The noncovalent locking of nanostructured thermoresponsive polyion complexes can be achieved via polymerization-induced electrostatic self-assembly (PIESA) using an arginine-like cationic monomer.
Polymerization-induced self-assembly
(PISA) is a powerful method
for the synthesis of polymeric kinetically frozen core nanoparticles.
However, the PISA synthesis of biologically important polymeric fluidic
materials is unexplored. Herein we present a liquid–liquid
phase separation mode PISA. The proof of concept is established by
means of complex coacervation in visible light-initiated RAFT dispersion
polymerization of anionic monomer in the presence of a protonated
polyethylenimine in water at 25 °C. We demonstrate a stage-by-stage
nano to micron droplet growth mechanism via an increase in growing
chain DP or electrical neutralization. Liquid coacervate droplets
and their glassy nanowires or vesicles can be interconverted upon
changing the ethanol/water solvent. As such, tunable construction
of coacervate droplets and nanowires or vesicles can be achieved using
this smart PISA method.
We herein present sequence-controlled polymerizationinduced self-assembly (PISA) via photoswitchable reversible addition−fragmentation chain transfer (RAFT) copolymerization of oppositely-charged monomers using polyethylene glycol chain transfer agent in water at 25 °C. Thorough block copolymerization leads to a polymerization-induced electrostatic self-assembly named ABC-mode polymerization-induced electrostatic self-assembly (PIESA), by which PEGylated (PEG, polyethylene glycol) polyion complex (PIC) spheres, lamellae, and vesicles are achieved. We demonstrate the inherent spontaneous zwitterionic alternating copolymerization nature, which leads to the charge-dictated alternating or gradient zwitterionic sequence. As such, we developed sequencecontrolled synthesis of nanostructured block-gradient zwitterionic terpolymer PICs via complete zwitterionic copolymerization starting from photoswitched incomplete first polymerization, i.e., AB(BC)-mode PIESA. This sequence-controlled PISA method provides the unprecedented control of the low-dimensional polyelectrolyte complex nanostructure involving not only shape but also size and thickness of micrometer-sized ultrathin PIC vesicles and lamellae, without necessarily changing the whole chemical composition and degree of polymerization.
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