Allylic Peroxidations with Bis(2‐pyridylimino)isoindolato‐Cobalt and ‐Iron Complexes

Several novel substituted bis(2‐pyridylimino)isoindolato (BPI) cobalt(II) and iron(II) complexes [M(BPI)(OAc)(H₂O)] (M = Co: 1 ‐ 6, Fe: 7) have been synthesized by reaction of bis(2‐pyridylimino)isoindole derivatives with the corresponding metal(II) acetates. Reaction of 1‐6 with 1.5 ‐ 2 molar equivalents of t‐BuOOH gave the corresponding alkylperoxocobalt(III) complexes [Co(BPI)(OAc)(OOtBu)] (10 ‐ 15). Using an aqueous solution of t‐BuOOH (70 %), cyclohexene was selectively catalytically oxidized to the dialkylperoxide cyclohex‐2‐ene‐1‐t‐butylperoxide.     

Zur praktischen Berechnung linear-viskoelastischer Probleme

Zusammenfassung Es wird gezeigt, daß bei Verwendung integraler Materialgesetze für das linear-viskoelastische Material Strukturen auftreten, die für eine direkte Angabe der viskoelastischen Lösung aus der elastischen Lösung genutzt werden können. Bei einfachen Problemen können die Kombinationen von Materialkonstanten in der elastischen Lösung durch Kombinationen von Kriech- oder Relaxationsfunktionen ersetzt werden. Im allgemeinen müssen sehr einfache Integralgleichungen vom Typ eines Faltungsintegrals gelöst werden. Damit ist ein Weg angegeben, der auch bei beliebiger Form der Kriechfunktion gangbar ist und als eine Verallgemeinerung des ersten Korrespondenzprinzips angesehen werden kann.

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Summary It is shown that using integral type constitutive laws of linear-viscoelastic materials there are structures to be seen which allow the direct solution of viscoelastic problems from elastic solutions. For simple problems the combinations of material constants in the elastic solution can be replaced by creep or relaxation functions, but in general very simply integral equations of convolution type have to be solved. The described method gives an elastic-viscoelastic analogy applicable also to creep functions which can not be described by rheological methods.

Mit 2 Abbildungen und 3 Tabellen     

A Teflon pressure-transducer-specimen bond for ultrasonic measurements over a wide temperature range

A major limitation for the application of megahertz ultrasonic techniques to the study of the properties of solids is the problem of finding transducer-specimen bonds useful over a wide temperature range. A Teflon pressure bond has been developed and tested. It appears to overcome most of the problems, and promises to allow for many studies previously more difficult or impracticable.     

Über das Verhalten einer Funktion von mehreren Veränderlichen in der Umgebung einer Stelle,an welcher sie die Form 0/0 hat

Ohne Zusammenfassung     

Zur Differentiation bestimmter Integrale nach einem Parameter

Ohne Zusammenfassung     

Über die Determinante von Wronski

Ohne Zusammenfassung     

The fixation of bis(2-pyridylimino)isoindolato (BPI) ligands to dendritic carbosilanes

Bis(2-pyridylimino)isoindolato (BPI) ligands, containing an alkynyl linker unit which allows their fixation to carbosilane dendrimers and dendrons, were synthesized by reaction of 4-nitrophthalodinitrile with 4-butynol giving the phthalodinitrile derivative containing the linker. These were subsequently reacted with two molar equivalents of 2-amino-4-methylpyridine and 2-amino-4-(t)butylpyridine yielding the respective BPI protioligands 2a and 2b. Lithiation with LDA and reaction with Si-Cl or Si-OTf (OTf=triflate) end groups in core or peripheral positions of dendritic carbosilanes gave the endodendrally and expdendrally functionalized dendrimers. Among these the first and second generation dendrimers [G-1](8-exo)-4-[C[triple bond, length as m-dash]CCH2CH2O]-10-MeBPI (8), [G-1]12-exo-4-[C[triple bond, length as m-dash]CCH2CH2O]-10-MeBPI (9) and [G-2](16-exo)-4-[C[triple bond, length as m-dash]CCH2CH2O]-10-MeBPI (10) were synthesized and fully characterized. The functional dendrimers were metallated by reaction with [(PhCN)2PdCl2] in dichloromethane to give the corresponding pallada-dendrimers.     

