Dithienylethene-Based Photoswitchable Phosphines for the Palladium-Catalyzed Stille Coupling Reaction.

Homogeneous transition metal catalysis is a constantly developing field in chemical sciences. A growing interest in this area is photoswitchable catalysis, which pursues in situ modulation of catalyst activity through noninvasive light irradiation. Phosphorus ligands are excellent targets to accomplish this goal by introducing photoswitchable moieties; however, only a limited number of examples have been reported so far. In this work, we have developed a series of palladium complexes capable of catalyzing the Stille coupling reaction that contain photoisomerizable phosphine ligands based on dithienylethene switches. Incorporation of electron-withdrawing substituents into these dithienylethene moieties allows variation of the electron density on the phosphorus atom of the ligands upon light irradiation, which in turn leads to a modulation of the catalytic properties of the formed complexes and their activity in a model Stille coupling reaction. These results are supported by theoretical computations, which show that the energy barriers for the rate-determining steps of the catalytic cycle decrease when the photoswitchable phosphine ligands are converted to their closed state.

Amplified photomodulation of a bis(dithienylethene)-substituted phosphine.

Phosphine ligands play a crucial role in homogeneous catalysis, allowing fine-tuning of the catalytic activity of various metals by modifying their structure. An ultimate challenge in this field is to reach controlled modulation of catalysis in situ, for which the development of phosphines capable of photoswitching between states with differential electronic properties has been proposed. To magnify this light-induced behavior, in this work we describe a novel phosphine ligand incorporating two dithienylethene photoswitchable moieties tethered to the same phosphorus atom. Double photoisomerization was observed for this ligand, which remains unhindered upon gold(I) complexation. As a result, the preparation of a fully ring-closed phosphine isomer was accomplished, for which amplified variation of phosphorus electron density was verified both experimentally and by computational calculations. Accordingly, the presented molecular design based on multiphotochromic phosphines could open new ways for preparing enhanced photoswitchable catalytic systems.

Hafnium Oxide-Based Nanoplatform for Combined Chemoradiotherapy.

Recently, the combined therapy has become one of the main approaches in cancer treatment. Combining different approaches may provide a significant outcome by triggering several death mechanisms or causing increased damage of tumor cells without hurting healthy ones. The supramolecular nanoplatform based on a high-Z metal reported here is a suitable system for the targeted delivery of chemotherapeutic compounds, imaging, and an enhanced radiotherapy outcome. HfO2 nanoparticles coated with oleic acid and a monomethoxypoly(ethylene glycol)-poly(ε-caprolactone) copolymer shell (nanoplatform) are able to accumulate inside cancer cells and release doxorubicin (DOX) under specific conditions. Neither uncoated nor coated nanoparticles show any cytotoxicity in vitro. DOX loaded onto a nanoplatform demonstrates a lower IC50 value than pure DOX. X-ray irradiation of cancer cells loaded with a nanoplatform shows a higher death rate than that for cells without nanoparticles. These results provide an important foundation for the development of complex nanoscale systems for combined cancer treatment.