Chemoselective Post-Synthesis Modification of Pyridyl-Substituted, Aromatic Phosphorus Heterocycles: Cationic Ligands for Coordination Chemistry

Triazaphospholes are potential polydentate ligands due to the presence of both phosphorus and nitrogen donor atoms within the aromatic 5-membered heterocycle. The incorporation of an additional pyridyl-substituent opens up the possibility of a post-synthesis modification via chemoselective and also stepwise alkylation exclusively of the nitrogen atoms. This can be controlled by the choice and by the stoichiometry of the electrophile and allows the targeted synthesis of a variety of novel mono- and dicationic ligands. Reaction with Cu(I)-halides causes the formation of cuprates of the type [CuXn](n-1)-, which enables coordination of the π-acidic phosphorus donor to the negatively charged metal core, which is favored over the coordination by a strongly σ-donating nitrogen atom. The use of cationic triazaphosphole derivatives can be used as a strategy to enforce the coordination of the ligand to an electron rich metal solely via the phosphorus atom. However, there is a subtle balance between the formation of either coordination polymers or dimeric structures, as the substitution pattern on the heterocycle and the nature of the halide have a large influence on the coordination motifs formed

Quantum Cuntz-Krieger algebras

Motivated by the theory of Cuntz-Krieger algebras we define and study C∗-algebras associated to directed quantum graphs. For classical graphs the C∗-algebras obtained this way can be viewed as free analogues of Cuntz-Krieger algebras, and need not be nuclear. We study two particular classes of quantum graphs in detail, namely the trivial and the complete quantum graphs. For the trivial quantum graph on a single matrix block, we show that the associated quantum Cuntz-Krieger algebra is neither unital, nuclear nor simple, and does not depend on the size of the matrix block up to KK-equivalence. In the case of the complete quantum graphs we use quantum symmetries to show that, in certain cases, the corresponding quantum Cuntz-Krieger algebras are isomorphic to Cuntz algebras. These isomorphisms, which seem far from obvious from the definitions, imply in particular that these C∗-algebras are all pairwise non-isomorphic for complete quantum graphs of different dimensions, even on the level of KK-theory. We explain how the notion of unitary error basis from quantum information theory can help to elucidate the situation. We also discuss quantum symmetries of quantum Cuntz-Krieger algebras in general

Prediction of left lobe hypertrophy after right lobe radioembolization of the liver using a clinical data model with external validation

In cirrhotic patients with hepatocellular carcinoma (HCC), right-sided radioembolization (RE) with Yttrium-90-loaded microspheres is an established palliative therapy and can be considered a “curative intention” treatment when aiming for sequential tumor resection. To become surgical candidate, hypertrophy of the left liver lobe to > 40% (future liver remnant, FLR) is mandatory, which can develop after RE. The amount of radiation-induced shrinkage of the right lobe and compensatory hypertrophy of the left lobe is difficult for clinicians to predict. This study aimed to utilize machine learning to predict left lobe liver hypertrophy in patients with HCC and cirrhosis scheduled for right lobe RE, with external validation. The results revealed that machine learning can accurately predict relative and absolute volume changes of the left liver lobe after right lobe RE. This prediction algorithm could help to estimate the chances of conversion from palliative RE to curative major hepatectomy following significant FLR hypertrophy