A semi-quantitative method for the determination of microgram amounts of manganese on millipore filters

A method is described in which the intensity of coloration of brown manganese dioxide on white Millipore filters is taken as the measure of the manganese content. A solution of manganese(II) is made strongly basic, whereupon manganese dioxide precipitates via its auto-oxidation. Optimum conditions for the precipitation are studied. Less than 0.5 μg of manganese can be determined.     

First lipase catalysed resolution of epoxy enol esters

We report the first enzyme-catalysed kinetic resolution of epoxy enol esters. The lipase-promoted hydrolysis of these compounds provided α-hydroxyketones or α-hydroxyaldehydes (arising from the spontaneous rearrangement of the epoxy enols) and the residual esters with moderate to good enantioselectivity (E up to 100).     

Novel heterocycles. 6. The condensation of ethyl o-fluorobenzoyl acetate with cyclic imino ethers

The reaction between ethyl o-fluorobenzoylacetate and cyclic imino ethers is described. The products, the corresponding 1,2-fused quinolines ( 13a-17a ), were isolated in good yields. In one instance the uncyclized condensation intermediate 18 was isolated and characterized.     

Mikronachweis der Salicylsäure als Silbersalicylat

Zusammenfassung Es wird eine Methode beschrieben, nach der die Salicylsäure über ihr Ammonsalz als Silbersalicylat in kleinsten Mengen nachgewiesen werden kann. Es bilden sich dabei monokline Prismen in Form von Rhomboiden, die durch die Kristallwinkel, die schiefe Auslöschung und deren Beziehung zum Kristallumriß als Silbersalicylat identifiziert werden können. Erfassungsgrenze: 0,4 Salicylsäure. Ferner wird das unter Umständen ebenfalls bei der Reaktion auftretende Silbersalz der Benzoesäure und seine Unterscheidung von Silbersalicylat auf optischem Wege besprochen. Die Reaktion gelingt auch mit Mikrosublimaten.

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Summary A method is described whereby minimal amounts of salicylic acid can be detected as silver salicylate, viâ the ammonium salt. Monoclinic prisms of the form of rhomboids are produced, which may be identified as silver salicylate from the crystal angles, the oblique extinction, and the relationship of these to the crystal outline. The limit of the method is 0,4 salicylic acid. The optical method for distinguishing between silver salicylate and silver benzoate, which is also formed in certain circumstances in the course of the reaction, is discussed. The reaction may be successfully applied to micro-sublimates.

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Résumé On décrit une méthode, qui permet de déceler des plus petites quantités de l'acide salicylique comme salicylate d'argent en préparant d'abord le salicylate d'ammonium. Des prismes monoclines, en forme rhombique, se forment d'abord, qui peuvent être identifiés comme salicylate d'argent par l'angle du cristal (Kristallwinkel), l'extinction oblique (schiefe Auslöschung) et les relations de ceux aux contoures du cristal (Kristallumriß). Limite d'identification: 0,4 d'acide salicylique. Ensuite on discute aussi la différence entre le salicylate d'argent et le benzoate d'argent, qui se forme parfois au cours de la réaction, d'un mode optique. — La réaction peut être appliquée aussi à des micro-sublimés.

     

The phenolic oxidation of a β-methylchalcone

The phenolic oxidation of 2',4-dihydroxy-4'-methoxy-β-methylchalcone using alkaline potassium ferricyanide gives an aurone rather than an isoflavone. This result is discussed in the context of current theories regarding the biosynthesis of flavonoid and isoflavonoid compounds.     

Mixed valence—Rydberg states

A survey of recent calculations involving the mixing of Rydberg and valence states in the spectra of molecular systems is undertaken. It is pointed out that when such states undergo curve crossings with one another, minimal energy splittings of 1.0–2.0 eV can occur at the respective 50-50 composition points. The significance of such large interactions between valence and low-lying Rydberg states is considered in terms of the properties of the resulting mixed CI states, particularly with reference to the oscillator strengths for the pertinent ground state transitions and also the spatial extension of the corresponding upper orbitals. It is thereupon argued that such mixings have important consequences in the spectra of a wide variety of systems, including those of O₂, ethylene and ethane.     

Synthesis of angiotensins,bradykinins and substance P octapeptides in which the residues Phe and Tyr have been replaced with car and of [Car1, Leu5]-enkephalin

Thirteen peptides, analogues of bradykinin (BK), enkephalin, Substance P (SP) and [Sar¹]-angiotensin II ([Sar¹]-AT_II) have been synthesized by the solid-phase method. In all these peptides the residue Phe and Tyr were substituted with the boron-containing amino-acid L -o-carboranylalanine (Car). The purity and identity of the peptides were established by TLC., cellulose-electrophoresis and amino acid analysis.     

Acetylenic amides. 3. The synthesis of 5-methylene-2,4-imidazolidinediones from 2-propynamides and isocyanates

2-Propynamides react with aryl isocyanates in the presence of triethylamine to give 5-methylene-2,4-imidazolidinediones 5 in good yields. If the propynamide contains a terminal trimethylsilyl group, Z-trimethylsilylidenehydantoin ( 7 ) is produced.     

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     

Creatinine biosensor based on ammonium ion selective electrode and its application in flow-injection analysis

A new, highly sensitive, fast responding and stable potentiometric biosensor for creatinine determination is developed. The biosensor is based on an ammonium ion-selective electrode. Creatinine deiminase (EC 3.5.4.21) is chemically immobilized on the surface of the polymeric ion-sensitive membrane in the form of monomolecular layer using a simple, one-step carbodiimide covalent attachment method. The resulting enzyme electrodes are useful for measurement under flow injection analysis (FIA) conditions. The biosensors exhibit excellent operational and storage stability. The enzyme electrodes retain over 70% of initial sensitivity after ten weeks of work under FIA conditions. The storage stability at 4 °C is longer than half a year without loss of sensitivity. Under optimized conditions near 30 samples per hour can be analyzed and the determination range (0.02-20.0 mmol l⁻¹) fully covers creatinine concentrations important from clinical and biomedical point of view. The simple biosensor/FIA system has been successfully used for determination of creatinine in urine, serum and posthemodialysate samples.