Aluminum Alkyl Induced Isomerization of Group IV meso Metallocene Complexes.

The synthesis of group IV metallocene precatalysts for the polymerization of propylene generally yields two different isomers: The racemic isomer that produces isotactic polypropylene (iPP) and the meso isomer that produces atactic polypropylene (aPP). Due to its poor physical properties, aPP has very limited applications. To avoid obtaining blends of both polymers and thus diminish the mechanical and thermal properties of iPP, the meso metallocene complexes need to be separated from the racemic ones tediously -rendering the metallocene-based polymerization of propylene industrially far less attractive than the Ziegler/Natta process. To overcome this issue, we established an isomerization protocol to convert meso metallocene complexes into their racemic counterparts. This protocol increased the yield of iPP by 400% while maintaining the polymer's excellent physical properties and was applicable to both hafnocene and zirconocene complexes, as well as different precatalyst activation methods. Through targeted variation of the ligand frameworks, methoxy groups at the indenyl moieties were found to be the structural motifs responsible for an isomerization to take place -this experimental evidence was confirmed by density functional theory calculations. Liquid injection field desorption ionization mass spectrometry, as well as 1H and 29Si nuclear magnetic resonance studies, allowed the proposal of an isomerization mechanism.

Ambient Catalytic Spinning of Polyethylene Nanofibers.

A novel single-atom Ni(II) catalyst (Ni-OH) is covalently immobilized onto the nano-channels of mesoporous Santa Barbara Amorphous (SBA)-15 particles and isotropic Anodized Aluminum Oxide (AAO) membrane for confined-space ethylene extrusion polymerization. The presence of surface-tethered Ni complexes (Ni@SBA-15 and Ni@AAO) is confirmed by the inductively coupled plasma-optical emission spectrometry (ICP-OES) and X-ray photoelectron spectroscopy (XPS). In the catalytic spinning process, the produced PE materials exhibit very homogeneous fibrous morphology at nanoscale (diameter: ~50 nm). The synthesized PE nanofibers extrude in a highly oriented manner from the nano-reactors at ambient temperature. Remarkably high Mw (1.62×106  g mol-1 ), melting point (124 °C), and crystallinity (41.8 %) are observed among PE samples thanks to the confined-space polymerization. The chain-walking behavior of surface tethered Ni catalysts is greatly limited by the confinement inside the nano-channels, leading to the formation of very low-branched PE materials (13.6/1000 C). Due to fixed supported catalytic topology and room temperature, the filaments are expected to be free of entanglement. This work signifies an important step towards the realization of a continuous mild catalytic-spinning (CATSPIN) process, where the polymer is directly synthesized into fiber shape at negligible chain branching and elegantly avoiding common limitations like thermal degradation or molecular entanglement.

Perfectly Isotactic Polypropylene upon In Situ Activation of Ultrarigid meso Hafnocenes.

For more than 40 years, the synthesis of C2 -symmetric indenyl-based racemic metallocenes for the isoselective polymerization of propylene relied on a tedious separation of the produced rac and meso isomers. Status quo, latter are considered wasteful as they produce atactic polypropylene (aPP) rather than isotactic polypropylene (iPP) if activated with methylaluminoxane (MAO). Unexpectedly, the in situ activation of meso hafnocene I yielded perfectly isotactic polypropylene. We verified an isomerization of the meso compound to the corresponding racemic one upon triisobutylaluminum (TIBA) addition via nuclear magnetic resonance (NMR) spectroscopy and established an easy and convenient polymerization protocol, enabling productivities comparable to pure rac-I if applied to pure meso-I or a mixture of both isomers. With this established isomerization protocol, the potential yield of iPP was enhanced by more than 400 %. This protocol was also shown to be applicable to other meso hafnocenes and some initial mechanistic insights were received.

Measured Composite Collision Models: Quantum Trajectory Purities and Channel Divisibility.

We investigate a composite quantum collision model with measurements on the memory part, which effectively probe the system. The framework allows us to adjust the measurement strength, thereby tuning the dynamical map of the system. For a two-qubit setup with a symmetric and informationally complete measurement on the memory, we study the divisibility of the resulting dynamics in dependence of the measurement strength. The measurements give rise to quantum trajectories of the system and we show that the average asymptotic purity depends on the specific form of the measurement. With the help of numerical simulations, we demonstrate that the different performance of the measurements is generic and holds for almost all interaction gates between the system and the memory in the composite collision model. The discrete model is then extended to a time-continuous limit.

Prevalence of antibody to Trypanosoma cruzi in Hispanic-surnamed patients seen at Parkland Health & Hospital System, Dallas, Texas.

BACKGROUND: Chagas disease constitutes an important public health threat in terms of morbidity and mortality in the areas in the United States where immigrant populations from Latin America are conspicuous. We conducted a survey to assess the prevalence of anti-T. cruzi antibody in Hispanic-surnamed patients seen at Parkland Memorial Hospital in Dallas, Texas. FINDINGS: Five hundred serum specimens from Hispanic-surnamed patients were tested by a preliminary ELISA method. On a subset of 50 sera confirmatory testing was also performed using an alternative ELISA, indirect immunofluorescence, and TESA immunoblot. For 274 of 500 Hispanic-surnamed patients, we were able to ascertain immigration status upon medical chart review. Of the 274 sera analyzed, one sample tested as positive for anti-T. cruzi antibody by the preliminary ELISA, and by the three confirmatory methods. CONCLUSIONS: The goal of this study is to increase the awareness of T. cruzi infection and Chagas disease in areas where the Latin American immigrant communities are growing. Our study highlights the importance of testing for Chagas disease in the populations most at risk, and the need for current data on the actual seroprevalence in areas where such immigrant populations are conspicuous. Larger-scale epidemiologic surveys on Chagas disease in the immigrant communities from Latin America are warranted.