Patterned and controlled polyelectrolyte fractal growth and aggregations

Two-dimensional patterned and controlled polyelectrolyte aggregations (e.g., tree-like ramified structures) created by microcontact printing have been demonstrated and discussed. Polyelectrolyte-micropatterned aggregations on surfaces were controlled by the micropattern size and shape of PDMS stamps. The formation of aggregates was dependent on the ink and surface conditions, and the aggregates consisted of two distinct layers; strongly adsorbed, primary uniform layers and weakly adsorbed, secondary aggregation layers positioned on top of the primary layers. The adsorption of the primary layers was strong enough not to be washed away, while the aggregated secondary layers were easily removed by washing. The aggregation of secondary layers showed typical tree-like ramified structures of fractal growth and aggregation. Directional and confined stamping led to directing and confining the growth of the fractal polyelectrolyte clusters, respectively. The micropatterned primary uniform layers were not removed by extensive washing, and they were identified by selective nickel plating and charged particle selective adsorption in which the surface formed positive and negative micropatterns. These functional and patterned surfaces have great potentials for advanced devices and sensors.     

Der massenspektrometrische Verlust von Vinylalkohol aus 1-Amino-3-aryloxy-2-propanolen. 24. Mitteilung über das massenspektrometrische Verhalten von Stickstoffverbindungen

Loss of vinyl alcohol from 1-amino-3-aryloxy-2-propanols under electron impact Under electron impact compounds of type 1 (see Scheme 1) split off 44 mass units from the molecular ion. This unusual reaction was studied using derivatives and deuterium labelled compounds. It could be demonstrated that for this fragmentation reaction 16 is the important structural feature from which H₂(C3)?C(2)HOH (44 mass units) is lost. The preferred reaction mechanism involves a transition state in which four members of the side chain are involved (Scheme 2, mechanism 2).     

Ein Dreikomponenten-Zweiphasensystem für die schnelle Flüssigkeits-Chromatographie

Zusammenfassung Für die Hochdruck-Flüssigkeits-Chromatographie wird ein Dreikomponenten-Zweiphasensystem beschrieben. Die Mischungslücke besteht zwischen dem wenig polaren Methylenchlorid und dem stark polaren Wasser und kann durch Zugabe von Äthanol als Lösungsvermittler geschlossen werden. Durch den Anteil der stark polaren Komponente in den jeweils koexistenten Phasen ist die Polarität von stationärer und mobiler Phase als stationäre gebunden und aus der mobilen immer wieder regeneriert. Durch Verteilungs-Chromatographie in der Mischungslücke ist eine Vielzahl von Stoffklassen der Trennung zugänglich, so z.B. Corticosteroide, Östrogene, Phenole, Phenolcarbonsäuren usw.

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A three-component two-phase system for high speed liquid chromatography

Summary High pressure liquid chromatography with a three-component two-phase system is described. For the less polar methylenechloride and the highly polar water a wide range of incomplete miscibility exists which can be decreased with ethanol. The water content of the coexistent phases determines the polarity of the stationary and the mobile phases. The more polar phase is adsorbed on silicagel as the column support material and serves as the stationary phase. Numerous compounds can be separated by partition chromatography between the coexistent phases, for instance; corticosteroids, estrogens, phenols, phenol-carboxylic acids and so on

     

Beitrag zur Massenspektrometrie substituierter α, ω-Alkandiamine. 29. Mitteilung über massenspektrometrische Untersuchungen

Contribution to the mass spectrometry of substituted α,ω-alkane diamines The main mass spectral fragmentation pattern of compounds of types 1 to 4 is discussed. After loss of C₆H₅ · CH₂ · from the molecular ion the acid correspondin to the N,N-disubstituted residue is splitted off. The mechanism of this fragmentation reaction depends on the member of CH₂-groups between the two nitrogen atoms (Schemes 1 and 3) and on the substitution pattern of both nitrogens (Scheme 2).     

Synthesis and characterization of new 1,1′-diester,diketone, and dinitrile derivatives of 2,2′-biimidazole

Substituted 1,1′-diester, diketone and dinitrile derivatives are prepared from 2,2′-biimidazole. The reactions involved include: Michael addition with halogenated olefins; nucleophilic substitution with ketones, nitriles, and esters; and condensation with amines.     

Sorellin und Hobartin,zwei neue Indolalkaloide aus Aristotelia peduncularis (LABILL.) HOOK. F. 173. Mitteilung über organische Naturstoffe

Sorelline and Hobartine, Two New Indole Alkaloids from Aristotelia peduncularis (LABILL .) HOOK . F. From Aristotelia peduncularis (LABILL .) HOOK . F. two new indole alkaloids, sorelline ( 1 ) and hobartine ( 2 ), have been isolated. Their structures were elucidated on the basis of spectroscopic data (the formulae represent their relative configurations). The alkaloids 1 and 2 have closely related structures with a monosubstituted indole moiety and an unrearranged monoterpene unit in the aliphatic part.     

Kopsirachin,ein ungewöhnliches Alkaloid aus der Apocynaceae Kopsia dasyrachis Ridl. 189. Mitteilung über organische Naturstoffe

Kopsirachine, an Unusual Alkaloid from the Apocynaceae Kopsia dasyrachis Ridl. From the leaves of Kopsia dasyrachis Ridl. a new type of alkaloid, kopsirachine ( 1 ), built up from catechin ( 2 ) and skytanthine ( 3 ) has been isolated. The structure elucidationis based on spectral and chemical evidence. Oxidative cleavage of its derivative 4 with KMnO₄ afforded veratric acid wich was identified as its methylester by comparison with an authentic sample. Pyrolysis of 1 yielded δ-skytanthine ( 3 ). The stereochemistry of the skytanthine substituents in 1 could not yet be established.     

Determination of oxidized and reduced glutathione, by capillary zone electrophoresis, in Brassica juncea plants treated with copper and cadmium

A rapid method of capillary zone electrophoresis is described to determine the oxidized (GSSG) and reduced (GSH) form of glutathione in plant tissue. In order to separate both analytes in a fused-silica capillary, the pH and composition of the electrolyte solution were optimized. The electrolyte composition was 100 mmol/L, borate 25 mmol/L Tris, and 0.2% w/v metaphosphoric acid (MPA), pH 8.2. Some instrumental conditions used to run the samples were hydrostatic injection for 30 s, 30 kV applied voltage, and UV detection (185 nm) at 25 degrees C. Linearity and useful range obtained for the calibration curves were optimum, with correlation coefficients about 0.999 in the 0-120 micromol/L range. The migration time was highly reproducible, less than 5 min being afforded to run a sample. Electrolyte buffer and samples required a careful pH control for optimal separation of both analytes. This aspect constitutes a critical analytical step when acids are used in the procedure for sample preparation. Simultaneous analysis of GSH and GSSG may provide a useful tool for comparative studies of plants in order to select those species with a potential capacity for detoxification from toxic elements or those appearing promising from phytoremediation for these elements.     

Molybdenum-phosphorus triple bond stabilization by ancillary alkoxide ligation: synthesis and structure of a terminal phosphide tris-1-methylcyclohexanoxide complex

Using alcoholysis, we converted terminal phosphide PMo(N[i-Pr]Ar)3 into a new, monomeric terminal phosphide PMo(OR)3, where R = 1-methylcyclohexyl or 1-adamantyl. Dimerization of the PMo unit was observed upon alcoholysis with 2,6-dimethylphenol, and the dimer [PMo(N[i-Pr]Ar)(O-2,6-C6H3Me2)2]2 was isolated and characterized by X-ray crystallography.