Superoxide-mediated dehydrohalogenation reactions of the pyrethroid permethrin and other chlorinated pesticides

Superoxide generated in DMF readily converts the dihalovinyl group of permethrin and related compounds to a haloethynyl moiety and yields major products from elimination reactions of DDT, $\text{cis}$-chlordane, and 1,2-dibromo-3-chloropropane (DBCP).     

Weighted majority games and the matrix of homogeneity

If a weighted majority game (not necessarily constant sum or super additive) is described by the weights (voting strength) of the players involved and a majority level, then it is desirable to know whether the game is in addition homogeneous. The paper provides a recursive procedure defining a test for homogeneity. This procedure involves the computation of a number theoretical function, the matrix of homogeneity. If this matrix is knownall majority levels with respect to which the given set of weights represents a homogeneous simple weighted majority game are known at once.

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Zusammenfassung Ein gewichtetes Majoritätsspiel (nicht notwendig superadditiv oder mit Konstantsummeneigenschaft) kann beschrieben werden durch die Gewichte (die Abstimmungsstärke) der beteiligten Spieler und durch eine Mehrheitsschranke. Wenn eine solche Darstellung gegeben ist, so ist es wünschenswert, das Spiel zusätzlich auf die Eigenschaft der Homogenität hin zu untersuchen. Die vorliegende Arbeit stellt eine rekursive Prozedur zur Verfügung, die einen Test auf Homogenität einer vorgelegten Darstellung eines Spieles impliziert. Die Prozedur ermöglicht die Berechnung einer zahlentechnischen Funktion, der Homogenitätsmatrix. Wenn diese Matrix bekannt ist, kann man bei einem vorgegebenen Gewichtssatz alle Majoritätsschranken angeben, bezüglich welcher die vorgelegten Gewichte ein homogenes einfaches gewichtetes Majoritätsspiel darstellen.

     

Application of the ellipsoid method in an interactive procedure for multicriteria linear programming

The research reported in this paper is concerned with an application of the ellipsoid algorithm in the interactive multicriteria linear programming step method (STEM) byBenayoun et al. [1971]. Due to this application we eliminate some drawbacks of the original version of STEM and, moreover, we avoid extra computations connected with sensitivity analysis in every iteration. Specifically, we use the ellipsoid algorithm to minimize the Euclidean norm in the criterion space instead of the Chebyshev norm, which ensures that every solution submitted to the decision maker is efficient. As follows from a computational experiment, in comparison with the application of the simplex method, the proposed modification of STEM shows a smaller increase of the computational effort when the number of criteria increases. However, the absolute computation time becomes worse for problems of larger size.

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Zusammenfassung In dieser Arbeit wird über eine Anwendungsmöglichkeit der Khachiyan-Shor-Algorithmus (Ellipsoid-Algorithmus) im Rahmen des STEM-Verfahrens zur interaktiven Lösung linearer Vektoroptimierungsmodelle berichtet. Auf diese Weise können einige spezifische Nachteile des STEM-Verfahrens in seiner Originalversion vermieden werden. Durch die Verwendung der Euklidischen Norm anstelle der beim STEM-Verfahren üblichen Tschebyscheff-Norm wird garantiert, daß dem Entscheidungsträger nur effiziente Lösungen vorgeschlagen werden. Die numerischen Erfahrungen zeigen, daß der Lösungsaufwand der hier vorgeschlagenen Modifikation des STEM-Verfahrens mit steigender Anzahl von Zielfunktionen weniger stark zunimmt als bei der üblichen Version. Dies gilt jedoch nicht hinsichtlich der allgemeinen Problemgröße.

     

Registrierende Messung des mechanischen Verlustes von Kunststoffproben

Zusammenfassung Ein neues Verfahren, das eine unmittelbare und kontinuierliche Registrierung des mechanischen Verlustwinkels über einen weiten Temperaturbereich erm?glicht, wird beschrieben. Die Probe wird einer periodischen Biegung (f=2,5 Hz) unterworfen; die Zeit des Kraftnulldurchgangs relativ zur Bewegung ist dem Verlustwinkel proportional und wird elektronisch ermittelt. Das Me\ergebnis ist weitgehend von der Probenform und deren ?nderung w?hrend der Messung (Krümmung der Probe, thermische Ausdehnung usw). unabh?ngig. Der Deutschen Forschungsgemeinschaft sei für die Unterstützung dieser Arbeit verbindlichst gedankt.     

Strukturviskosität von verdünnten Lösungen von Biopolymeren

The importance of the rheological behaviour of solutions of macromolecules is briefly evaluated. The viscosity of the solutions depends on concentration, shear rate and time of shear, this relation being determined by the structure of the dissolved molecules. In dilute solutions shear dependence of viscosity is very frequently caused by the preferential orientation of anisotropic molecules. In such a case the particle dimensions can be calculated from the true limiting viscosity number, an anisotropy factor, the rotational diffusion constant and the effective particle density. These numbers can be derived from the flow curve, which has been extrapolated to zero concentration. It is necessary to measure the flow curve at shear gradients, which are sufficiently low to allow for an extrapolation to vanishing shear rate. By comparing the experimental flow curve with a choice of theoretical ones, the rotational diffusion constant and the anisotropy factor (axial ratio) can be found. From the limiting viscosity number and the axial ratio, the particle density can be calculated.     

