Crystal Chemistry and Physical Properties of the Nonmagnetic Kondo Compound HfAs1.7Se0.2

Single crystals of HfAs_1.7Se_0.2 are grown by chemical transport reaction and their chemical composition characterized in detail by various analytical methods. Chemical analyses and crystal structure investigations by single‐crystal X‐ray diffraction as well as powder diffraction with synchrotron radiation reveal a tetragonal PbFCl structure type with strong disorder caused by a significant arsenic deficiency (As_0.9) on the 2a site and mixed occupancy of the 2c site (As_0.8Se_0.2). HfAs_1.7Se_0.2 is a diamagnetic metal which transforms into a superconducting state at T_c=0.52 K. Similar to other PbFCl‐type arsenide selenides, the title compound displays a magnetic‐field‐independent ?AT^1/2 term in the low‐temperature electrical resistivity. This unusual term presumably originates from the electron scattering of structural two‐level systems. According to the experimental results, HfAs1.7Se0.2 appears to be a rare example of a nonmagnetic Kondo material.     

Structure of (NH4)3GaF6 investigated by multinuclear magic-angle spinning NMR spectroscopy in comparison with rietveld refinement

The structure of ammonium gallium cryolite (NH(4))(3)GaF(6) was investigated by (19)F and (69,71)Ga magic-angle spinning (MAS) NMR in comparison with X-ray powder diffraction followed by Rietveld refinement. In agreement with previous thermodynamic measurements, NMR experiments on (NH(4))(3)GaF(6) support the model of rigid GaF(6) octahedra. At high spinning speeds (30 kHz), the scalar coupling between the six equivalent (19)F nuclei and (69,71)Ga can be directly observed in the powder spectra. The coupling constants are J(19)F(69)Ga = 197 Hz and J(19)F(71)Ga = 264 Hz. To explain the (71)Ga spectra recorded at 3 kHz a small distribution of quadrupolar frequencies has to be included. The spread of the spinning sidebands hints to a largest nu(Q) value of 28 kHz for (71)Ga. This can be explained by the occurrence of highly symmetric GaF(6) octahedra, which are tilted against the surrounding atoms. In addition, the incomplete motional excitation does not average out the quadrupolar effects. NMR findings are in discrepancy to those of Rietveld refinement. As result it appears that X-ray diffraction is not sensitive enough to deliver proper results.     

Highly Extensible Bio‐Nanocomposite Fibers

Here, we show that a poly(ethylene oxide) polymer can be physically cross‐linked with silicate nanoparticles (Laponite) to yield highly extensible, bio‐nanocomposite fibers that, upon pulling, stretch to extreme lengths and crystallize polymer chains. We find that both, nanometer structures and mechanical properties of the fibers respond to mechanical deformation by exhibiting strain‐induced crystallization and high elongation. We explore the structural characteristics using X‐ray scattering and the mechanical properties of the dried fibers made from hydrogels in order to determine feasibility for eventual biomedical use and to map out directions for further materials development.

     

Thermosensitive and Dissolution Properties in Nanocomposite Polymer Hydrogels

We investigate the phase transition behavior and dissolution resistant properties of thermo‐sensitive nanocomposite hydrogels made from PEO‐PPO‐PEO triblock copolymer (Pluronic F127) and Laponite silicate nanoparticles. The rapid dissolution properties of F127 copolymer hydrogels usually limit their use as sustained release drug carriers. We overcome this limitation by synergistic combination of nanoparticle gelation characteristics with polymer thermo‐sensitivity. We present a proof of concept that the temperature‐dependent phase transitions can be shifted as a function of hydrogel composition and that the dissolution of the polymer hydrogels as well as the release of a model drug, albumin, can be significantly slowed down by addition of nanoparticles. The dissolution resistant properties generated will prove useful in the future formulation, processing and application of our polymer hydrogels for sustained release drug delivery carriers.

     

Characterization of Chlorine‐, Amine‐ and Acrylate‐Functionalized TEMPO‐Capped and Bis‐TEMPO‐Capped Polystyrenes Using MALDI‐TOF MS

Chlorine‐functionalized TEMPO‐capped polystyrenes were investigated using the matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) technique. Amine‐ and acrylate‐functionalized agents and bifunctional TEMPO‐capped polystyrene were also analyzed to demonstrate the applicability of this method. Using this technique allowed to analyze the conversion of the chlorine function to an acrylate function, which was previously difficult to detect with other methods.

MALDI‐TOF mass spectrum of a polystyrene described in this article, as obtained with DHB as the matrix.     

Integration of parallel-operating quality systems

Since the 1980s, quality systems have become an essential element in successful companies and institutions. Today those systems are indispensable to fulfill the needs of the customers and last but not least the requirements of the society. Depending on the company's activities and fields of services, it is necessary to establish various quality systems. The Institut Fresenius (IF) Group runs a number of analytical laboratories and sampling groups. The whole group was accredited according to DIN EN 45001 in 1994. Good Laboratory Practice (GLP) was introduced in 1992 and was certified by the national authority. For certain customers, IF Group is also obliged to work according DIN EN ISO 9001 or GMP. A comparison of these systems with respect to their different priorities shows the possibility of integrating their rules into one comprehensive quality system. The IF Group has therefore installed a quality system operating in parallel. Multilocation accreditations and/or certifications are taking these efforts into account. The benefits are: high transparency of the system for the customers, auditors and personnel, a reduction of maintenance costs, and great flexibility to react to new standards. Could these activities lead to a new Integrated Management System?     

Influence of micromixing on the free-radical polymerization in a discontinuous process

With the help of a simple reaction-diffusion model with constant striation thickness the influence of micromixing on free-radical polymerization was investigated for several test reactions with discontinuous prepolymerization and jerky addition of selected reactants. Monomer conversion or mean values of molar mass and chemical composition cannot be expected to be very sensitive to micromixing effects. If molar mass distributions are to be used, problems will arise from the fact that the distribution of the polymer accumulated during prepolymerization covers mixing influences occurring after reactant feed. The instantaneous molar mass distribution would be more suitable. Time-integral distributions of chemical composition or sequence length in combination with appropriate test reactions proved to be feasible indicators for the effects of micromixing as it becomes possible to separate the distribution of the prepolymer from that of the polymer which is formed after addition when micromixing is to be investigated.