A facile route to hierarchically organized multicompartmentalized proteinosomes based on a recursive Pickering emulsion procedure using amphiphilic protein–polymer nanoconjugate building blocks is described. The number of incarcerated guest proteinosomes within a single host proteinosome is controlled, and enzymes and genetic polymers encapsulated within targeted subcompartments to produce chemically organized multi‐tiered structures. Three types of spatiotemporal response—retarded concomitant release, synchronous release or hierarchical release of dextran and DNA—are demonstrated based on the sequential response of the host and guest membranes to attack by protease, or through variations in the positioning of disulfide‐containing cross‐links in either the host or guest proteinosomes integrated into the nested architectures. Overall, our studies provide a step towards the construction of hierarchically structured synthetic protocells with chemically and spatially integrated proto‐organelles.

A new fluorescent 2-(2′-aminophenyl)benzimidazole derivatized sensor BMD was designed and synthesized. In CH₃CN/H₂O (2 : 8, v/v, HEPES 10 mM, pH 7.4) solution, sensor BMD displays two emission bands and exhibits a highly selective and ratiometric response to Zn²⁺ ions with a distinctly longer-wavelength emission blue shifted through the inhibition of the excited-state intramolecular proton transfer (ESIPT) process. BMD can clearly discriminate Zn²⁺ from Cd²⁺ and other metal ions. Moreover, the in situ generated BMD-Zn²⁺ solution exhibits a highly selective and ratiometric response to S²⁻ among various anions and thiol-containing amino acids via Zn²⁺ displacement approach, which results in a revival of the ESIPT phenomenon of free BMD. These results demonstrate that BMD can serve as a ratiometric sensor for sequential recognition of Zn²⁺ and S²⁻ in aqueous solution through inhibition and turn-on of ESIPT process.

Multi-responsive drug delivery systems are playing a very important role in nanomedicine, as they can feature as smart carriers releasing their payload on demand. In this study, magnetic, reductive and thermo triple-responsive nanocarriers based on core–shell magnetic mesoporous silica nanoparticles (MMSNPs) modified with a thermo responsive polymer poly(N-isopropylacrylamide) (PNIPAAm) have been developed. Photoinduced electron/energy transfer-reversible addition fragmentation chain transfer (PET-RAFT) polymerization, mediated by a ruthenium-based photoredox Ru(bpy)₃Cl₂ catalyst was used to graft PNIPAAm onto MMSNPs. A series of characterization and testing techniques were applied to confirm the structures of the synthesized nanocarriers to assess their efficiency as drug delivery systems. Doxorubicin (DOX) was easily encapsulated into the nanocarriers with a high loading capacity, and quickly released in response to the triple-responsive systems. The MMSNPs remained intact in all synthetic steps, during the loading of the drug and the in vitro release tests. Thus, these multi responsive polymer grafted Fe₃O₄-capped-MSN models are not only magnetically guided, but also represent a promising candidate in the formulation of targeted delivery of therapeutic agents to temperature and more reductive environment tissues, such as tumors and inflammatory sites.