Redox‐Sensitive Stomatocyte Nanomotors: Destruction and Drug Release in the Presence of Glutathione

The development of artificial nanomotor systems that are stimuli‐responsive is still posing many challenges. Herein, we demonstrate the self‐assembly of a redox‐responsive stomatocyte nanomotor system, which can be used for triggered drug release under biological reducing conditions. The redox sensitivity was introduced by incorporating a disulfide bridge between the hydrophilic poly(ethylene glycol) block and the hydrophobic polystyrene block. When incubated with the endogenous reducing agent glutathione at a concentration comparable to that within cells, the external PEG shells of these stimuli‐responsive nanomotors are cleaved. The specific bowl‐shaped stomatocytes aggregate after the treatment with glutathione, leading to the loss of motion and triggered drug release. These novel redox‐responsive nanomotors can not only be used for remote transport but also for drug delivery, which is promising for future biomedical applications.     

Recombinant Synthesis of Hybrid Lipid–Peptide Polymer Fusions that Self‐Assemble and Encapsulate Hydrophobic Drugs

Inspired by biohybrid molecules that are synthesized in Nature through post‐translational modification (PTM), we have exploited a eukaryotic PTM to recombinantly synthesize lipid–polypeptide hybrid materials. By co‐expressing yeast N‐myristoyltransferase with an elastin‐like polypeptide (ELP) fused to a short recognition sequence in E. coli, we show robust and high‐yield modification of the ELP with myristic acid. The ELP's reversible phase behavior is retained upon myristoylation and can be tuned to span a 30–60 °C. Myristoylated ELPs provide a versatile platform for genetically pre‐programming self‐assembly into micelles of varied size and shape. Their lipid cores can be loaded with hydrophobic small molecules by passive diffusion. Encapsulated doxorubicin and paclitaxel exhibit cytotoxic effects on 4T1 and PC3‐luc cells, respectively, with potencies similar to chemically conjugated counterparts, and longer plasma circulation than free drug upon intravenous injection in mice.     

Photooxidase‐Mimicking Nanovesicles with Superior Photocatalytic Activity and Stability Based on Amphiphilic Amino Acid and Phthalocyanine Co‐Assembly

Enzyme mimics have broad applications in catalysis and can assist elucidation of the catalytic mechanism of natural enzymes. However, challenges arise from the design of catalytic sites, the selection of host molecules, and their integration into active three‐dimensional structures. Herein, we describe the development of a photooxidase mimic by synergetic molecular self‐assembly. 9‐Fluorenylmethyloxycarbonyl‐l ‐histidine undergoes efficient co‐assembly with phthalocyanine into nanovesicles with tunable particle size and membrane thickness. The obtained nanovesicles can be used as catalysts for reactive‐oxygen‐mediated photosensitive oxidation with improved efficiency and stability. This work highlights the co‐assembly of simple building blocks into a supramolecular photocatalyst, which might give insight into possible evolutionary paths of photocatalytic membrane systems, and might allow facile transfer into photosensitive nanoreactors or artificial organelles.