Triphilic pentablock copolymers with perfluoroalkyl segment in central position

Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)-b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid–solid phase transition at 63°C before the final crystal melting at 95°C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy.     

Monitoring genomic alterations with a panel of oligonucleotide probes specific for various simple repeat motifs

Germline and somatic instability of the human genome was studied, using synthetic oligonucleotides specific for simple repeat motifs. The following probes were used: (GTG)5, (GACA)4, (GATA)4, (CT)8, (TTAGGG)3, (GT)8, (GAA)6 and (GGAT)4. Each of them is unique with respect to the target regions recognized in the genome. Thus compilation of the various fingerprint data provides a complex map of the genome (and its deviations). While the fingerprints of differentiated somatic tissues never showed any alterations, in tumor tissues (namely gliomas) many changes could be detected. Most of the latter reflect secondary karyological aberrations. In nearly one third of the gliomas, drastically amplified and apparently monomorphic DNA fragments were identified. This marker should make it possible to deal with causal pathogenetic mechanisms as well as novel diagnostic strategies.     

Evidence for complex magnetic order in U2Zn17: A μ+ SR studySR study

μ⁺ SR-measurements in transversally applied magnetic fields of 2000 G and 4000 G on heavy-electron single crystal U₂Zn₁₇ are presented. They reveal that at least two types of interstitial sites are occupied by the positive muons. One of these sites (1/3, 2/3, 5/6) could be identified via induced local dipolar fields which aboveT _N=9.7 K can exactly be derived from the magnetic susceptibility. The corresponding component of the μ⁺-signal exhibits a steplike decrease by about 40% atT _N which is caused by the onset of a very broad distribution of static internal magnetic fields (ΔB≈1000 G) with zero average. Such a field distribution is in distinct contrast to dipolar-field calculations performed for the simple antiferromagnetic structure deduced from neutron diffraction. The remaining 60% of the muons contributing to this component belowT _N are subject to a narrow static field distribution (ΔB≈1 G). The induced dipolar fields at the site (1/3, 2/3, 5/6) are temperature-independent belowT _N. A weak dipolar coupling to the U-moments renders similar observations for muons occupying the second type of interstitial impossible.     

Positive muons in bismuth: determination of their sites,detection of a large local lattice contraction and giant associated electric field gradients,evidence for short and long range diffusion

Using a high purity Bi single crystal the temperature and orientation dependence of the zero and transverse field muon spin relaxation rate has been studied in detail. The results imply that the ⁺ occupies one of the two possible interstitial sites in the distorted rhombohedral crystal structure of Bi below 10 K and the other site above 80 K. At both sites the nearest neighbor Bi atoms are found to be shifted towards the ⁺ by 10% of their nominal distance, implying a large local lattice contraction. In concomitance extremely strong electric field gradients are manifest at the nn Bi nuclei. An almost temperature independent reduced relaxation rate in the temperature range from 20 K to 60 K is interpreted in terms of short range diffusion along a limited chain of alternating types of sites. Above 100 K both long range and short range diffusion are indicated.