Structural studies on aryl‐substituted enaminoketones and their thio analogues. Part II. Experimental and DFT calculated carbon–carbon coupling constants,nJ(CC)'s (n = 1–3)

Spin–spin carbon–carbon coupling constants across one, two and three bonds, J(CC), have been measured for a series of aryl‐substituted Z‐s‐Z‐s‐E enaminoketones and their thio analogues. As a result, a large set, altogether 178, of J(CC)s has been obtained. It consists of 82 couplings across one bond, 31 couplings across two bonds and 65 couplings across three bonds. Independently, the DFT calculations at the B3PW91/6‐311++G(d,p)//B3PW91/6‐311++G(d,p) level yielded a set of theoretical J(CC) values. A comparison of these two sets of data gave an excellent linear correlation with parameters a and b close to ideal; a = 0.9978 which is not far from unity and b = 0.22 Hz which is close to zero. The ¹J(CC) couplings determined for the crucial fragment of the molecules, i.e. ? C?C? C?O (or ? C?C? C?S), are: ¹J(C?C) ≈ 68 Hz (67 Hz) and ¹J(C? C) = 60.5 Hz (60.0 Hz). The corresponding couplings found for the Z‐s‐Z‐s‐E isomer of the parent enaminoketone, 4‐methylamino‐but‐3‐en‐2‐one are 64.1 and 59.3 Hz, respectively. The most sensitive towards substitution of the oxygen atom by sulfur are two‐bond couplings between the α‐vinylic and aromatic C_ipso carbon atoms, which attain 12 Hz in the enaminoketone derivatives and decrease to 5 Hz in their thio analogues. Copyright © 2009 John Wiley & Sons, Ltd.     

Coordination properties of 1-allyl-2-methylimidazole relative to some metal ions in the solid state and aqueous solution

Cobalt(II) and copper(II) complexes with 1-allyl-2-methylimidazole (L), of general formula [ML₂(NO₃)₂], have been prepared in the solid state. The compounds were characterised by structural, spectroscopic and magnetic measurements. The metal ions in both six coordinate complexes are surrounded by two nitrogen atoms of the imidazole rings and four oxygen atoms of the chelating nitrato group (the CoN₂O₄ and CuN₂O₄ chromophores). The structure of both chromophores is described by a very distorted tetragonal bipyramid. The formation of successive complexes of the azole with Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Cd²⁺ in aqueous solution was followed potentiometrically. An irregularity in the K_n constants of successive Co²⁺ and Zn²⁺ complexes suggests a change in the coordination sphere of the central ions from octahedral to tetrahedral. With the Co²⁺–1-allyl-2-methylimidazole system, the change has been proven by inspection of the visible absorption spectra.     

DSC studies of γ -irradiation influence on amylose-lipid complex transition in wheat flour

DSC studies were carried out in the heating-cooling cycles for non-irradiated and irradiated with -rays (⁶⁰Co) using 30 kGy dose wheat flour. The differences between gelatinisation and reversible transition of amylose-lipid complexes occurring in suspensions of non-irradiated and the irradiated flour (characterized by a dry matter to water ratio of 1:1 and 1:3) depend on the conditions applied in DSC measurements (concentration, heating/cooling rate) and on the preceding treatment of samples. An essential decrease in the temperature of amylose-lipid complex transition was discovered after irradiation. Retrogradation is inhibited in the dense gels of the irradiated samples as compared to the initial ones. The results are discussed in terms of radiation-induced destruction of the polysaccharide chains and lipid modification.     

Determination of microgram amounts of thiuram disulphides by means of the induced iodine-azide reaction

A simple method for the determination of thiuram disulphides was developed. These compounds induce the iodine-azide reaction after cleavage of the SS bond. The consumption of iodine in this reaction is proportional to the amount of the inductor. Inducing properties of the compounds examined were estimated from an induction coefficient ([I]/[S]) which indicates how many times the consumption of iodine in the induced reaction is higher than that in the iodimetric reaction. Under analytically optimum conditions the induction coefficients are in the range 176–211 for eight thiuram disulphides. The identical behaviour of thiuram disulphides in the induced reaction and of the corresponding dithiocarbamates allows the analysis of their mixture in the same sample. The method is sensitive, selective, accurate, cheap and rapid. Other compounds that induce the iodine-azide reaction interfere.     

