Trennung des Eisens von Cer durch Verteilen zwischen zwei L?sungsmitteln

Zusammenfassung Eisen und Cer lassen sich in Gegenwart von Ammoniumthiocyanat in salzsaurer Lösung durch Ausschütteln mit Äther + Tetrahydrofuran quantitativ trennen. Die Trennung ist in 8–10 min durchzuführen.     

New highlights in the synthesis and reactivity of 1,4-dihydropyrazine derivatives

In the course of our investigations on the synthesis of original nitrogen heterocyclic derivatives, we were interested in the synthesis and study of original 1,4-dihydropyrazine rings. To this aim the desired bisvinylphosphate derivative was prepared from N-Boc piperazine-2,5-dione and then was engaged in palladium catalyzed reactions (reduction, Suzuki and Stille cross-coupling reactions). The 1,4-dihydropyrazine and the corresponding 2,5-disubstituted derivatives were obtained in fair to good yields and were then functionalized under anionic conditions. Aromatization into 1,4-pyrazines was investigated in a second stage.     

Impact of selective excitation on carbon longitudinal relaxation: Towards fast solid-state NMR techniques

The effect of selective pulses on the apparent carbon longitudinal relaxation is investigated in three fully ¹³C-labeled systems, histidine as a model system and two proteins MerP and YajG. It is shown that the longitudinal relaxation of a selectively excited carbon spin is greatly enhanced, mainly because of fast spin-diffusion. This relaxation enhancement allows reducing the time necessary for polarization recovery between two experiments. This effect can be exploited either to improve the sensitivity of NMR experiments or to reduce the experimental time. Using selective carbon excitation combined with fast pulsing on fully ¹³C-labeled proteins, a sensitivity improvement of 20–45% over standard cross-polarization methods is predicted from the measured relaxation times.     

Cytotoxic and Photocytotoxic Effects of Cercosporin on Human Tumor Cell Lines

Cercosporin is a naturally occurring perylenequinone. Although other perylenequinones have been extensively studied as photosensitizers in photodynamic therapy of cancer (PDT), cercosporin has been studied in this light only within the remits of phytopathology. Herein, we investigated the photocytotoxicity of cercosporin against two glioblastoma multiforme (T98G and U87) and one breast adenocarcinoma (MCF7) human cell lines. Cercosporin was found to be a potent singlet oxygen producer upon 532 nm excitation, while its cell loading was similar for MCF7 and U87, but approximately threefold higher for T98G cells. The subcellular localization of cercosporin was in all cases in both mitochondria and the endoplasmic reticulum. Light irradiation of cercosporin‐incubated cells around 450 nm showed that T98G cells were more susceptible to cercosporin PDT, mainly due to their higher cercosporin uptake. Metabolic studies before and 1 h following cercosporin PDT showed that cercosporin PDT instigated a bioenergetic collapse in both the respiratory and glycolytic activities of all cell lines. In the dark, cercosporin exhibited a synergistic cytotoxicity with copper only in the most respiratory cell lines (MCF7 and T98G). Cercosporin is a potent photosensitizer, but with a short activation wavelength, mostly suitable for superficial PDT treatments, especially when it is necessary to avoid perforations.     

The effective medium and the average field approximations vis-à-vis the Hashin-Shtrikman bounds. I. The self-consistent scheme in matrix-based composites

The effective medium approximation (EMA) and the average field approximation (AFA) are two classical micromechanics models for the determination of effective properties of heterogeneous media. They are also known in the literature as ‘self-consistent’ approximations. In the AFA, the basic idea is to estimate the actual average field existing in a phase through a configuration in which a typical particle of that phase is embedded in the homogenized medium. In the EMA, on the other hand, one or more representative microstructural elements of the composite is embedded in the homogenized effective medium subjected to a uniform field, and the demand is made that the dominant part of the far-field disturbance vanishes. Both parts of this study are concerned with two-phase, matrix-based, effectively isotropic composites with an inclusion phase consisting of randomly oriented particles of arbitrary shape in general, and ellipsoidal shape in particular. The constituent phases are assumed to be isotropic. It is shown that in those systems the AFA and EMA give different predictions, with the distinction between them becoming especially striking regarding their standing vis-à-vis the Hashin-Shtrikman (HS-bounds). While due to its realizability property the EMA will always obey the bounds, we show that there are circumstances in which the AFA may violate the bounds. In the AFA for two-phase matrix-based composites, the embedded inclusion is a particle of the inclusion phase. If the particle is directly embedded in the effective medium, the method is called here the self-consistent scheme-average field approximation (SCS-AFA), and will obey the HS-bounds for an inclusion shape that is simply connected. If the embedded entity is a matrix-coated particle, then the method is called the generalized self-consistent scheme-average field approximation (GSCS-AFA), and may violate the HS-bounds. On the other hand, in the EMA for matrix-based composites with well-separated inclusions, we indicate that in view of its premises the embedding with a matrix-coated particle generally becomes the appropriate one, and the method is thus called the generalized self-consistent scheme-effective medium approximation (GSCS-EMA). Part I of this study is concerned with SCS-AFA in dielectrics and elasticity, and Part II with the GSCS-AFA and GSCS-EMA in dielectrics.     

A Note on the Set Covering Problem

A previously published work on a ‘probabilistic’ formulation of the set covering problem is discussed. Attention is drawn to the dependence of the feasible locations of facilities on the way the continuous space of incidents is divided into subregions when using either the above formulation or the standard deterministic formulation of the set covering problem.     

One way to solve the parametric quadratic programming problem

A method is presented for the solution of the parametric quadratic programming problem by the use of conjugate directions. It is based on the method for quadratic programming proposed by the author in [1].While engaged in this research the author had a part-time post with the Manpower Services Commission.     

An asymptotic theory for coupled thermoelastic wave propagation in rods

A systematic approach to obtain successive approximations to the coupled thermoelastic dynamic problem of a circular cylindrical rod is developed. The equations governing the first two terms of the asymptotic series are derived. The lowest order approximation gives the classical one-dimensional thermoelastic rod equations. The second-order term describes the lateral inertia correction for the coupled thermoelastic rod.

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Zusammenfassung Ein systematisches Verfahren zur Herleitung sukzessiver Näherungstheorien für das dynamische, gekoppelte, thermoelastische Problem eines kreiszylindrischen Stabs wird entwickelt. Die expliziten Differentialgleichungen der ersten zwei Näherungen werden aufgestellt. Die tiefste Ordnung ergibt die klassischen, eindimensionalen, thermoelastischen Stabgleichungen. Die zweite Ordnung stellt die Korrektur der lateralen Trägheit dar.

     

Gold(I)/Gold(III) Catalysis that Merges Oxidative Addition and π‐Alkene Activation

Heteroarylation of alkenes with aryl iodides was efficiently achieved with a (MeDalphos)AuCl complex through Au^I/Au^III catalysis. The possibility to combine oxidative addition of aryl iodides and π‐activation of alkenes at gold is demonstrated for the first time. The reaction is robust and general (>30 examples including internal alkenes, 5‐, 6‐, and 7‐membered rings). It is regioselective and leads exclusively to trans addition products. The (P,N) gold complex is most efficient with electron‐rich aryl substrates, which are troublesome with alternative photoredox/oxidative approaches. In addition, it provides a very unusual switch in regioselectivity from 5‐exo to 6‐endo cyclization between the Z and E isomers of internal alkenols.