l-Leucanthemit als Inhaltsstoff von Gymnospermae

Zusammenfassung Die Bildung und das Vorkommen von Cycliten inThuja occidentalis wurden mit Hilfe der Methode der Photoassimilation in einer Atmosphäre von¹⁴CO₂ untersucht. Nebenmyo-Inosit, Sequoyit,d-chiro-Inosit undd-Pinit wurde auchl-Leucanthemit (l-1,2,4/3-Cyclohexentetrol), ein Cyclit, der bisher nur als Inhaltsstoff mehrerer Angiospermae bekannt ist, nachgewiesen. Das Vorkommen vonl-Leucanthemit konnte auch inPinus austriaca sichergestellt werden. Methoden zur Isolierung vonl-Leucanthemit ausThuja occidentalis wurden ausgearbeitet.

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The formation and the occurrence of cyclitols inThuja occidentalis has been studied, using the method of photoassimilation in an atmosphere of¹⁴CO₂. Besidesmyo-inositol, sequoyitol,d-chiro-inositol, andd-pinitol, alsol-leucanthemitol (l-1,2,4/3-cyclohexentetrol), a cyclitol which so far has only been found in Angiospermae, was identified. The occurrence ofl-leucanthemitol could also be established inPinus austriaca. Methods have been elaborated which permit the isolation ofl-leucanthemitol fromThuja occidentalis.

     

Potassium addition to Fe/MgO, Ni/MgO and Ni/SiO2: Reducibility, dispersity and stabilization of the promoter by the support

The influence of potassium addition on the morphological properties of Fe/MgO and Ni/MgO has been investigated: KNO₃ addition to precursors results in a decrease of the reducibility and in a smaller dispersity of the metallic phase. A loss of potassium is observed at reduction temperatures in excess of 773 K. Silica-supported Ni behaves differently: silica inhibits the potassium volatilization and nickel reducibility is enhanced. This illustrates how promoter effects can be influenced by the nature of support.

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Fe/MgO Ni/MgO: KNO₃ . , 773 K. , : . .

     

Thermal investigations on the crystallization of sorbitol

The melting and crystallization of sorbitol were investigated with the DSC method and thermal microscopy. Sorbitol was found to have two crystalline modifications (confirmed by X-ray diffraction) with different melting points, while rapid cooling of molten sorbitol resulted in an amorphous form. The effect of inoculation on the crystallization of the melt was studied too. Powders of both crystalline modifications were used for this purpose. A new technological process for rapid crystallization of molten sorbitol has been worked out on the basis of the thermal analysis results.     

Quelques precisions sur les effets catalytiques des micelles cationiques hydroxylees

The alkaline hydrolysis of p-nitrophenyl acetate and of CH₃CO₂(CH₂)₂N⁺(CH₃)₂C₁₆H₃₃, Br^? was studied in the presence of micelles C₁₆H₃₃N⁺(CH₃)₂CH₂CH₂OH, Br^? and CTAB, C₁₆H₃₃N⁺(CH₃)₃,Br^?. A pathway involving an intermediate is suggested for the hydrolysis of the ester. Hydrolysis rate of the intermediate in the presence of micelles is the same as hydrolysis rate for the ester in the absence of micelles. Consequently, hydrolysis of p-nitrophenyl acetate is not catalysed by one type of micelle, while it is enhanced by another type of micelle.     

Complete thermodynamic analysis of the ionization of ortho-methoxybenzoic acid. Influence of the medium on the ortho effects

The ionization and solution enthalpies of o-methoxybenzoic acid have been measured in H₂O-DMSO mixtures. In the same solutions, the ΔG⁰ values for the ionization process have been determined by potentiometric measurements. A study of the ortho effects by means of a linear combination of the ordinary polar, proximity polar, and steric effects was also performed. The CH₃O group seems to undergo a partial steric inhibition of resonance. Finally, the proton transfer process from the ortho derivative to benzoic acid, compared with the same process in the gaseous phase, is presented.     

