Effect of vibrational excitation of HBr on the H+HBr abstraction and exchange reactions

The effect of vibrational excitation of HBr on the H+HBrH₂+Br and H+HBrH+HBr reactions has been investigated on the extended LEPS surface (ELEPS) constructed on the basis of quantum chemically calculated points of PES. Together with this surface the LEPS surface of Sudhakaran and Raff [1] was used for comparison at two relative translational energies. A quasiclassical trajectory method was used to study the abstraction and exchange reaction dynamics. The reactive cross section was calculated as a function of the relative collision energy and the vibrational state of HBr. The following conclusions can be drawn from the results of the study: (i) vibrational excitation v=0 v=2 more than doubles the reaction cross section, (ii) the increase in the collision energy is most effectively channelled into the product translational energy.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday     

Saturated heterocycles. 57. Synthesis of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydro-2H-pyrimido[6,1-a]isoquinolin-2-ones

A large number of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones were prepared by the reaction of 1-(ethoxycarbonylmethyl)-6,7-dialkoxy-1,2,3,4-tetrahydroisoquinolines with iminoethers. Reaction of the corresponding isoquinoline-1-acetic acid derivatives with iminoethers led to the formation of N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides. In the hydrolysis of the prepared 4-substituted-pyrimido[6,1-a]isoquinolin-2-ones, the corresponding N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides were obtained. While reduction of the 4-phenyl derivative resulted in the corresponding 1,3,4,6,7,11b-hexahydropyrimidinone. The steric structures of the tetrahydro- and hexahydropyrimido[6,1-a]isoquinolines were determined by nmr spectroscopy.     

Radiolysis of aqueous-ethanolic solution of tryptophan

The effect of ethanol on radiation stability of tryptophan during -irradiation of its aqueous solutions was investigated. In comparison with radiation losses of tryptophan irradiated in pure water, the losses in aqueous-ethanolic solutions are considerably higher and they increase with increasing ethanol concentration. Basic radiation products of tryptophan formed on irradiation of its aqueous-ethanolic solutions in consequence of the reaction of tryptophan with acetaldehyde as the main product of radiolysis of ethanol were followed by paper electrophoresis.     

Thermal Analysis of the System Na3AlF6–NaVO3

Summary. The phase diagram of the system Na₃AlF₆–NaVO₃ was determined by means of thermal analysis. The system is a simple binary eutectic one. The eutectic point was estimated at x(NaVO₃) = 0.975 and t _eut = 617°C. The XRD patterns of samples after thermal analysis revealed the presence of cryolite and NaVO₃ only supporting the above assumption of a simple eutectic binary system.     

Tritium volume activity in natural waters of the NPP Temelín region

With the use of the tritium monitoring network the samples of river water, air humidity and precipitation are collected and analysed for HTO in the vicinity of Temelín nuclear power plant.     

Differential pulse polarographic determination of salicylaldehyde as its Girard-P derivative

A method for the determination of salicylaldehyde (2 × 10^–6–10^–4 M) by differential-pulse polarography, based on the in situ formation of its Girard-P derivative in aqueous solution at pH 2.5, is proposed. The relative standard deviation was 1.5% (ten determinations of 4 × 10^–5 M level). The applicability of this method was checked in synthetic samples containing salicyl alcohol,o-aminophenol, 2-methylphenol, salicylic acid and 4-aminobenzoic acid.     

Novel method for the preparation of anionic surfactant-selective electrodes

A simple one-step synthesis is described for the functionalization of poly(vinyl chloride) used for the preparation of anionic surfactant-selective membrane electrodes. The method is based on the nucleophilic substitution of a fraction of the chlorine atoms bound to the poly(vinyl chloride) backbone by trimethylamine. The prepared slightly charged polymer gave rise to high-quality surfactant-selective electrode membranes, which had a Nernstian response, short response time, and appropriate stability.     

Human topoisomerase I poisoning: docking protoberberines into a structure-based binding site model

Summary Using the X-ray crystal structure of the human topoisomerase I (top1) – DNA cleavable complex and the Sybyl software package, we have developed a general model for the ternary cleavable complex formed with four protoberberine alkaloids differing in the substitution on the terminal phenyl rings and covering a broad range of the top1-poisoning activities. This model has the drug intercalated with its planar chromophore between the −1 and +1 base pairs flanking the cleavage site, with the nonplanar portion pointing into the minor groove. The ternary complexes were geometry-optimized and relative interaction energies, computed by using the Tripos force field, were found to rank in correct order the biological potency of the compounds; in addition, the model is also consistent with the top1-poisoning inactivity of berberine, a major prototype of the protoberberine alkaloids. The model might serve as a rational basis for elaboration of the most active compound as a lead structure, in order to develop more potent top1 poisons as next generation anti-cancer drugs.     

Studies on the conversions of diols and cyclic ethers—49: Stereochemistry of cyclodehydration of 1,4-diols on the action of brönsted and lewis acids: a comprehensive study

The stereochemistry of the cyclodehydration of (±)- and meso-2,5-hexanediol on the action of various dehydrating agents was investigated. The earlier assumed and confirmed intramolecular S_N2 mechanism for acid-catalysed ring-closure was found to hold in most cases. Various extents of racemisation can be observed on the action of certain Lewis acids, and the solvents concentrated H₂SO₄ and HMPT (hexamethyl phosporic acid triamide) under previously unexamined reaction conditions.     

Ein weiterer Beitrag zum Scandiumdicarbidproblem

Zusammenfassung Die bei 1850, 2000 bzw. 2300°C durch die Reduktion von Scandiumoxid mittels Kohlenstoff in dem der Scandiumdicarbidbildung entsprechenden Molverhältnis hergestellten Produkte wurden mit Wasser zersetzt und mit Hilfe der gleichzeitigen gaschromatographischen und massenspektrometrischen Analyse untersucht. Aus den Ergebnissen geht hervor, daß bei der Scandiumdicarbidbildung gleichzeitig ein weiteres Scandiumcarbid, höchstwahrscheinlich ein Sesquicarbid, entsteht.

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Scandium(III) dicarbide problem. Further experimental results

Products obtained by the reduction of Sc₂O₃ with carbon at 1850, 2000 and 2300°C, resp., in the molar ratio corresponding to the scandium dicarbide were hydrolysed with water. Gaseous reaction products were analysed using gas chromatography combined with mass spectrometry. Results show, that during dicarbide formation another scandium carbide, probably sesquicarbide, is also formed.

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Herrn Prof. Dr.H. Nowotny gewidmet.

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7. Mitt.: Coll. Czech. Chem. Commun., im Druck.