Uptake of silicone oil in the polystyrene matrix of the two phase system polystyrene/silicone oil as detected by NMR

The decrease of the droplet radii of silicone oil dispersed in a polystyrene matrix at a temperature of 140°C with increasing time was measured by NMR dynamic imaging. From this time dependence the diffusion coefficient of the silicone oil into the matrix was calculated to be 7 · 10⁻¹⁸ m² · s⁻¹. The uptake of the silicone oil in the polystyrene matrix was confirmed by broad line NMR measurements.     

A Water- and Base-Stable Iminopyridine-Based Cage That Can Bind Larger Organic Anions

Catalysis inside molecular cages and capsules has attracted an increasing amount of attention over the last decade. While many examples of the catalysis of reactions with cationic intermediates and transition states are known, those with anionic counterparts are scarce. One limiting factor is access to suitably sized cationic iminopyridine-based cages that are stable towards water and anionic/nucleophilic guest molecules. This study aimed at identifying such suitable cages. In this full paper, we describe the journey that finally led to the synthesis of a novel iminopyridine-based tetrahedron that can bind larger organic anions with binding constants of up to 850 M⁻¹ in MeCN−d₃/H₂O=9 : 1. Importantly, it also displays stability in basic aqueous acetonitrile. Surprisingly, investigations towards catalysis of reactions with anionic transition states did not indicate rate accelerations in the presence of the cage.