Formation and Crystal Structure of [(F5TeOXe)+·SO2ClF][Sb(OTeF5)6-]

Xe(OTeF₅)₂ reacts with Sb(OTeF₅)₃ under the formation of [Xe₂(OTeF₅)₃]⁺[Sb(OTeF₅)₆]^-. From SO₂ClF solution a yellow solvate [F₅TeOXe]⁺·SO₂ClF· [Sb(OTeF₅)₆]^- is formed with the crystal data: a = 1028.1(1), b = 1040.9(1), c = 1780.2(3) pm, α = 98.07(1), β = 97.68(1), γ = 105.82(1)°, space group . The O-Xe···O fragment is essentially linear (176.1(2)°), and the two Xe-O distances are quite different 197.1(4) and 242.6(4) pm.     

Time dependence of viscosity of dilute polyisobutylene solutions

Summary Shearing at constant gradient of polyisobutylene (PIB) solutions in viscous polybutene oils results in time dependent changes of their viscosities. Two PIB fractions (M=8·10⁶ and 3.8·10⁶) have been studied in a variety of solvents, covering the viscosity range from 5 to 0.5·10⁻² poise. The overall phenomenon is similar to that already observed for polymethylmethacrylate, polystyrene, and polyethylene oxide solutions in Aroclor. Results have been discussed in terms of polymer molecular weight and concentration, solvent viscosity and gradient. The systems investigated are free from strong polar interactions and tendency toward molecular aggregation; time dependent changes of viscosity are therefore observable also for true molecularly dispersed solutions.

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Zusammenfassung Scherung mit konstantem Geschwindigkeitsgradienten von Polyisobutylen (PIB)-L?sungen in viskosen Polybuten-?len ergibt zeitabh?ngige ?nderungen ihrer Viskosit?ten. Zwei PIB-Fraktionen (M=8·10⁶ und 3,8·10⁶) wurden in einer Vielzahl von L?sungsmitteln untersucht, die den Viskosit?tsbereich von 5 bis 0,5·10⁻² Poise überdeckten. Das ph?nomenologische Erscheinungsbild ist ?hnlich dem schon beobachteten für Polymethylmethacrylat, Polystyrol und Poly?thylenoxid-L?sungen in Aroclor. Die Ergebnisse wurden hinsichtlich des Polymer-Molekulargewichts und der Konzentration, der L?sungsmittelviskosit?t und des Gradienten diskutiert. Die untersuchten Systeme sind frei von starken polaren Wechselwirkungen und von Tendenzen in Richtung auf molekulare Aggregation. Zeitabh?ngige ?nderungen der Viskosit?t sind deshalb auch für wahre molekulardisperse L?sungen beobachtbar.

     

Préparation de quelques 4-nitroisoxazoles à partir de pseudonitrosites de cétones éthyléniques du type chalcone

The Synthesis of some 4-Nitroisoxazoles from Pseudonitrosites of Chalcones The action of dinitrogen trioxide with α,β-unsaturated ketones of the chalcone type leads to pseudonitrosites (Table 1) which are cyclized to 4-nitro-3,5-diarylisoxazoles (Table 2).     

Absolute line intensity measurements of hot bands for carbonyl sulfide at 12 microm

Using diode-laser spectroscopy, the intensities of 58 lines of the v(1) + v(1/2) - v(1/2) band and 36 lines of the 2v(1) - v(1) band of OCS have been measured. The corresponding band strengths S(0)(v) and the vibrational transition dipoles micro(v) have been derived through least squares fitting of these individual intensities. The band strengths values have been determined with a precision better than 2.5%.     

LBGK method coupled to time splitting technique for solving reaction-diffusion processes in complex systems

A new approach to numerically solve a reaction-diffusion system is given, specifically developed for complex systems including many reacting/diffusing species with broad ranges of rate constants and diffusion coefficients, as well as complicated geometry of reacting interfaces. The approach combines a Lattice Boltzmann (LB) method with a splitting time technique. In the present work, the proposed approach is tested by focusing on the typical reaction process between a metal ion M and a ligand L, to form a complex ML with M being consumed at an electrode. The aim of the paper is to systematically study the convergence conditions of the associated numerical scheme. We find that the combination of LB with the time splitting method allows us to solve the problem for any value of association and dissociation rate constant of the reaction process. Also, the method can be extended to a mixture of ligands. We stress two main points: (1) the LB approach is particularly convenient for the flux computation of M and (2) the splitting time procedure is very well suited for reaction processes involving association-dissociation rate constants varying on many orders of magnitude.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XLIV. Tetrakis(alkoxycarbonylmethyl)titan-Verbindungen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLIII. Tetrakis(alkoxycarbonylmethyl)titanium Compounds Organotitanium(IV) compounds of the type (ROCOCH₂)₄Ti (R ? C₂H₅, i-C₃H₇, t-C₄H₉, C₆H₅, C₆H₅CH₂) were obtained by reactions of ROCOCH₂Li derivatives with TiCl₄ at low temperature. The compounds which decompose only above 90°C were characterized by the hydrolysis products, anaerobic reactions with iodine, and the i.r. spectra. The bond conditions are discussed.     

