A novel ferrocenium capped amphiphilic pillar[5]arene (FCAP) was synthesized and self-assembled to cationic vesicles in aqueous solution. The cationic vesicles, displaying low cytotoxicity and significant redox-responsive behavior due to the redox equilibrium between ferrocenium cations and ferrocenyl groups, allow building an ideal glutathione (GSH)-responsive drug/siRNA co-delivery system for rapid drug release and gene transfection in cancer cells in which higher GSH concentration exists. This is the first report of redox-responsive vesicles assembled from pillararenes for drug/siRNA co-delivery; besides enhancing the bioavailability of drugs for cancer cells and reducing the adverse side effects for normal cells, these systems can also overcome the drug resistance of cancer cells. This work presents a good example of rational design for an effective stimuli-responsive drug/siRNA co-delivery system.

Photothermal therapy at the NIR‐II biowindow (1000–1350 nm) is drawing increasing interest because of its large penetration depth and maximum permissible exposure. Now, the supramolecular radical dimer, fabricated by N,N′‐dimethylated dipyridinium thiazolo[5,4‐d]thiazole radical cation (MPT.+) and cucurbit[8]uril (CB[8]), achieves strong absorption at NIR‐II biowindow. The supramolecular radical dimer (2MPT.+‐CB[8]) showed highly efficient photothermal conversion and improved stability, thus contributing to the strong inhibition on HegG2 cancer cell under 1064 nm irradiation even penetrating through chicken breast tissue. This work provides a novel approach to construct NIR‐II chromophore by tailor‐made assembly of organic radicals. It is anticipated that this study provides a new strategy to achieve NIR‐II photothermal therapy and holds promises in luminescence materials, optoelectronic materials, and also biosensing.

Experimental procedures and supporting figures (PDF).

Polymeric supra-amphiphiles are amphiphiles that are fabricated by linking polymeric segments, or small molecules and polymeric segments, by noncovalent interactions or dynamic covalent bonds.

Two novel supramolecular photoinitiators (supra-photoinitiators) based on the host−guest complexation of macrocycles (pillar[6]arene, P6; prism[5]arene, NP5) and diphenyl-iodonium salt (Iod) were fabricated. Under light irradiation, macrocycle P6 or NP5 could donate electrons to the guest molecule Iod, which generated highly active free radicals and cationic fragments to achieve efficient polymerization. Compared to a commercial activator, the electron transfer between macrocycles and Iod were under nondiffusion control, endowing a much higher photopolymerization rate and epoxy resin final conversion. In addition, the host−guest complexation of NP5 extended the initiating wavelength of Iod from ultrashort ultraviolet to near-ultraviolet, which could better match the environment-friendly LED light source. It is anticipated that a supra-photoinitiator may open a new route for designing novel photoinitiators with high performance.