.