The first fully characterized neutral and cationic rhodium(I)-complexes containing DMSO as the only dative ligand; S-, O- and bridging S,O-bidentate binding modes

Isolation and characterisation of novel neutral and cationic Rh(I) complexes having only DMSO molecules as dative ligands give complexes showing S-, O- and bridging S,O-bidentate binding modes of DMSO.     

Reciprocity and sensitivity of opposed-solenoid endovascular MRI probes

Several forms of catheter-mounted "inside-out" probes for endovascular imaging have been proposed in the literature. The "opposed-solenoid" structure has been studied in relatively little detail, although it has some potential advantages over the others. Using a small water sample as a voxel, we measure point by point the spatial variation of the sensitivity and the rf field strength of such a probe, and connect the two by the reciprocity relation. By itself, the corresponding plot provides a nice example of the reciprocity relation at work; and for the characterization of the probe it gives a check on data quality. The results can be understood from simple considerations and agree well with the sensitivity observed in the image of a phantom.     

New 1,3-Thiazoles and 1,3-Thiazines from 1-Thiocarbamoylpyrazoles

Summary. New 1,3-thiazoles and 1,3-thiazines are prepared from 1-thiocarbamoyl-pyrazoles. The structures of the title compounds are established by a single crystal structure analysis. Furthermore, antiprotozoal activities of one compound have been determined.     

Proteome‐Wide Profiling of Targets of Cysteine reactive Small Molecules by Using Ethynyl Benziodoxolone Reagents

In this study, we present a highly efficient method for proteomic profiling of cysteine residues in complex proteomes and in living cells. Our method is based on alkynylation of cysteines in complex proteomes using a “clickable” alkynyl benziodoxolone bearing an azide group. This reaction proceeds fast, under mild physiological conditions, and with a very high degree of chemoselectivity. The formed azide‐capped alkynyl–cysteine adducts are readily detectable by LC‐MS/MS, and can be further functionalized with TAMRA or biotin alkyne via CuAAC. We demonstrate the utility of alkynyl benziodoxolones for chemical proteomics applications by identifying the proteomic targets of curcumin, a diarylheptanoid natural product that was and still is part of multiple human clinical trials as anticancer agent. Our results demonstrate that curcumin covalently modifies several key players of cellular signaling and metabolism, most notably the enzyme casein kinase I gamma. We anticipate that this new method for cysteine profiling will find broad application in chemical proteomics and drug discovery.     

Tuning and predicting biological affinity: aryl nitriles as cysteine protease inhibitors

A series of aryl nitrile-based ligands were prepared to investigate the effect of their electrophilicity on the affinity against the cysteine proteases rhodesain and human cathepsin L. Density functional theory calculations provided relative reactivities of the nitriles, enabling prediction of their biological affinity and cytotoxicity and a clear structure-activity relationship.