Komplexe von 2,6-Dimethylpyridin-1-oxid mit Lanthanidjodiden

Complexes of 2,6-dimethylpyridine 1-oxide with lanthanide iodides of the formulaeLn(2,6-LTNO)₅I₃ whereLn=La, Tb and Yb,Ln(2,6-LTNO)₄I₃ whereLn=Pr and Nd and Er(2,6-LTNO)_4.5I₃ have been prepared and characterised by chemical analysis, infrared and conductance studies. Infrared and conductance data have been interpreted in terms of dimeric (or polymeric) structures involving bridging amine oxide groups.

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Mit 2 Abbildungen     

Über die Synthese von 5-(o-Trifluormethylphenyl)-1H-thieno[3,4—e]-1,4-diazepin-2(3H)-onen

The synthesis of 5-(o-trifluoromethylphenyl)-1H-thieno-[3,4-e]1,4-diazepin-2(3H)-one (7) and its nitration and chlorination in pos. 8 are described.     

Berechnung von mittleren Schwingungsamplituden einiger tetraedrischer Moleküle und Ionen nach der Methode der charakteristischen Schwingungen

Mean amplitudes of vibration of a series of tetrahedralXY ₄ molecules and ions (hydrides, halides, oxides and oxoanions) have been calculated using the “Method of the Characteristic Vibrations” ofA. Müller. The results indicate that this method leads to very good values for most of the investigated species, and especially in the cases of highM _X/M_Y mass ratio.     

Generation of High-Oxidation States of Myoglobin in the Nanosecond Time-Scale by Laser Photoionization

Abstract— The 248 nm laser flash photolysis of myoglobin in various redox states (oxy, met and ferryl) in neutral aqueous solution yielded hydrated electrons with concurrent changes in the visible absorption spectrum of the heme. The results could be ascribed to the photoionization of both the peptide and the heme group, in approximately equal yields. The ionization of met- and ferrylmyoglobin was biphotonic, but that of oxymyoglobin was a mixture of mono- and biphotonic processes. Using appropriate electron and radical scavengers, the changes in the heme absorption could be investigated at times ≥100 ns and were shown to be associated with a +1 increase of the formal oxidation state of the heme. Using this method, the formal iron(V) state of native myoglobin could be spectroscopically characterized for the first time. Its absorption, blue-shifted and less intense relative to the ferryl state, is reminiscent of that of the compound I of peroxidases, which contains a ferryl-oxo (iron[IV]) group and a porphyrin radical cation. On this basis, the same structure is proposed for the formal iron(V) state of native myoglobin. The transition from oxy- to metmyoglo-bin took -5 μs, which may reflect the kinetics of exchange of oxygen with water as ligand. The transitions from the met to the ferryl state, and from ferryl to iron(V) states were faster (∽250 ns), consistent with processes that involve proton or electron movements but no changes in the iron coordination state.     

An unexpected P-cluster like intermediate en route to the nitrogenase FeMo-co

The nitrogenase MoFe protein contains two different FeS centers, the P-cluster and the iron–molybdenum cofactor (FeMo-co). The former is a [Fe₈S₇] center responsible for conveying electrons to the latter, a [MoFe₇S₉C-(R)-homocitrate] species, where N₂ reduction takes place. NifB is arguably the key enzyme in FeMo-co assembly as it catalyzes the fusion of two [Fe₄S₄] clusters and the insertion of carbide and sulfide ions to build NifB-co, a [Fe₈S₉C] precursor to FeMo-co. Recently, two crystal structures of NifB proteins were reported, one containing two out of three [Fe₄S₄] clusters coordinated by the protein which is likely to correspond to an early stage of the reaction mechanism. The other one was fully complemented with the three [Fe₄S₄] clusters (RS, K1 and K2), but was obtained at lower resolution and a satisfactory model was not obtained. Here we report improved processing of this crystallographic data. At odds with what was previously reported, this structure contains a unique [Fe₈S₈] cluster, likely to be a NifB-co precursor resulting from the fusion of K1- and K2-clusters. Strikingly, this new [Fe₈S₈] cluster has both a structure and coordination sphere geometry reminiscent of the fully reduced P-cluster (P^N-state) with an additional μ²-bridging sulfide ion pointing toward the RS cluster. Comparison of available NifB structures further unveils the plasticity of this protein and suggests how ligand reorganization would accommodate cluster loading and fusion in the time-course of NifB-co synthesis.

The K-cluster of NifB as a key intermediate in the synthesis of the nitrogenase active site supports [Fe₄S₄] cluster fusion occurs before carbide and sulfide insertion and displays ligand spatial arrangement reminiscent to that of the P-cluster.