Cellulose hydrolysis – the role of monocomponent cellulases in crystalline cellulose degradation

Changes in the molecular structure of cellulose during hydrolysis with four recombinant -1,4-glycanases from the cellulolytic bacterium Cellulomonas fimi were assessed and compared in an attempt to elucidate the mechanism of crystalline cellulose degradation. It was apparent that the two endoglucanases, Cel6A and Cel5A, degraded sigmacell cellulose differently; Cel5A liberated more soluble sugars (cellobiose and cellotriose) and significantly altered the molecular weight distribution, while Cel6A had a limited effect on the polymer size and liberated primarily cellobiose and glucose. Additionally, both endoglucanases slightly increased the crystallinity of cellulose. In contrast, the cellobiohydrolases, Cel6B and Cel48A, had no effect on cellulose molecular weight and liberated only cellobiose and cellotriose. However, Cel48A was shown to be effective at reducing the crystallinity of the cellulosic substrate, while Cel6B increased the crystallinity index. Synergistic hydrolysis using combinations of the different enzymes showed that, although the cellulose was extensively hydrolysed, the molecular structure of the substrate was similar to the original material. This phenomenon suggests that the actions of individual monocomponent enzymes are offset by the concurrent modification by the complementing enzymes during synergistic hydrolysis.     

Molecular field effects in Mössbauer spectra of FeSb2O4

Mössbauer effect measurements have been made using⁵⁷Fe in FeSb₂O₄. At liquid helium temperature a combined electric quadrupole and magnetic hyperfine interaction is observed withH _eff=185±2 kOe, 1/2e ² qQ=2.94±0.09 mm/sec and =0.37±0.09. The direction ofH _eff is perpendicular to thec axis of the crystal and at 33° to the <110> direction. Thec axis is determined to be the direction of the intermediate principal EFG tensor axis. Calculations are made using a molecular field term in the Hamiltonian for the Fe²⁺ orbitals. The results of these calculations are used to explain the observed values of 1/2e ² qQ and and permit a determination of the ordring of the T_2g orbitals among the T_2g energy levels.     

Comparison of high-resolution MRI, optical microscopy and SEM for quantitation of trabecular architecture in the rat femur

Magnetic resonance imaging (MRI) has been used to analyze trabecular bone architecture in femur heads taken from adult Wistar rats. The aim of this study was to validate the use of MRI in assessing trabecular structure and morphology by comparing standard measures of bone morphology in the rat femur obtained from high resolution MRI with those obtained by conventional optical microscopy and by scanning electron microscopy (SEM). MR images were obtained on a Bruker 4.7 T micro-imaging system using a three-dimensional spin echo sequence with spatial resolution of 23 microm in-plane and a slice thickness of 39 microm. Optical images were obtained by de-calcifying the bone in EDTA and then sectioning 5-microm-thick slices. SEM images were obtained from bone embedded in epoxy resin with surface preparation by diamond polishing. Values of standard bone morphological parameters were compared and correlation coefficients between the MRI and the optical- and SEM-derived measures of morphology were calculated. Partial volume effects in MRI were minimized in this study by the use of very thin slices, yielding better agreement with optical- and SEM-derived measures of trabecular bone morphology than have been obtained in previous studies. Correlations between the MRI and optical data were significantly lower than those between the MRI and SEM data. Effects of de-calcification were also investigated. The results indicate that comparison of MRI with thin (de-calcified) optical images may be inherently flawed due to the destructive de-calcification and sectioning process used to prepare samples for the optical imaging.