Determination of magnetic parameters by means of brillouinscattering. Examples: Fe,Ni, Ni0.8Fe0.2

We have used the new technique of Brillouin scattering from spinwaves in thin films for a determination of their magnetic parameters. Films of Fe, Ni and Ni_0.8Fe_0.2 (permalloy) have been investigated and we find good agreement with the results obtained by other methods. We also display spectra from all three materials and discuss some of their characteristic features. For Fe epitaxial growth on epipolished sapphire is reported here for the first time.     

Nucleophilic reactivities of Schiff base derivatives of amino acids

Treatment of α-imino esters derived from glycine esters and benzophenone or benzaldehydes with potassium tert butoxide in DMSO gave persistent solutions of carbanions at 20?°C. The kinetics of their reactions with quinone methides and benzylidene malonates (reference electrophiles) have been followed photometrically under pseudo-first order conditions. The reactions followed second-order rate laws. Since addition of 18-crown-6 ether did not affect the reaction rates, the measured rate constants correspond to the reactions of the non-paired carbanions. Plots of the second-order rate constants against the electrophilicity parameters E of the electrophiles are linear, which allowed us to derive the nucleophile-specific parameters N and s_N, according to the linear Gibbs energy relationship lg k₂(20?°C)?=?s_N(N + E). The Ph₂C?=?N- and PhCH?=?N- groups act as very weak electron acceptors with the consequence that Ph₂C?=?N-CH^–-CO₂R and PhCH?=?N-CH^–-CO₂R have a similar nucleophilicity as Ph-CH^–-CO₂Et, the anion of ethyl phenylacetate.     

A Dogma in Doubt: Hydrolysis of Equatorial Ligands of PtIV Complexes under Physiological Conditions

Due to their high kinetic inertness and consequently reduced side reactions with biomolecules, Pt^IV complexes are considered to define the future of anticancer platinum drugs. The aqueous stability of a series of biscarboxylato Pt^IV complexes was studied under physiologically relevant conditions. Unexpectedly and in contrast to the current chemical understanding, especially oxaliplatin and satraplatin complexes underwent fast hydrolysis in equatorial position (even in cell culture medium and serum). Notably, the resulting hydrolysis products strongly differ in their reduction kinetics, a crucial parameter for the activation of Pt^IV drugs, which also changes the anticancer potential of the compounds in cell culture. The discovery that intact Pt^IV complexes can hydrolyze at equatorial position contradicts the dogma on the general kinetic inertness of Pt^IV compounds and needs to be considered in the screening and design for novel platinum‐based anticancer drugs.     

Tensile strengths and Young’s modulus of thin copper and copper-nickel (CuNi44) substrates

In this paper we report a method to determine tensile strengths and Young’s modulus of cubic biaxial textured metal tapes used as substrate materials for coated conductors (CC). Simplicity, rapidity and reproducibility of the procedure are important for the evaluation of continuous in-house productions. Our approach is based on the EN 10002-1 B tensile test method. A key role for satisfactory results is the sample preparation of 100–250 μm thick tapes, which will be described in detail. Copper (E-Cu57) can be successfully transformed to cubic biaxial textured substrates. Best results were achieved by annealing between 750°C and 850°C in reducing atmosphere. Best FWHM values for the ψ scan are 5.51° and for the ϕ scan are 4.5°. Pole figure analysis verified the sharp {001} <100> texture of the tape. Vickers hardness measurements (HV 0.1) for the cold worked material yielded values of 135 and for the annealed tape, values of 37. The ultimate tensile yield strength Rm of the textured substrate is 150 MPa and thus significantly lower than that for the cold worked material (413 MPa). Cubic biaxial substrates could be manufactured from Isotan CuNi44 (WM49) bars. Best results were achieved by annealing at 1200°C in reducing atmosphere. Pole figure analysis verified the {001} <100> texture with other low intensity texture components. Vickers hardness measurements (HV 0.1) for the cold worked material yielded values of 236 and for the annealed tape values of 92. The ultimate tensile yield strength R _m of the textured substrate is 300 MPa and thus significantly lower than that for the cold worked material (723 MPa).      

Electrophilicity parameters of 5-benzylidene-2,2-dimethyl[1,3]dioxane-4,6-diones (benzylidene Meldrum's acids)

Kinetics of the reactions of four benzylidene Meldrum's acids 1 with acceptor-substituted carbanions 2 were studied photometrically in DMSO at 20 degrees C. The reactions follow second-order kinetics, and the second-order rate constants were found to follow the correlation log k2 (20 degrees C) = s(N + E) (eq 1), which was used to calculate the electrophilicity parameters E for compounds 1. Hammett correlations are given, which allow one to assign electrophilicity parameters for various beta,beta-acceptor substituted styrenes and thus to predict a large number of absolute rate constants for a manifold of Michael additions. The reactions of primary and secondary amines are approximately 2 orders of magnitude faster than predicted by the correlation (1), supporting transition states which are stabilized by hydrogen bridges from NH to the carbonyl groups of the benzylidene Meldrum's acids.