Reductive allylation of poly(chlorotrifluoroethylene)

Treatment of poly(chlorotrifluoroethylene) with allyltin reagents results in the clean replacement of chlorine by the allyl group under free-radical–chain conditions (AIBN, allyltributyltin), affording about a 10% degree of functionalization. An improved method using one-electron reduction of the polymer with cobalt(II) (generated by reduction of chloro(pyridine)bis(dimethylglyoximato)cobalt(III) with Mg) and allyltributyltin gives 50% functionalization. Further modification of the allyl group is realized through hydroboration-oxidation to the alcohol and subsequent Cr(VI) oxidation to the acid. A mechanistic discussion is provided. © John Wiley & Sons, Inc.     

Substituent effect in anionic polymerization of β-lactones initiated by alkali metal alkoxides

The influence of methyl substituent on the mechanism of the ring-opening polymerization of β-lactones initiated by alkali metal alkoxides is discussed. Attention has been paid to the effect of the substituent position in the monomer molecule on the ring-opening mechanism, the 3,3-dimethyl-2-oxetanone (pivalolactone), 4-methyl-2-oxetanone (β-butyrolactone) and 2-oxetanone (β-propiolactone) being chosen as model monomers. Moreover, it was found unexpectedly that in the case of pivalolactone polymerization, besides open-chain polymers, cyclic oligomers are produced.     

New cationic group 4 metal alkyl complexes

Cationic group 4 metal alkyl complexes containing tetradentate Schiff base ligands, (acen) Zr(R)⁺ and (F6-acen) Zr(R)⁺, are prepared by protonolysis of suitable neutral dialkyl precursors. These complexes display electrophilic behavior and are moderately active ethylene polymerization catalysts in the presence of 1 molar equivalent of AlR₃.     

Auger electron emission in proton-induced interactions in living matter: A TILDA-V Monte Carlo tracking

The present work focuses on studying the contribution of the Auger electron emission in proton-induced interactions in biological matter. The Monte Carlo track-structure code, TILDA-V, was then used for modeling the protons beams of 10 keV to 100 MeV in biological matter, namely, water vapor and hydrated DNA. The main ionizing processes are described by means of an extensive set of ab initio differential and total cross sections computed within a quantum-mechanical CDW-EIS approximation.     

Highly charged ions in a new era of high resolution X-ray astrophysics

X-ray astronomy and ground-based atomic physics have a long history of fruitful collaboration: Sound understanding of the underlying atomic physics is the key to reliable interpretation of the spectra from celestial sources; conversely, astronomical spectra have been used to benchmark and advance atomic physics. This interplay is about to become even more important as we enter a new era of high-resolution X-ray astrophysics with large effective collection area. Although high-resolution observations with the gratings on the Chandra and XMM-Newton observatories continue to drive new science, upcoming planned and proposed missions will open up new discovery space in the near future that is currently challenging to access: high-resolution spectroscopy on extended sources, in the Fe K band, and on short time scales. This review summarizes open questions in these areas and the design parameters for the Hitomi, XRISM, Athena, and Arcus observatories. The expected high quality of spectra taken with these observatories puts new constraints on the accuracy of atomic reference data required to take full advantage of the diagnostic potential of these spectra.     

Optimization of STEM-HAADF Electron Tomography Reconstructions by Parameter Selection in Compressed Sensing Total Variation Minimization-Based Algorithms

A novel procedure to optimize the 3D morphological characterization of nanomaterials by means of high angle annular dark field scanning-transmission electron tomography is reported and is successfully applied to the analysis of a metal- and halogen-free ordered mesoporous carbon material. The new method is based on a selection of the two parameters (μ and β) which are key in the reconstruction of tomographic series by means of total variation minimization (TVM). The parameter-selected TVM reconstructions obtained using this approach clearly reveal the porous structure of the carbon-based material as consisting of a network of parallel, straight channels of ≈6 nm diameter ordered in a honeycomb-type arrangement. Such an unusual structure cannot be retrieved from a TVM 3D reconstruction using default reconstruction values. Moreover, segmentation and further quantification of the optimized 3D tomographic reconstruction provide values for different textural parameters, such as pore size distribution and specific pore volume that match very closely with those determined by macroscopic physisorption techniques. The approach developed can be extended to other reconstruction models in which the final result is influenced by parameter choice.     

Geometry Optimization of Thermoelectric Modules: Deviation of Optimum Power Output and Conversion Efficiency

Besides the material research in the field of thermoelectrics, the way from a material to a functional thermoelectric (TE) module comes alongside additional challenges. Thus, comprehension and optimization of the properties and the design of a TE module are important tasks. In this work, different geometry optimization strategies to reach maximum power output or maximum conversion efficiency are applied and the resulting performances of various modules and respective materials are analyzed. A Bi₂Te₃-based module, a half-Heusler-based module, and an oxide-based module are characterized via FEM simulations. By this, a deviation of optimum power output and optimum conversion efficiency in dependence of the diversity of thermoelectric materials is found. Additionally, for all modules, the respective fluxes of entropy and charge as well as the corresponding fluxes of thermal and electrical energy within the thermolegs are shown. The full understanding and enhancement of the performance of a TE module may be further improved.