Two end-decorated homopolymers, poly(styrene)-beta-cyclodextrin (PS-beta-CD) and poly(ethylene oxide)-ferrocene (PEO-Fc), can orthogonally self-assemble into a supramolecular diblock copolymer (PS-beta-CD/PEO-Fc) in aqueous solutions based on the terminal host-guest interactions. These assemblies can further form supramolecular vesicles, and their assembly and disassembly behaviors can be reversibly switched by voltage through the reversible association and disassociation of the middle supramolecular connection. The vesicles possess an unprecedented property that their assembly or disassembly speed can be controlled by the applied voltage strength. Luminescence spectroscopy demonstrates that the vesicles act as nanocapsules carrying molecules within their hollow cavities and that the external voltage strength accurately regulates the drug release time.

Vesicles breathe CO2! A new type of vesicle that self‐assembles from amidine‐containing diblock copolymer displays “breathing” features. Treating the vesicles with CO2 or Ar can reversibly tune the expansion and contraction of the vesicular volume, as if a bubble is breathing (see picture, PAD=poly((N‐amidino)dodecyl acrylamide), PEO=poly(ethylene oxide), Rh=hydrodynamic radius).

Take a deep breath: The membrane permeability and the scale of membrane nanochannels of polymer vesicles are modulated by CO2 control of vesicular expansion and contraction. These polymersomes can act as size‐selective nanoseparators for particle sieving and as nanoreactors for enzymatic reactions that require compartmentalization. GSH=glutathione.

Two homopolymers can orthogonally self-assemble into pseudo-copolymer based on terminal host-guest interactions, and these supramolecular copolymers further fabricate one-dimensional nanotubes in water. By applying alternate UV/visible light, the aggregates can reversibly assemble and disassemble by means of the association and disassociation of active connection.

Vesicles breathe CO2! A new type of vesicle that self‐assembles from amidine‐containing diblock copolymer displays “breathing” features. Treating the vesicles with CO2 or Ar can reversibly tune the expansion and contraction of the vesicular volume, as if a bubble is breathing (see picture, PAD=poly((N‐amidino)dodecyl acrylamide), PEO=poly(ethylene oxide), Rh=hydrodynamic radius).