Ligand exchange reactions of some Cr(III) complexes investigated by cyclic voltammetry

From cyclic linear sweep voltammograms of some Cr(III) complexes it is evident that after electron transfer ligand groups are expelled relatively slowly inDMSO and the tetra coordinated complex is formed. The rate constants could be determined in some cases by the methods of cyclic voltammetry. The following compounds were examined: [Cr(en)₃]³⁺, [Cr(acac)(en)₂]²⁺, [Cr(acac)₃]. [Cr(dien)₂]³⁺, [Cr(DMSO)₆]³⁺, [Cr(ur)₆]³⁺. For [Cr(en)₃]³⁺ the energy of activation could be determined as well.The dependence of the velocity of ligand elimination on complex structure is discussed.

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Untersuchung von Ligandenaustauschreaktionen einiger Cr(III)-Komplexe mittels cyclischer Voltammetrie

Zusammenfassung Bei der Reduktion einiger der folgenden Cr(III)-Komplexe inDMSO läßt sich auf Grund der Voltammogramme auf eine Ligandenabspaltung und Bildung der vierfach koordinierten Cr(II)-Komplexe schließen: [Cr(en)₃]³⁺, [Cr(acac)(en)₂]²⁺, [Cr(acac)₃], [Cr(dien)₂]³⁺, [Cr(DMSO)₆]³⁺, [Cr(ur)₆]³⁺. Für das [Cr(en)₃]³⁺ konnten Geschwindigkeitskonstante und Aktivierungsenergie dieser nachgelagerten Reaktion bestimmt werden.Der Einfluß der Struktur des Komplexes auf die Zerfallsgeschwindigkeit wird diskutiert.

     

Photoinduced morphism of gemini surfactant aggregates

The photochemical behaviour of an azobenzene chromophore inserted in a gemini surfactant imparts photocontrol to the resulting amphiphile assemblies, including the collapse, upon irradiation, of the multi lamellar vesicles formed in aqueous solution.     

New hardware for radio frequency powered glow discharge spectroscopies and its capabilities for analytical applications

A new radio frequency (rf) hardware is developed for glow discharge spectroscopic methods. The resulting features and its capabilities for analytical applications are discussed. The electrical equipment developed allows to work as quickly, stably, reliably and easily as known from the direct current (dc) mode. Moreover, the rf power measurement has been improved. The hardware has been developed, optimised and tested for glow discharge optical emission spectroscopy (GDOES), but nevertheless it is possible to use it for all procedures applying glow discharge sources.     

Regioselective Synthesis of Mixed Indole 2,3-Bis(sulfides). A Study of the Mechanism of the Second Sulfenylation of Indole

Sulfenylation of indole using sulfenyl chlorides leads to the initial formation of a 3-indolyl sulfide, while excess reagent introduces a second sulfide at the 2-position of the ring. The mechanism of this second sulfenylation has not, to date, been rigorously elucidated. The development of the first, regioselective synthesis of mixed indole 2,3-bis(sulfides) has allowed the study of the sulfenylation of 3-indolyl sulfides using a different sulfenyl chloride. Our results afford evidence that the reaction proceeds via an intermediate 3,3-disulfenylated indolenine species, with subsequent migration of one of the sulfide groups to the 2-position.     

An efficient synthesis of [1,1]ferrocenophane via 1,1′-bis(6-fulvenyl)ferrocene

[1,1]Ferrocenophane can be prepared by reduction of 1,1′-bis(6-fulvenyl)ferrocene with complex borohydrides to give the dianion of 1,1′-bis(cyclopentadienylmethyl)ferrocene. Reaction of this dianion with ferrous chloride produces the ferrocenophane in good yield.     

Very general formation of tetrahydropterin cation radicals during reaction of iron porphyrins with tetrahydropterins: model for the corresponding NO-synthase reaction

Electron transfer from tetrahydropterins to iron porphyrins, with formation of intermediate tetrahydropterin cation radicals, is a very general reaction that was shown to occur not only with tetrahydrobiopterin, as originally found in NO-synthases, but also with another important biological cofactor, tetrahydrofolate, and various iron porphyrins, either in their ferric state, or in the Fe(II)O(2) state, as in the first model of the corresponding NO-synthase reaction described in this paper.     

Chemical modification of acetylcholinesterase with methoxypolyethylene glycol

Acetylcholinesterase (AChE) (EC 3.1.1.7) was modified with activated monomethoxypolyethylene glycol (mPEG). A decrease of 50% in the catalytic activity was measured during the coupling reaction and the change in the surface properties of AChE was used to separate by hydrophobic interaction chromatography the native and the modified enzyme. The native and the modified enzymes were found to have the same optimalcatalytic conditions. Moreover, the Michaelis constant of both enzymes were similar, whereas theV _m and the bimolecular-velocity constant calculated for organophosphorus inhibitors were slightly higher for the modified AChE. Finally, the modification with mPEG did not improve the thermal stability, whereas the stability in a few organic solvents increased.     

Quantitative depth profiling in glow discharge spectroscopies – A new deconvolution technique to separate effects of an uneven erosion crater shape

An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system.     

Photochemistry of condensed isoxazolines

Summary The condensed bridged isoxazolines4 are rearranged on irradiation with a low-pressure mercury lamp exclusively into condensed derivatives of tetrahydropyridine5. The selectivity of the rearrangement is due to a stabilization of the biradical8 by the overlap of the radical-electrons with -electrons of the C=C double bond and the heterocyclic ring. Quantum yields of the photorearrangement, established from the consumption of the starting materials4, were determined.

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Photochemie kondensierter Isoxazoline

Zusammenfassung Die kondensierten überbrückten Isoxazoline4 werden durch Bestrahlen mit einer Niederdruckquecksilberlampe ausschließlich zu kondensierten Tetrahydropyridinderivaten (5) umgelagert. Die Selektivität der Umlagerung beruht auf der Stabilisierung des Diradikals8 durch Überlappung der ungepaarten Elektronen mit -Elektronen der C=C-Doppelbindung und des Heterocyclus. Aus dem Verbrauch an Ausgangsmaterial (4) wurden Quantenausbeuten der Photoumlagerung bestimmt.