Umsetzung von hydrobromiertem 1,4-Polybutadien mit lithiumorganischen Verbindungen

Ohne ZusammenfassungMit 1 Abbildung und 1 Tabelle     

Energy-adjustedab initio pseudopotentials for the second and third row transition elements

Summary Nonrelativistic and quasirelativisticab initio pseudopotentials substituting the M^(Z–28)+-core orbitals of the second row transition elements and the M^(Z–60)+-core orbitals of the third row transition elements, respectively, and optimized (8s7p6d)/[6s5p3d]-GTO valence basis sets for use in molecular calculations have been generated. Additionally, corresponding spin-orbit operators have also been derived. Atomic excitation and ionization energies from numerical HF as well as from SCF pseudopotential calculations using the derived basis sets differ in most cases by less than 0.1 eV from corresponding numerical all-electron results. Spin-orbit splittings for lowlying states are in reasonable agreement with corresponding all-electron Dirac-Fock (DF) results.     

Kraftfeldrechnungen an linearen Oligopyrrolen: 2,2′-Bipyrrol, 2,2′-Furylpyrrol und Prodigiosen

Using a specific force field model, relative stabilities of 2,2-bipyrrole and 2,2-furylpyrrole conformers as well as of prodigiosene tautomers, configurations, and conformations, are studied. 2,2-Bipyrrole adopts anantiperiplanar conformation in accord with other theoretical calculations and experimental findings. Its rotational barrier calculated by this method compares favourably to the one derived by other means. For the parent prodigiosene the (Z)sp,sp arrangement is found to be the most stable one. The two possible tautomers within its dipyrrin fragment do not show a significant energy difference.

     

Observation of the ND4 Schüler band in a neutralized ion beam experiment

The emission of the ND₄ Schüler band was observed after neutralization of a mass-selected ND ₄ ⁺ ion beam. Thus the assignment of this band to the ammonium radical was confirmed. The lifetime of the upper state (3p ² F ₂) was determined to be 4.2 ns, which is much shorter than ab initio values of the radiative lifetime, showing that this state decays predominantly by predissociation. The Schuster band was not observed, neither after neutralization of ND ₄ ⁺ , nor of ND ₃ ⁺ .     

Measurement of γp→K + Λ and γp→K + Σ 0 at photon energies up to 1.47 GeV

The reactions pK ⁺ and pK ^{+ 0} have been measured with the multiparticle detector system SAPHIR at ELSA in Bonn. Besides the differential cross sections the polarization and, for the first time, the ⁰ polarization have been determined in a photon induced reaction. All data are presented as functions of the photon energy (from threshold up to 1.47 GeV) and of the kaon production angle (0°–180°). The polarization of both and ⁰ is substantial at all energies and varies strongly with the production angle.This work is supported by the Bundesminister für Forschung und Technologie (BMFT), FK 06 BN 621 I     

Production of fast evaporation residues by the reaction20Ne+208Pb at projectile energies of 8.6, 11.4 and 14.9 A.MeV

Velocity distributions and production cross sections of evaporation residues have been measured in the reaction²⁰Ne+²⁰⁸Pb at projectile energies of 8.6, 11.4, 14.9 A.MeV. Essential deviations from statistical model of deexcitation have been observed. Monte Carlo simulations involving emission of non-equilibrium particles have been used in order to reproduce experimental velocity, charge and mass distributions of evaporation residues and to estimate indirectly multiplicities of pre-equilibrium particles. Communicated by V. Metag     

Synthesis of a new class of chiral 1,5-diphosphanylferrocene ligands and their use in enantioselective hydrogenation

A new family of ferrocenylphosphane ligands has been prepared. Their flexible synthesis allows many structural modifications. The asymmetric induction of these ligands was examined in the hydrogenation of functionalized C=C, C=O, and C=N bonds. The enantioselectivity of the reaction was strongly dependent on the substituent R at the position alpha to the ferrocene moiety. In many cases, both enantiomeric beta-hydroxyesters of the reduction product can be obtained by simply replacing a dimethylamino group in the ligand with a methyl group.     

Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either 1-phenylethylbromide or 1,4-dibromoxylene as initiators for ATRP. Diverse bromo(ester) (macro)initiators were also devised and involved in the formulation of fluorinated pentablock as well as amphiphilic triblock copolymers with a central polyether segment. Amphiphilic star-shaped fluoropolymers, hydrophobic fluorinated nanoparticles, or segmented fluorinated star-shaped block copolymers are further designed by use of different multifunctional initiators. The composition of the novel materials with PFS is determined by combination of SEC and ¹H NMR. Glass transition temperatures and thermal stabilities of the hydrophobic star-shaped PFSs on a six arm dipentaerythritol core are investigated in a wide range of molecular masses and further discussed.     

The isotopes259106,260106, and261106

In irradiations of²⁰⁷Pb and²⁰⁸Pb, respectively, with⁵⁴Cr theα-decay of the isotopes²⁵⁹106,²⁶⁰106, and²⁶¹106 could be observed for the first time. For²⁶⁰106 a spontaneous fission branch of (50 _?20 ⁺³⁰ )% was observed. The isotopes were identified by genetic relationships of α-decay after separation in-flight with the velocity filter SHIP and implantation into a position-sensitive silicon surface-barrier detector. The measured partial fission halflife of the doubly even isotope²⁶⁰106 of (7.2 _?2.7 ^+4.8 )ms exceeds the predicted values by at least a factor of 40. This result could be explained by the high shell corrections of the ground state mass, derived from the measured α-decay energies. The experimental results show evidence for an island of purely shell stabilized nuclei in the region of deformed isotopes beyond the actinides.     

Rapid identification and quantitation of compounds with forensic interest using fast liquid chromatography-ion trap mass spectrometry and library searching

A fast liquid chromatography-electrospray tandem mass spectrometric (LC-ESI-MS-MS) method by using a monolithic column, gradient elution and ion trap mass spectrometer was developed for 14 forensically interesting and chemically different compounds. All compounds were eluted within 2.5 min and the total analysis time was 5 min including stabilisation time required for the next injection. All the compounds, basics, neutrals and acids were efficiently ionised by positive ion ESI. A laboratory library including MS-MS spectra and retention times was developed and tested. Results with 476 standard samples and 50 authentic samples showed that the compounds studied can be unambiguously identified with the library. A quantitative method was developed for the compounds using external calibration. The evaluation process showed good linearity of the method and reasonable repeatability. Limits of detection ranged from 10.0 to 50.0 ng/ml.