Strukturanalyse organischer Sulfide mit Hilfe der Gras-Chromatographie

Zusammenfassung Eine Methode der Identifizierung von Alkyl- und Arylgruppen organischer Sulfide wurde ausgearbeitet, die die Spaltung dieser Stoffe mit Raney-Nickel zur gaschromatographischen Bestimmung der dabei entstandenen Kohlenwasserstoffe ausnützt.

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Summary A method was developed for identifying alkyl- and aryl groups of organic sulfides. The method employs the cleavage of these materials with Raney nickel for the gas chromatographic determination of the resulting hydrocarbons.

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Résumé On a mis au point une méthode d'identification des groupes alkylés et arylés des sulfures organiques exploitant la dissociation de ceux-ci par le nickel Raney pour le dosage par chromatographic en phase gazeuse des carbures d'hydrogène qui se forment.

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Die Autoren danken den Kollegen Dr.M. Veea, Ing.J. Petránek und Ing.J. Gaspari für die Überlassung von Proben organischer Sulfide.     

An application of neural networks in chemistry. Prediction of13C NMR chemical shifts

Basic definitions of neural networks are given in terms of oriented graphs. Partial derivatives of an objective function with respect to the weight and threshold coefficients are derived. These derivatives are very important for the adaptation process, carried out by a version of the gradient method of We neural network considered. The stability of the adapted neural network toward small changes — perturbation — of input activities is described by sensitivities. The theory is illustrated by application of simple neural networks that reflect the topology of molecules to the classification of¹³C NMR chemical shifts of secondary carbons in acyclic alkanes.     

Influence of medium on the kinetics of oxidation of iron(II) ion with t-butyl hydroperoxide

The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent mixture (φ_r = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN⁻ at constant 0.8 mmol dm⁻³ HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant in the presence of Cl⁻ only. The oxidation rate measured in the [FeCl]²⁺ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching the physiological pH conditions the rate constant attained the value of an order of magnitude of 10³ dm³ mol⁻¹ s⁻¹, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the presence of Cl⁻ strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm⁻³ HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity, and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step. Presented at the 20th International Conference on the Coordination and Bioinorganic Chemistry organized by the Slovak Chemical Society, Slovak University of Technology, Comenius University, and the Slovak Academy of Sciences, Smolenice Castle, 5–10 June 2005.     

Polarographische Bestimmung des Pyridoxols in pharmazeutischen Präparaten

Zusammenfassung Es wird eine neue polarographische Methode zur direkten Bestimmung des Pyridoxols in Injektionspräparaten und Tabletten beschrieben. Die ausgearbeitete Methode beruht auf der polarographischen Reduktion des Pyridoxolmoleküls im Milieu von Ammoniak-Ammoniumchlorid-Puffern und weiter auf der Bildung einer katalytischen Stufe des Pyridoxols in Veronalpuffern. Die polarographische Methode ist rascher und in manchen Fällen genauer und empfindlicher als die bisher in Gebrauch stehenden Methoden. Die Anwesenheit der in den Präparaten laufend vorkommenden Begleitstoffe des Pyridoxols stört nicht die polarographische Bestimmung. Die Methode kann auch zur Bestimmung des 3-Hydroxy-4-methoxymethyl-5-oxymethyl-2-methylpyridins benutzt werden, das ein Zwischenprodukt bei der Pyridoxolerzeugung ist.

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Summary A new polarographic method is described for the direct determination of pyridoxol in injection preparations and tablets. This method is based on the polarographic reduction of the pyridoxol in ammonia-ammonium chloride buffer medium and also on the formation of a catalytic stage of the pyridoxol in veronal buffers. The polarographic method is faster and in many cases more accurate and more sensitive than the methods now in use. The presence of the materials which always accompany the pyridoxol in the preparations does not interfere with the polarographic determination. The method can likewise be used for determining 3-hydroxy-4-methoxymethyl-5-oxymethyl-2-methylpyridine, which is an intermediate product in the manufacture of pyridoxol.

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Résumé On décrit une nouvelle méthode polarographique pour le dosage direct du pyridoxol dans les préparations pour injections et dans les comprimés. La méthode élaborée repose sur la réduction polarographique de la molécule de pyridoxol dans le milieu tampon ammoniaque-chlorure d'ammonium, et, en outre, sur la formation d'une phase catalytique du pyridoxol dans les tampons au véronal. La méthode polarographique est plus rapide et dans de nombreux cas plus exacte et plus sensible que les méthodes utilisées jusqu'ici. La présence d'impuretés existant couramment dans les préparations à côté du pyridoxol ne gêne pas le dosage polarographique. On peut aussi utiliser la méthode pour le dosage de l'hydroxy-3 méthoxyméthyl-4 oxyméthyl-5 méthyl-2 pyridine, substance intermédiaire dans la préparation du pyridoxol.

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Herrn Dr.P. Zuman danken wit für Ratsehläge bei der Abfassung dieser Arbeit.     

On the tautological ring of ℳ g

We prove that any product of tautological classes of _g of degreed (in the Chow ring of _g with rational coefficients) vanishes ford>g–2 and is proportional to the class of the hyperelliptic locus in degreeg–2.Oblatum 28-I-1195 & 15-IV-1995In memory of Nicolaas H. Kuiper (1920–1994)     

Large deviations for martingales with some applications

Let(X _i ) be a martingale difference sequence. LetY be a standard normal random variable. We investigate the rate of uniform convergence

Kneser-type oscillation criteria for self-adjoint two-term differential equations

It is proved that the even-order equationy ⁽²ⁿ⁾ +p(t)y=0 is (n,n) oscillatory at if

q-Sigma-algebra generated by balls

The q--algebra, i.e., the system of sets closed under complementation, countable disjoint unions, and containing the empty set, generated by the system of open balls coincides with the -field of Borel sets inR sun forn=1,2, and 3. A first step to extend the proof forn=4, 5, 6, and 7 is indicated.     

Encapsulation of magnetite in vesicles

The encapsulation of fine magnetite particles of 10 nm size and marker ANS within asolectin vesicles has been made by sonication of the mixture in water. For the proof of encapsulation of magnetite in vesicles the electron microscope and spectrofluoriphotometer technique were used. The theory for the calculation of the magnetic force acting on the system consisted of non-capsulated magnetic particles dispersed in water and magnetic vesicles was developed.This work was supported by the Slovak Academy of Sciences within the framework of Project GAV No. 1361.     

On the critical regimes in the theory of randomly forced magnetohydrodynamic turbulence

In this paper large-scale properties of developed magnetohydrodynamic turbulence have been investigated by using double expansion method in the frame of quantum field renormalization group. It has been shown that universal kinetic scaling regime exists, but the double expansion in general leads to qualitatively different results than those provided by the usual -expansion treatment.This work was supported by Slovak Grant Agency for Science.