Single-Site Organochromium Catalysts: Synthesis,Characterisation by Paramagnetic NMR and Olefin Polymerisation

Chromium(III)-complexes with monoanionic spectator ligands allow the preparation of highly active catalysts for ethylene polymerisation. We summarize the synthesis and NMR-spectroscopic investigations of precatalysts with quinolyl-functionalised Cp-ligands. These complexes have advantageous properties. For spectroscopic investigations the rigidity of the ligand framework helps to identify the species present in solution as fewer conformers are possible. For the application as polymerisation catalysts the high stability of the activated catalyst is important. We obtained meaningful analytical data by paramagnetic NMR, combined with DFT-calculation of the spin-density. These and other investigations lead to the conclusion, that the active species is a cationic chromium(III)alkyl complex. However, at present we have not enough information about the exact structure of this species in the absence of coordinating solvent molecules.     

Simulation of a deformable multibody system with hydraulics and control

Numerous contributions have been made concerning multibody systems, hydraulic actuators or the design of feedback controllers. A system that combines these fields has been studied rarely. In the present work the systematic simulation of an entire machine, which consists of structural mechanical elements where single masses are transported, hydraulic actuation systems and a closed loop controller is studied. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of Conjugated Polymer Nanoparticles in Non‐Aqueous Emulsions

Summary: A novel non‐aqueous emulsion system, consisting of cyclohexane as the continuous and acetonitrile as the dispersed phase, is described. Stabilization of the system can be achieved by using polyisoprene‐block‐poly(methyl methacrylate) copolymers as emulsifiers. The suitability of this system for performing water‐sensitive, catalytic, and oxidative polymerizations and polycondensations is demonstrated by the synthesis of poly(3,4‐ethylenedioxythiophene), poly(thiophene‐3‐yl‐acetic acid), and polyacetylene. In all cases spherical nanoparticles with diameters as small as 23 nm can be obtained.

     

Synthesis of Poly(tartar amides) as Bio‐Inspired Antifreeze Additives

Summary: Multifunctional poly(tartar amides) have been synthesized and used as bio‐inspired antifreeze additives. It is shown that these polymers strongly interfere with the crystallization process of water in comparison to commercially available commodity polymers. While the addition of the poly(tartar amides) results in minor freezing point depression, as is shown by differential scanning calorimetry, a strong change in the ice crystal morphology is evident. Wide‐angle X‐ray scattering and optical microscopy indicate that the hexagonal structure of undisturbed ice‐crystals is oriented and partly deformed.

Light microscopy image of ice crystals at 223 K after a freezing assay with poly(tartar amides) shown at a polymer concentration of 2 wt.‐%.     

Special Chromatographie: Qualitätskontrolle von hochreinem Wasserstoff

Mit Gaschromatographie in Gasproben einzelne Komponenten nachzuweisen, die in ppb‐Mengen vorliegen, stellt Analytiker and Instrumentierung vor echte Herausforderungen.     

Numerical Simulation of Thermal Effects in Electric Circuits via Energy Transport equations

In this work we present the coupling of stationary energy-transport (ET) equations with Modified Nodal Analysis (MNA)-equations to model electric circuits containing semiconductor devices. The one-dimensional ET-equations are discretised in space by an exponential fitting mixed hybrid finite element approach to ensure current continuity and positivity of charge carriers. The discretised ET-equations are coupled to MNA-equations and the resulting system is solved with backwarddifference formulas. Numerical examples are shown for a test circuit containing a pn-diode, and the results are compared to those achieved using the drift-diffusion model to describe the semiconductor devices in the circuit. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Homogenization of fibre composites using X-FEM

A successful material design process for novel textile reinforced composites requires an integrated simulation of the material behaviour and the estimation of the effective properties used in a macroscopic structural analysis. In this context the Extended Finite Element Method (X-FEM) is used to model the behavior of materials that show a complex structure on the mesoscale efficiently. A homogenization technique is applied to compute effective macroscopic stiffness parameters. This contribution gives an outline of the implementation of the X-FEM for complex multi-material structures. A modelling procedure is presented that allows for the automated generation of an extended finite element model for a specific representative volume element. Furthermore, the problem of branching material interfaces arising from complex textile reinforcement architectures in combination with high fibre volume fractions will be addressed and an appropriate solution is proposed. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Polymer‐Bound Thiol Groups on Poly(2‐oxazoline)s

A new 2‐oxazoline monomer with a protected thiol group, 2‐[2‐(4‐methoxybenzylsulfanyl)ethyl]‐2‐oxazoline, MOB‐SOx , was synthesized from commercially available compounds. MOB‐SOx and 2‐ethyl‐2‐oxazoline (EtOx) were simultaneously polymerized yielding well defined copolymers with narrow molar mass distributions and target polymer chain length. The copolymerization was initiated by N‐methyl‐2‐methyl‐2‐oxazolinium triflate ( MeOxOTf ). After quantitative deprotection, poly(2‐oxazoline) with pendant thiol groups was obtained. The thiol groups were quantitatively added to the double bond of N‐phenyl‐acrylamide ( PhA ) and benzylmaleimide ( BzM ). Graft copolymers were obtained by reaction of those SH containing polymers with poly(2‐methyl‐2‐oxazoline)s bearing acrylamide ( PMeOx ₁₀ A ) and maleimide ( PMeOx ₁₀ M ) as terminal reactive groups.

     

“Grafting From” -Living Cationic Polymerization of Poly(isobutylene) from Silica-Nanoparticle Surfaces

Summary: This publication discusses the development of new methods for producing organic-inorganic core-shell-nanoparticles (NP's) via a combination of “grafting-from” techniques and living cationic polymerization reactions. Based on the surface initiated, quasiliving cationic polymerization of isobutylene, polymeric shells of polyisobutylene (PIB) were attached onto nanoparticles (silica NP's of different sizes, r = 12–40 nm) with a high degree of precision. “Grafting-from” polymerization provides an ideal method to control the number of polymer chains per particle by means of the degree of initial derivatization and the length of the polymeric chains. The resulting nanocomposite materials were analyzed using DLS, TEM, GPC, TGA, DSC.     

Comparative Analysis of the Antitumor Activity of Cis- and Trans-Resveratrol in Human Cancer Cells with Different p53 Status

Resveratrol, a natural plant phytoalexin, is produced in response to fungal infection or− UV irradiation. It exists as an isomeric pair with cis- and trans-conformation. Whereas multiple physiological effects of the trans-form, including a pronounced anti-tumoral activity, are nowadays elucidated, much less knowledge exists concerning the cis-isomer. In our work, we analyzed the antiproliferative and cytotoxic properties of cis-resveratrol in four different human tumor entities in direct comparison to trans-resveratrol. We used human cell lines as tumor models for hepatocellular carcinoma (HCC; HepG2, Hep3B), colon carcinoma (HCT-116, HCT-116/p53^(−/−)), pancreatic carcinoma (Capan-2, MiaPaCa-2), and renal cell carcinoma (A498, SN12C). Increased cytotoxicity in all investigated tumor cells was observed for the trans-isomer. To verify possible effects of the tumor suppressor p53 on resveratrol-induced cell death, we used wild type and p53-deleted or -mutated cell lines for every tested tumor entity. Applying viability and cytotoxicity assays, we demonstrated a differential, dose-dependent sensitivity towards cis- or trans-resveratrol among the respective tumor types.