Die Deprotonierung von Metallaquoionen II: Aquochrom(III)-ion. Zur Struktur aktiver Chromhydroxide

On alkalinization of solutions of the chromiun(III)-aquo ion simple deprotonation takes place first. The degree of hydroxylation n _OH however can be brought up to only about 1 (the exact value depending on the total concentration [Cr]_t), before the uncharged complex Cr(OH)₃(OH₂)₃ is precipitated. The structure of the very sparingly soluble complex (solubility ～10^?7M ) is held together by hydrogen bonds of type I between the molecules, so that its formula may be written as Cr(OH)₂H_6/2-lattice. The formation of the well ordered structure is extremely fast. On aging, the metallic centers become connected by μ-hydroxo-bridges (type II) and the substances become amorphous and very insoluble. The dinuclear (H₂O)₄Cr(OH)₂Cr(OH₂)₄⁴⁺ behaves similar on deprotonation. Concerning the various equilibria constants see Table 1.     

On a new method for constructing good point sets on spheres

We use quadrature formulas with equal weights in order to constructN point sets on spheres ind-space (d 3) which are almost optimal with respect to a discrepancy concept, based on distance functions (potentials) and distance functionals (energies). By combining this approach with the probabilistic method, we obtain almost best possible approximations of balls by zonotopes, generated byN segments of equal length.Editors' note: We learned with sadness of Gerold Wagner's untimely death as a result of an avalanche in the Alps shortly after the submission of this paper. When one of the referees, Joram Lindenstrauss, suggested that Wagner's results might be extended to dimensions >6, we invited Professor Lindenstrauss to submit a paper containing that extension which we would publish alongside the Wagner paper. The result is the paper by Bourgain and Lindenstrauss that follows the present one.     

Dielectric Shielding of Ionic Charges in Aqueous Solutions of Different Ionic Strength

The thermodynamic functions of the proton transfer H₂tn²⁺+tn → 2 Htn⁺ (tn = 1,3-diaminopropane) have been determined in aqueous solutions containing different amounts of KCl (0.05 ? μ ? 3.01). The free energy (?ΔG) of the process decreases, whereas the enthalpy (-ΔH) increases with μ. There is reason to believe that the reaction is entirely controlled by the Coulomb forces between the two protonic charges. The electrostatic energy involved can be described in terms of a model incorporating an effective dielectric constant εe, such that δε_e/δμ and δ²ε_e/δμδT are both positive. The polarisation of pure water is produced by orientation of hydrogen-bonded dipole molecules H₂O, whereas the electrolyte solution is polarised in addition by dislocation of the ions K⁺ and Cl^?. Our results demonstrate that the former type of polarisation is much more temperature dependent than the latter.     

Renormalization group and high-temperature series for the two-dimensional ising model

We employ high-temperature series to investigate a two-parameter class of renormalization group transformations for the two-dimensional Ising model on the triangular lattice. For the static case we identify an optimal organization of the high-temperature expansion and an optimal transformation matrix and thus find, in second order, =0.96 and the magnetic eigenvaluey=2-/2=1.76.From recursion relations for flip rates we find the dynamic exponent to be the same for all transformations in our two-parameter class,z=2.32.Our fixed-point flip rates do not describe a Markov process even though the corresponding master equation for the single-event probability displays no explicit memory effects. The non-Markovian nature shows up only in a violation of the Markovian detailed balance conditions.     

Purification of astilbin and isoastilbin in the extract of smilax glabra rhizome by high-speed counter-current chromatography

Purification of astilbin from the rhizome extract of Smilax glabra was conducted using a high-speed counter-current chromatograph equipped with a 700 mL column. In a single operation, 1.5 g of crude sample was separated to yield 105 mg of component astilbin and 48 mg of isoastilbin while the upper phase of the two-phase solvent system composed of n-hexane-n-butanol-water (1:1:2, v/v/v) was used for stationary phase. The chemical structures of the two flavonoid glycosides were confirmed by electrospray ionization ion trap multiple mass spectrometry and nuclear magnetic resonance experiments.     

Extension of conjugation leading to bathochromic or hypsochromic effects in OPV series

Four OPV series 1-4 (a-d) with a terminal dialkylamino group as electron donor were prepared by Wittig-Horner reactions. To study the influence of the push-pull effect on the long-wavelength absorption, three of the four series contained terminal acceptor groups (CN, CHO, NO(2)). The length of the chromophores strongly affects the intramolecular charge transfer (ICT)-an effect which superimposes upon the extension of the conjugation. Increasing numbers n of repeat units cause an overall bathochromic shift for the purely donor-substituted series 1 a-4 a and the series 1 b-4 b with CN as weak acceptor. The two effects annihilate each other in the series 1 c-4 c with terminal CHO groups, so that the absorption maxima are almost independent of the length of the chromophore. A hypsochromic shift is observed for the series 1 d-4 d, which contains the strong acceptor group NO(2). This anomaly disappears on protonation of the dialkylamino group because the push-pull effect disappears in the ammonium salts. The results can be explained by semiempirical quantum mechanics (AM1, INDO/S). The HOMO-LUMO transition, which is mainly responsible for the ICT, becomes less important in the electron transitions S(0)-->S(1) when the distance between donor and acceptor is increased. The commonly used VB model, which contains an electroneutral and a zwitterionic resonance structure, is contrasted with a MO model with dipole segments at both ends of the OPV chains. The latter model turned out to be more appropriate-at least for donor-acceptor-substituted OPVs with n >/= 2.