Polymers for medical uses

An increasing demand for biomaterials corresponds to the deficiency in the knowledge on biocompatibility. To increase this knowledge the modification of polymer surfaces, their characterization, and the investigation of the response of the biosystem is considered to be a suitable approach. Surface modification may be performed in the wet-chemical way (heterogeneous reaction) or by means of treatment with a suitable plasma (glow discharge). Surface sensitive methods such as X-ray photoelectron spectroscopy, infrared spectroscopy in the attenuated total reflexion mode as well as surface energy measurements are useful for surface characterization. To determine the bioresponse to the polymer surface, enzyme-linked immunosorbent assays, cell growth and full blood tests may be used. In the present paper several systems are described with respect to their surface modification, characterization, and bioresponse. It is shown that the protein adsorption is triggered by the surface, that SO₂ plasma treatment enhances cell growth and that there seems to be a biocompatibility window for a surface characterized by a ξ-potential between −4 and −8 mV and a ratio of dispersive to polar contributions of surface energy around 12. It is stressed, however, that the final solution for a biomaterial is a material which, in the course of degradation, constantly presents a new biocompatible surface.     

Diffusion of Gold Nanoparticles in Inverse Opals Probed by Heterodyne Dynamic Light Scattering

The diffusive behavior of nanoparticles inside porous materials is attracting a lot of interest in the context of understanding, modeling, and optimization of many technical processes. A very powerful technique for characterizing the diffusive behavior of particles in free media is dynamic light scattering (DLS). The applicability of the method in porous media is considered, however, to be rather difficult due to the presence of multiple sources of scattering. In contrast to most of the previous approaches, the DLS method was applied without ensuring matching refractive indices of solvent and porous matrix in the present study. To test the capabilities of the method, the diffusion of spherical gold nanoparticles within the interconnected, periodic nanopores of inverse opals was analyzed. Despite the complexity of this system, which involves many interfaces and different refractive indices, a clear signal related to the motion of particles inside the porous media was obtained. As expected, the diffusive process inside the porous sample slowed down compared to the particle diffusion in free media. The obtained effective diffusion coefficients were found to be wave vector-dependent. They increased linearly with increasing spatial extension of the probed particle concentration fluctuations. On average, the slowing-down factor measured in this work agrees within combined uncertainties with literature data.

     

Post-polymerization modification of aromatic polyimides via Diels-Alder cycloaddition

We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials.     

Selective deoxygenation of leurosine: concise access to anhydrovinblastine

Straightforward access to anhydrovinblastine starting from the parent alkaloid leurosine is reported. The key deoxygenation step was first optimized on a model substrate. However, applied to leurosine, only the low-valent Cp2TiCl gave satisfactory results.     

The first coordination compound containing three different types of spin carriers: 2p-3d-4f (TCNQ.-, Cu2+ and Gd3+)

A novel heterospin system, [(CuL)2Gd(TCNQ)2].TCNQ-.CH3OH.2CH3CN, is obtained by reacting the mononuclear complex, [CuL], with gadolinium(III) nitrate, followed by the substitution of the nitrato ions with anionic organic radicals.     

Zur Existenz optimaler Quadraturformeln mit freien Knoten bei Integration analytischer Funktionen

Summary In the present paper we discuss the optimal quadrature rules for integration with positive continuous weight function in Hardy space H₂ of functions analytic in a circle of the complex plane. The new representations of the optimal weights and the norm of the error functional as functions of the nodes are obtained. On this basis we give an elementary proof for the existence of the optimal quadrature formula with free nodes.