The biochemistry of cell-adhesion

The proposition is examined that adhesion between cells of animal tissues, and between cells and their extracellular matrix, is brought about by specific molecules present at cell-surfaces. Evidence is surveyed which has begun to emerge from the use of antibodies which inhibit or reverse adhesion. Putative cell-adhesion molecules in cellular slime-moulds and cells of chick and mouse embryos have been identified by their ability to neutralize the adhesion-inhibiting activity of monovalent fragments of polyspecific antibodies. In some instances antibodies have also been used to investigate the role of the cell-adhesion molecules in morphogenetic phenomena. A possible parallel is discussed between the effects of calcium ions on the cell-adhesion molecule uvomorulin from mouse blastomeres, and its effects on certain other cell-adhesion molecules.Although the role of fibronectin in promoting attachment and spreading of cells on artificial substrates and on denatured collagen is firmly established, there is little evidence that this glycoprotein is involved in direct intercellular adhesion. The observation that cells spread on adsorbed fibronectin, whereas binding of individual fibronectin molecules to cells is difficult to demonstrate may merely indicate that fibronectin is a relatively weak ligand for cell-surfaces. It is suggested that rather than being a necessary intermediate in the adhesion of cells to collagen, fibronectin may form matrix in its own right which shares with native collagen the ability to promote cell-attachment and spreading.The long-held view that cell-surface oligosaccharides act as receptors in cell-adhesion appears still to be largely unsubstantiated. However the poorly adhesive properties of cells from many different lines with glycosylation defects strongly suggest N-linked oligosaccharides of glycoproteins are involved in some way as yet not determined.     

Synthese neuer N-Vinylpyrrole

Syntheses of New N-Vinylpyrroles The reactions of pyrrolyl potassium ( 1 ) with (ethoxymethylene)malonic acid derivatives 2a–e yielded the carbanions 3a–e , which could be hydrolyzed to 4a–e , but with the exception of 4b they were not isolated, because a transformation to the N-vinylpyrroles 5a , c–e by elimination of ethanol took place; 1 reacted with 2b at 80°C to give 4b and 6 . Hydrolysis of 4b with KOH yielded 4g , which eliminated 1 mol of ethanol to form 5f , decarboxylation of which led to N-vinylpyrrole 7 . By cyclization of 5e under various conditions the pyrrolizines 8a , b are obtained, the hydrolysis of which did not give ketone 9 but only amino alcohol 10 . Some other cyclizations of 11a–c and 13 yielded the 3H-pyrrolizine derivatives 12a–c and 14 , respectively.     

Triterpene glycosides of Acanthophyllum gypsophiloides IV. The structure of acanthophyllosides B and C

Summary Alternative structures for the acyloside chain of acanthophylloside B and C have been established.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 728–734, November–December, 1975.     

Synthesis and properties of anthracene-containing polybenzyls

A number of alternating copolymers containing anthryl and aryl units in the polymer chain have been prepared by Friedel-Crafts arylation of the anthracene (polymer type B) or by condensation of 9,10-bis(chloromethyl) anthracene with opportune aromatic substrates (polymer type A). Polymers of type A were all found to contain 9,10-disubstituted anthracene units, but polymers of type B were found to contain 1,4-disubstituted anthracene units. Structure of the polymers were established through their NMR and ultraviolet spectra, and through analogy with appropriate model compounds. It has been found that the inclusion of anthracene units in the polymer chain yields higher melting and more soluble materials with respect to polybenzyls containing only aryl units. Anthracene units introduce, also, some interesting fluorescence characteristics in the polymers, which show intense emission at about 440 mμ.     

PHOTOREDUCTION OF ZINC PORPHIN BY ASCORBIC ACID*

Abstract— Zinc porphin is photoreduced to zinc chlorin through an intermediate dihydroporphin (PH₂) by ascorbic acid in ethanol containing 1% to 10% (v/v) piperidine. Under the same conditions zinc chlorin is more slowly photoreduced to zinc tetrahydroporphin. The reactions leading to chlorin are photosensitized by the product chlorin and so are autocatalytic in red light. Quantum yields for these reactions range up to 0.05.Other aliphatic amines catalyze these reactions, but at rates peculiar to the amine. The immediate product of reduction of zinc porphin, PH₂, is distinguished by an intense band at 437 nm; it reverts to porphin in the dark in the presence of oxygen or dehydroascorbic acid. Its conversion to chlorin is effected by light absorbed by porphin or chlorin, but not by light absorbed by PH₂ itself. A suggested structure for PH₂, compatible with the observed reactions, has added hydrogens on one bridge carbon and one β-pyrrole carbon. The possibility of an analogy between these reactions and the biochemical conversion of protochlorophyll to chlorophyll is discussed.