1.2 Anorganische analyse

Ohne Zusammenfassung     

Stereoselectivity in Reactions of Metal Complexes. Part XI. 2,6-Bis(pyrrolidin-2-yl)pyridine: Synthesis and resolution of the meso and the optically active isomers. Complex formation with copper(II) ion in aqueous solution

The new linear triamine 2,6-bis(pyrrolidin-2-yl)pyridine ( II ) has been synthesized, and the (R, S)-, (R, R)-, and (S, S)-isomers have been separated. Compared to other triamines showing a similar structure, these new ligands form very stable Cu²⁺ complexes. No significant difference is observed between the meso and the racemic forms for their binary or ternary mixed-ligand complexes with the amino acids alanine and proline.     

Single-server queues with spatially distributed arrivals

Consider a queueing system where customers arrive at a circle according to a homogeneous Poisson process. After choosing their positions on the circle, according to a uniform distribution, they wait for a single server who travels on the circle. The server's movement is modelled by a Brownian motion with drift. Whenever the server encounters a customer, he stops and serves this customer. The service times are independent, but arbitrarily distributed. The model generalizes the continuous cyclic polling system (the diffusion coefficient of the Brownian motion is zero in this case) and can be interpreted as a continuous version of a Markov polling system. Using Tweedie's lemma for positive recurrence of Markov chains with general state space, we show that the system is stable if and only if the traffic intensity is less than one. Moreover, we derive a stochastic decomposition result which leads to equilibrium equations for the stationary configuration of customers on the circle. Steady-state performance characteristics are determined, in particular the expected number of customers in the system as seen by a travelling server and at an arbitrary point in time.     

New disc-shaped mesogens based on pentakis(phenylethynyl)benzene derivatives

First examples of amphiphilic alkyl pentakis(phenylethynyl)benzene ethers containing functional groups at the terminal position of their alkoxy chains were synthesized by etherification of pentabromophenol with 11-bromoundecan-1-ol and 11-bromoundecanoic acid ethyl ester, respectively, and subsequent palladium catalyzed, fivefold coupling reactions with the substituted phenylacetylene. Two undecanoic acid derivatives with different pentakis(phenylethynyl)phenoxy substituents in the ω-position were prepared by ester cleavage from the corresponding ethyl esters. The thermal behaviours of five penta-alkynes in their pure states, as well as of their charge transfer complexes formed from mixtures with 2,4,7-tri-nitrofluorenone, were examined.     

Orientation and relaxation of polymer–clay solutions studied by rheology and small-angle neutron scattering

The influence of shear on viscoelastic solutions of poly(ethylene oxide) (PEO) and clay [montmorillonite, i.e., Cloisite NA+ (CNA)] was investigated with rheology and small-angle neutron scattering (SANS). The steady-state viscosity and SANS were used to measure the shear-induced orientation and relaxation of the polymer and clay platelets. Anisotropic scattering patterns developed at much lower shear rates than in pure clay solutions. The scattering anisotropy saturated at low shear rates, and the CNA clay platelets aligned with the flow, with the surface normal parallel to the gradient direction. The cessation of shear led to partial and slow randomization of the CNA platelets, whereas extremely fast relaxation was observed for laponite (LRD) platelets. These PEO–CNA networklike solutions were compared with previously reported PEO–LRD networks, and the differences and similarities, with respect to the shear orientation, relaxation, and polymer–clay interactions, were examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3102–3112, 2004     

Mass transport in anharmonic potentials

We investigate the effect of nuclear shell structure on the mass transport in low-energy heavy-ion collisions. The shell-correction energy leads to anharmonic driving potentials and thus, to nonlinear drift coefficients in the Fokker-Planck equation. Results for²³⁸U (7.42 MeV/nucleon)+²³⁸U are presented. The drift towards the closed Pb-shell enhances the fluctuations in the mass transport and provides an explanation for the large variances found experimentally. Local maxima in the mass distribution at the shell minima disappear due to the temperature dependence of the driving potential.