On the determination of polarity parameters of silica by means of solvatochromic probe dyes

Empirical solvent parameters of silica surfaces are determined by means of solvatochromic dyes, e.g., Cu(tmen) (acac)⁺ ClO ₄ ^– /B(C₆H₅) ₄ ^– , Fe(phen)₂(CN)₂, and Michlers Ketone dissolved in 1,2-dichloroethane or cyclohexane. The values obtained by UV/VIS-measurements are compared with both the polarity scales of Kamlet and Taft and with Gutmann's donor and acceptor numbers. Kamlet and Taft's -parameter (the hydrogen-bond donation capacity of a solvent) is determined independently by means of salicylideneaniline. The ^* of silica is determined using 5-N,N-dimethylamino-5-nitro-2,2-bithiophene and the complex of tetracyanoethylene with Michlers Ketone, respectively. Further on the reliabilities of the obtained Kamlet-Taft parameters , , and ^* are checked by comparism with experimental and calculated values of theE _T(30)-parameter of silica by means of multi-parameter regression analysis. The surface properties of silica are influenced mainly by HBD-properties (75%) and dipolarity/polarizability ^* (20%), but hardly by the HBA-properties (<5%). UV/VIS-measurements were carried out in a special equipment with glass fiber optics, A drawing of the apparatus is given.     

Die Strommer-Zykliden des Flaggenraumes

According to H. BRAUNER a flag space is a three-dimensional affine space with an absolute {,f,F}, wheref is a line in the plane of infinity andF a point onf. A cyclide is a surface of order 4 that intersects only atf. A STROMMER-cyclide is a cyclide generated by translation of a circle in an isotropic plane. In this paper we proof that all STROMMER-cyclides can be generated by translation of an isotropic circle along a divergent Newton-parabola or a conic in a full isotropic plane. We give normal-forms and CAD-pictures of these surfaces. Finaly some geometrical results about STROMMER-cyclides are developed.

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Herrn o.Prof. Dr. Gy. Strommer zum 70. Geburtstag gewidmet.     

Density fluctuations in amorphous and semicrystalline polymers

Summary The small-angle scattering of amorphous and semicrystalline polymers contains an intensity component due to density fluctuations within the crystalline and amorphous domains.For amorphous polymers, the density fluctuations aboveT _g correspond to the theoretical value for a fluid system in thermodynamic equilibrium. BelowT _g , a temperature dependence proportional to T is observed over a range of about 50°. At lower temperatures, a linear relationship with a smaller slope has been found which extrapolates to a non-zero value at 0 °K. This value corresponds to the frozen-in disorder, the slope at low temperatures is related to thermal vibrations and can be evaluated in terms of photon-phonon scattering.Semicrystalline polymers show a temperature dependence of the density fluctuation similar to that of the amorphous polymers. At constant temperature the density fluctuations vary linearly with crystallinity.Natural rubber shows an increase of the density fluctuations with increasing cross-linking densities from which information on the density changes in the vicinity of a cross-link and on the statistics of the distribution of cross-linking can be obtained.

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Zusammenfassung Die Kleinwinkelstreuung amorpher und teilkristalliner Polymere besitzt eine Intensitätskomponente, die von Dichtefluktuationen innerhalb der kristallinen und amorphen Bezirke herrührt. Für amorphe Polymere entspricht die Dichtefluktuation oberhalb vonT _g dem theoretischen Wert für ein fluides System im thermodynamischen Gleichgewicht. UnterhalbT _g wird eine Temperaturabhängigkeit proportional zuT über einen Bereich von etwa 50° beobachtet. Bei tieferen Temperaturen wird eine lineare Beziehung mit einer geringeren Steigung gefunden, welche zu einem endlichen Wert bei 0 °K extrapoliert werden kann. Dieser Wert bezieht sich auf die eingefrorene Fehlordnung, die Steigung bei tiefen Temperaturen ist auf thermische Schwingungen zurückzuführen und kann als Photon-Phonon-Streuung ausgewertet werden.Teilkristalline Polymere zeigen eine Temperaturabhängigkeit der Dichtefluktuation, die der von amorphen Polymeren ähnlich ist. Bei konstanter Temperatur ändert sich die Dichtefluktuation linear mit der Kristallinität.Naturkautschuk zeigt eine mit der Vernetzungsdichte ansteigende Dichtefluktuation, aus der man Information über die Dichteänderung in der Umgebung eines Netzpunktes und die Statistik der Netzpunktverteilung erhalten kann.

     

Xylanase production by Trichoderma reesei rut C-30 on rice straw

Xylanase production of Trichoderma reesei Rut C-30 was examined at different initial pH values (4.8, 5.9, and 7.0) on rice straw in shake flasks, and in a fermentor, for the best pH condition. Enzyme performance was tested on ammonia-treated dwarf elephant grass. The maximum xylanase activities, 92 and 122 IU/mL, were obtained at pH 4.8 in the shake flasks and fermentor, respectively, in which good growth of the fungus was observed during the first 24 h and consumption of proteins dissolved from the rice straw caused the pH to rise later to values between 6.4 and 6.7 (optimal for xylanase production). The xylanases from T. reesei were as effective as Multifect XL, a commercial enzyme preparation, in hydrolyzing ammonia-treated elephant grass.