Reaction of 1,1,3,3-tetramethyldisiloxane with p-substituted acetophenones in the presence of platinum and rhodium complexes

Hydrosilylation of p-substituted acetophenones XC₆H₄COCH₃ (X = H, Me, MeO, HO, F, Cl, NO₂) with 1,1,3,3-tetramethyldisiloxane in the presence of rhodium and platinum complexes was studied. The Pt(II) complexes are less active but more selective catalysts of hydrosilylation of acetophenones. Six new 1-(1-arylethoxy)-1,1,3,3-tetramethyldisiloxanes were prepared.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1804–1811.Original Russian Text Copyright © 2004 by Zuev, de Vekki, Kuchaev, Vorobev, Skvortsov.This revised version was published online in April 2005 with a corrected cover date.     

Voltamperometric determination of kinetin with a carbon paste modified electrode

The electrochemical behaviour of kinetin (6-furfurylaminopurine) on a carbon paste modified with OV-17 silicone electrode, is studied. The determination of kinetin is possible working in square wave voltammetric techniques, reaching limits of determination of 38.7 ng ml⁻¹. The proposed method was successfully applied to determine the cytokinin in extracts of apples (previously spiked with kinetin) and the obtained results were in accordance with the results obtained with HPLC-UV.     

Purification of adipoyl-7-amino-3-deacetoxycephalosporanic acid from fermentation broth using stepwise elution with a synergistically adsorbed modulator

Multicomponent adsorption data of a fermentation broth containing adipoyl-7-amino-3-deacetoxycephalosporanic acid (adipoyl-7-ADCA), a cephalosporin precursor for 7-ADCA, and two key impurities, alpha-hydroxyadipoyl-7-ADCA and alpha-aminoadipoyl-7-ADCA were obtained from batch equilibrium and frontal chromatography tests. Amberlite XAD-1600 was chosen as the resin. A rate model was applied to simulate the chromatograms. An alkaline buffer, which by itself has no affinity for the resin, was used as the eluent. The widely used reversed-phase modulator model is inaccurate in explaining the stepwise elution data. A new model, the induced competition model, has been developed to account for apparent retention of the buffer in the presence of adsorbed species. Close agreement between the simulations and the data was achieved with the new model.     

Methods of separation of subcellular particles

Summary Some recent developments in the field of tissue fractionation are briefly reviewed. Separation techniques have been improved considerably, thanks mainly to the construction of various automatic rotors for density gradient centrifugation. Progress has also been made in the analysis of the fractions, through automation of biochemical techniques, and especially through the use of quantitative morphological methods.

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Trennverfahren subcellularer Teilchen

Zusammenfassung Ein Überblick über neuere Entwicklungen auf dem Gebiet der Gewebefraktionierung wird angegeben. Die Trennverfahren konnten wesentlich verbessert werden, hauptsächlich durch die Konstruktion verschiedener automatischer Rotoren zum Zentrifugieren mit Dichtegradient. Auch die Analyse der Fraktionen wurde durch Automation biochemischer Verfahren und besonders durch den Einsatz quantitativer morphologischer Methoden weitgehend verbessert.

     

Mechanical properties and molecular mobility in oriented polyolefines

The static modulus of elasticity (E) and the correlation time of rotation ( _c ) of 2,-2,6,6-tetramethylpiperidine-1-oxyl are studied as a function of the temperature (210<T <350°K) for oriented films of isotactic polypropylene and polyethylene of high and low density.E and _c change both upon heating and polymer orientation; this result indicates that sample properties are influenced by the microstructure of the amorphous phase where probes are localized.     

Stable gaseous aziridinium ions

Gaseous protonated aziridine ions are produced at the threshold from β-phenoxyethylamine molecular ions. The evidence for this is collisional activation spectra, using various precursors (including labelled analogues) under electron impact and field ionization conditions. Partial conversion to the acyclic \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm CH = }\mathop {\rm N}\limits^ + {\rm H}_{\rm 2} $\end{document} isomer occurs at higher electron energies and is rationalized by means of a potential energy surface constructed from energetic data.     

Synthesis of N-tetrasubstituted cyclam derivatives appended with sulfonyl or sulfinyl groups via aza-Michael addition

Azamacrocycles bearing four arylsulfonyl or arylsulfinyl pendant arms have been synthesised with good yields through nucleophilic addition of 1,4,8,11-tetraazacyclotetradecane (cyclam) to phenylvinylsulfone, phenylvinylsulfoxide or (R)-tolylvinylsulfoxide in isopropanol/water media. The crystal structure of the tetraethylsulfonylphenyl substituted macrocycle has been determined by X-ray crystallography. Preliminary studies of the coordination properties of these functionalised macrocyles towards Cu(II) and Eu(III) indicate that pendant sulfoxide groups act as oxygen donor coordinating groups.     

The determination of starting conditions for modifier optimization in reversed-phase HPLC

Summary After a brief introduction of the subject, the paper focusses on the first step in any optimization procedure: the delineation of the parameter space, wherein the global optimum is to be found. For organic modifier optimization in reversed-phase liquid chromatography it is shown that the necessary information can be derived from a single water-methanol gradient. It first yields an estimate of the total number of solutes in the sample, which is vital to define the peak capacity needed to achieve separation at a certain confidence level. Next, the gradient allows the prediction of suitable isocratic methanol binary solvents, and transfer rules formulate the iso-eluotropic composition of the common binary solvents (tetrahydrofuran and acetonitrile). Because all predictions are based on a statistical analysis of a limited data base, attention is given to the practical situation where an actual sample deviates from the average solute behaviour. Such deviations are revealed in the first isocratic run and can be used to arrive at a better estimate of solute retention.     

Classical and quantum algebras of non-local charges in σ models

We investigate the algebras of the non-local charges and their generating functionals (the monodromy matrices) in classical and quantum non-linear models. In the case of the classical chiral models it turns out that there exists no definition of the Poisson bracket of two monodromy matrices satisfying antisymmetry and the Jacobi identity. Thus, the classical non-local charges do not generate a Lie algebra. In the case of the quantum O(N) non-linear model, we explicitly determine the conserved quantum monodromy operator from a factorization principle together withP,T, and O(N) invariance. We give closed expressions for its matrix elements between asymptotic states in terms of the known two-particleS-matrix. The quantumR-matrix of the model is found. The quantum non-local charges obey a quadratic Lie algebra governed by a Yang-Baxter equation.Laboratoire associé au CNRS No. LA 280     

A theorem on asymptotic expansion of Feynman amplitudes

For any Feynman amplitude, where any subset of invariants and/or squared masses is scaled by a real parameter going to zero or infinity, the existence of an expansion in powers of and ln is proved, and a method is given for determining such an expansion. This is shown quite generally in euclidean metric, whatever the external momenta (exceptional or not) and the internal masses (vanishing or not) may be, and for some simple cases in minkowskian metric, assuming only finiteness of the — eventually renormalized — amplitude before scaling. The method uses what is called Multiple Mellin representation, the validity of which is related to a generalized power-counting theorem.On leave of absence from University of Bahia (Brazil). Fellow of CAPES, Brazil