Determination of the stoichiometry of semiconductor systems of the type CdvHg1?vSe and CdxHg1?xTe by X-ray fluorescence spectrometry

Summary Semiconductors of the composition Cd _v Hg_1–v Se and Cd _x Hg_1–x Te are gaining growing industrial interest. The energy gap between the bands of such systems depends significantly on the magnitude of the mole fractions v and x. X-ray fluorescence analysis of acid solutions of these crystals is a simple and precise procedure to determine the stoichiometry. Sample preparation, calibration series and results are discussed.

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Bestimmung der Stöchiometrie von Halbleitersystemen des Typs Cd_vHg_1–vSe und Cd_xHg_1–xTe, durch Röntgenfluorescenz-Spektrometrie

Zusammenfassung Halbleiter der Typen Cd _v Hg_1–v Se und Cd _x Hg_1–x Te gewinnen zunehmend industrielles Interesse. Der Energieabstand der Bänder in solchen Systemen hängt entscheidend von der Größe der Molenbrüche v und x ab. Ein einfaches und sicheres Analysenverfahren zur Ermittlung der Stöchiometrie ist die Röntgenfluorescenzanalyse von sauren Lösungen dieser Kristalle. Die Probenvorbereitung, Eichreihen und Resultate werden diskutiert.

Delegated to Central Institute of Analytical Chemistry, Nuclear Research Establishment (KFA), Jülich, FRG.     

Synthesis of AB diblock copolymers by atom-transfer radical polymerization (ATRP) and living polymerization of alpha-amino acid-N-carboxyanhydrides

The synthesis of poly(methyl acrylate)-block-poly(gamma-benzyl-L-glutamate) (PMA-b-PBLG) diblock copolymers, using atom-transfer radical polymerization (ATRP) of methyl acrylate and living polymerization of gamma-benzyl-L-glutamate-N-carboxyanhydride (Glu-NCA) is described. Amido-amidate nickelacycle end groups were incorporated onto amino-terminated poly(methyl acrylates), and the resulting complexes were successfully used as macroinitiators for the growth of polypeptide segments. This method allows the controlled preparation of polypeptide-block-poly(methyl acrylate) diblock architectures with control over polypeptide chain length and without the formation of homopolypeptide contaminants.     

Evaluation of critical points in technology transfer of cryopreservation protocols to international plant conservation laboratories

Cryopreservation of plant tissues in liquid nitrogen is now used for long-term conservation of vegetatively-propagated crops. Development of standard techniques for cryopreservation is important to the international plant-conservation community for successful implementation of storage protocols in diverse and internationally dispersed laboratories. Evaluation of the critical points of each preservation technique will greatly assist in developing and validating internationally-used cryopreservation protocols. The goals of this project were to assess critical points of two major cryopreservation techniques (PVS2 vitrification and encapsulation dehydration) during their transfer to international laboratories; analyze post-storage viability for each technique and location; and develop recommendations based on the assessments and data from the participating laboratories. Investigators from Germany, Kazakhstan, Poland and UK participated in a 2-week training workshop in cryopreservation methods after which the techniques were tested in the home laboratories of the participants. After one-year site visits by the technology trainers identified critical points in the protocols. Critical points were identified as 1) Cryogenic (cryoprotection, LN exposure, rewarming); 2) Non-cryogenic (plant health status, pre- and post-storage culture); 3) Operational (skills transfer, training, interpretation of procedures); 4) Facility (growth room, ambient conditions, media preparation, equipment). The most critical factors in all laboratories were culture health, operator skills and experience, and clarification of the technical details of the procedures. Final results showed that correction of critical factors improved the post-storage recovery in all the laboratories.     

Numerical Behaviour of Higham's Scaled Method for Polar Decomposition

We present a rounding error analysis of Higham's scaled method for computing the polar decomposition of a nonsingular complex matrix. Under certain natural conditions we prove that the method computes acceptable polar factors.     

Total Curvature and Spiralling Shortest Paths

This paper gives a partial confirmation of a conjecture of Agarwal, Har-Peled, Sharir, and Varadarajan that the total curvature of a shortest path on the boundary of a convex polyhedron in R ³ cannot be arbitrarily large. It is shown here that the conjecture holds for a class of polytopes for which the ratio of the radii of the circumscribed and inscribed ball is bounded. On the other hand, an example is constructed to show that the total curvature of a shortest path on the boundary of a convex polyhedron in R ³ can exceed 2. Another example shows that the spiralling number of a shortest path on the boundary of a convex polyhedron can be arbitrarily large.