Der Einfluß von Grenzflächenerscheinungen auf den Stoffübergang und die Prozeßführung in Gegenstromkolonnen mit überkritischem CO2

Zusammenfassung Mittels des Einsatzes einer Hochdrucksichtzelle wurden Eigenschaften der Kontaktbereiche in Trennverfahren mit unterschiedlichen wäßrigen Lösungen und CO₂ unter hohen Drücken untersucht. Die Methode des hängenden Tropfens wurde zur Messung der Grenzflächenspannung bis zu Drücken von 280 bar angewandt. Der mit dem Druck abnehmende Verlauf weist nach der Gibbs'schen Theorie auf die Anreicherung von CO₂ in der Phasengrenze. Weiterhin wurde die für Packungskolonnen bedeutsame Feststoffbenetzung in Abhängigkeit von Druck und Oberflächenbeschaffenheit des Feststoffes untersucht. Der die Feststoffbenetzung charakterisierende Kontaktwinkel wurde mittels der Methode der gekippten Platte vermessen und ergab eine schlechtere Benetzung bei höheren Drücken und glatten Stahloberflächen.

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The effect of interfacial phenomena on mass transport and performance of separations in countercurrent columns with supercritical CO₂

Interfacial phenomena affecting countercurrent separation processes have been studied in systems containing aqueous solutions and CO₂ at elevated pressures by means of a high pressure optical cell. The pendant drop method was applied in order to measure the interfacial tension up to 280 bar. The decreasing course as a function of the pressure is due to the adsorption of CO₂ at the interface according to Gibbs' law. Further, wetting characteristics have been investigated as they are of considerable importance to packed columns. Therefore, the contact angle was determined by the method of the tilting plate and came out to increase with pressure and smoothness of the solid surface, indicating the loss of wettability.

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Synthesis of some 4-substituted-2-(o-halogenophenyl)-1,2,3-triazoles

Mesoaldehyde 1,3-dioxime was treated with either 2,4,6-trichlorophenyl- (a), o-fluorophenyl- (b), or o-bromophenyl- (c) hydrazine to give the corresponding mesoaldehyde 1,3-dioxime-2-halogenophenylhydrazones (1a,b,c). The latter were O-acetylated with acetic anhydride, and cyclized to triazole 4-oximes (3b, c) or triazole 4-O-acetyloximes ( 6a,b,c ) with cesium carbonate, then converted to nitriles ( 7a,b,c ) by refluxing with acetic anhydride followed by pyrolysis, or to aldehydes ( 4a,b,c ) by hydrolysis. The nitriles ( 7a,b,c ) were also converted to acids ( 9a,b,c ), esters ( 10a,b,c ), amides ( 8a,c ), an alcohol (11a), and an amine ( 12a ). In addition, tetrazoles of two types were prepared. The first ( 13d,e ) were obtained from the acid chlorides by the action of 5-aminotetrazole, whereas the second ( 14f ) was produced from the respective nitrile by the action of ammonium azide.     

The effect of crown ethers on the alkylation of a cyclic β-keto ester

The effects of crown ethers (6 and 7) on the reactions of sodium (2a) and potassium enolates (2b) of 2-ethoxycarbonylcyclohexanone (1) with isopropyl iodide in dimethylsulfoxide and dimethoxyethane have been investigated. When the addition of crown ether promoted dissociation of ion pair 2 in either of the two solvents, the total rate of reaction (k_t) increased and the ratio of carbon- (3) to oxygen-alkylation (4 and 5) products decreased. The results are consistent with the involvement of both the ion pair and more dissociated species in alkylation and with greater reactivity for the latter.     

Enantioselective enzymes for organic synthesis created by directed evolution

A new concept for the creation of enzymes displaying improved enantioselectivity in a given reaction is described; it is based on "evolution in the test tube". Accordingly, proper molecular biological methods for random mutagenesis, gene expression, and high-throughput screening systems for the rapid assay of enantioselectivity are combined. Several rounds of mutagenesis and screening are generally necessary in order to create mutant enzymes that show high degrees of enantioselectivity, as in the case of the lipase-catalyzed hydrolytic kinetic resolution of a chiral ester in which the original enantioselectivity of 2 % ee (E = 1) increases to > 90% ee (E = 25).     

High performance liquid chromatographic determination of metoclopramide in plasma and urine and its application to biopharmaceutical investigations

An optimized HPLC method for the quantification of metoclopramide (MCP) in human plasma and urine is described. MCP and internal standard are extracted from alkalinized substrate into diethyl ether and back-extracted into dilute acid. The analytes are separated with a ternary mobile phase at cyanopropyl-silica and detected at 312 nm (UV detection). The lower limit of quantification is 0.5 ng/ml in plasma and 50 ng/ml in urine. Optimization of extraction, chromatography, and detection is discussed. The method is selective to numerous common drug substances with excellent accuracy and precision data. After validation, the method is applied to the samples of a pharmacokinetic study. Pharmacokinetic parameters indicate the need for a sophisticated method as tool for optimization of metoclopramide formulations.