Isomerisierung bei der Komplexbildung von 3-Acetyl-tetramsäure: Struktur und magnetische Eigenschaften des CuII- und NiII-Komplexes von 2,7-Bis(1′, 5′, 5′-trimethylpyrrolidin-2′, 4′-dion-3′ -yl)-3, 6-diazaocta-2, 6-dien

Isomerization at the Complexation of 3-Acetyltetramic Acid: Structure and Magnetic Properties of the Cu^II- and Ni^II-Complex of 2,7-Bis (1′, 5′, 5′ -trimethylpyrrolidin-2′,4′ -dion-3′ -yl)-3,6-diazaocta-2,6-dien 2,7-Bis(1′, 5′, 5′ -trimethylpyrrolidin-2′, 4′ -dion-3′ -yl)-3,6-diazaoctadien formes Cu^II and Ni^II complexes with different constitutions (because of the Z/E isomerization). Results of X-ray analysis of N,N′ -ethylenbis(1′, 5′, 5′ -trimethylpyrrolidin-2′, 4′ -dion-3′ -acetiminato)nickel(II) 1 respectively -copper(II) 2 shows, that the complexing agent in 1 occurs in the E-form, whereas the ligand of the Cu^II complex forms the Z-form. Magnetic susceptibility and shift effects of the ¹³C-NMR signals point to a weak paramagnetism of the Ni^II complex. ESR-spectra are obtained from 2 only. Furthermore, the Cu^II complex reduces the relaxation times T₁ and T₂ of ¹H and ¹⁷O nuclei spins from water. From the temperature dependence of the shortening of the relaxation times an activation energy is calculated which describes the reorientation of the copper complex in the “water matrix”.     

Oscillatory dynamics protect enzymes and possibly cells against toxic substances

We have used the oscillating peroxidase-oxidase (PO) reaction as a model system to study how oscillatory dynamics may affect the influence of toxic reaction intermediates on enzyme stability. In the peroxidase-oxidase reaction reactive intermediates, such as hydrogen peroxide, superoxide, and hydroxyl radical are formed. Such intermediates inactivate many cellular macromolecules such as proteins and nucleic acids. These reaction intermediates also react with peroxidase itself to form an inactive enzyme. The fact that the PO reaction shows bistability between an oscillatory and a steady state gives us a unique possibility to compare such inactivation when the system is in one of these two states. We show that inactivation of peroxidase is slower when the system is in an oscillatory state, and using numerical simulations we provide evidence that oscillatory dynamics lower the average concentration of the reactive intermediates.     

Conditioning of Random Conic Systems Under a General Family of Input Distributions

We consider the conic feasibility problem associated with the linear homogeneous system Ax≤0, x≠0. The complexity of iterative algorithms for solving this problem depends on a condition number C(A). When studying the typical behavior of algorithms under stochastic input, one is therefore naturally led to investigate the fatness of the tails of the distribution of C(A). Introducing the very general class of uniformly absolutely continuous probability models for the random matrix A, we show that the distribution tails of C(A) decrease at algebraic rates, both for the Goffin–Cheung–Cucker number C _G and the Renegar number C _R . The exponent that drives the decay arises naturally in the theory of uniform absolute continuity, which we also develop in this paper. In the case of C _G , we also discuss lower bounds on the tail probabilities and show that there exist absolutely continuous input models for which the tail decay is subalgebraic. R. Hauser was supported by a grant of the Nuffield Foundation under the “Newly Appointed Lecturers” grant scheme (project number NAL/00720/G) and through grant GR/S34472 from the Engineering and Physical Sciences Research Council of the UK. The research in this paper was conducted while T. Müller was a research student at the University of Oxford. He was partially supported by EPSRC, the Oxford University Department of Statistics, Bekker-la-Bastide fonds, Dr. Hendrik Muller’s Vaderlandsch fonds, and Prins Bernhard Cultuurfonds.     

A historical note on the entropy principle of Müller and Liu

Received July 12, 2001 / Published online February 28, 2002     

Mössbauer investigations of intermolecular interactions of Fe(CO)5 in frozen organic solutions

The Mössbauer spectra of Fe(CO)₅ dissolved in 39 organic solvents were investigated. An influence on the quadrupole split was found only for those solvents containing carbonylic CO, but not for solvents containing another polar group. The change of the quadrupole split means always a reduction and is independent of temperature. The concentration dependence of the additional split indicates that it is caused only by nearest neighbours.—These results give a hint for a specific weak interaction between the carbonylic CO group of Fe(CO)₅ and the solvents. This cannot be a general dipole-dipole interaction because of the missing influence of other polar solvents, so that a weak chemical bond is suggested.     

Röntgenkleinwinkeluntersuchungen der Eisen(III)-oxidhydrat-Micelle des Ferritins in Lösung

Ohne Zusammenfassung     

First direct observation of coulomb explosion during the formation of exotic atoms

A Doppler broadening of x-ray transitions from pionic nitrogen and muonic oxygen, which is attributed to Coulomb explosion of the molecules, has been observed by using a crystal spectrometer. Large linewidths indicate fast ionization of the molecules and a charge of (3-4)e for the accelerated fragments.