Nanostructured polyion complexes (PICs) are appealing in biomaterials applications. Yet, conventional assembly suffers from the weakness in scale-up and reproducibility. Only a few low-dimensional PICs are available to date. Herein we report an efficient and scalable strategy to prepare libraries of low-dimensional PICs. It involves a visible-light-mediated RAFT polymerization of ionic monomer in the presence of a polyion of the opposite charge at 5-50 % w/w total solids concentration in water at 25 °C, namely, polymerization-induced electrostatic self-assembly (PIESA). A Vesicle, multi-compartmental vesicle, and large-area unilamellar nanofilm can be achieved in water. A long nanowire and porous nanofilm can be prepared in methanol/water. An unusual unimolecular polyion complex (uPIC)-sphere-branch/network-film transition is reported. This green chemistry offers a general platform to prepare various low-dimensional PICs with high reproducibility on a commercially viable scale under eco-friendly conditions.
Nanostructured polyion complexes (PICs) are expected to serve as novel platforms to stabilize and deliver drugs, proteins, and nucleic acids. Yet, traditional self-assembly suffers from lack of scale-up and reproducibility. Particularly for one-component PICs, only spheres are available to date. Here, we report an efficient and scalable strategy to prepare one-component low-dimensional PICs. It involves visible-light-mediated RAFT iterative polymerization of opposite-charge monomers at 25% w/w solids in water at 25 °C. Sphere-film-vesicle transition and charge-/medium-tunable shape selectivity are reported. One-component PIC nanowire, ultrathin film, vesicle, tube, and surface-charged vesicle are easily prepared, and vesicle-polymerization is fulfilled, using this new strategy. This strategy provides a general platform to prepare one-component low-dimensional PICs with tailorable morphologies and high reproducibility on commercially viable scale under eco-friendly conditions.
Block copolymer nanoparticles have been widely used for advanced materials. However, the stabilization is challenging. Herein, we present a method for convenient yet reliable synthesis of stabilized polyion complex (PIC) nanometer-sized spheres and micrometer-sized ultrathin lamellae and vesicles by taking advantage of the wavelength orthogonality of UV-induced disulfide exchange and visible light-initiated polymerization-induced electrostatic self-assembly (PIESA). Disulfide-containing PIC vesicles are synthesized at scale using this PIESA, undergoing a small sphere-to-larger sphere-tolamella-to-vesicle transition. As such, surface-neutralized and surface-charged micrometer-sized vesicles can be achieved. UV irradiation of the vesicles (5.0 mg/mL in water) in ambient air induces very fast exchange reaction of locally confined/enriched disulfide motifs, leading to cross-linking, shape transition, and cystamine salt release in 4 min. As such, cross-linked PIC spheres, lamellae, and vesicles can be achieved, in one pot, from one single vesicle precursor. The wavelength orthogonality is evident from disabled PIESA synthesis under UV light and ineffective postpolymerization functionalization under visible light. The cross-linked PIC spheres and micrometer-sized ultrathin lamellae and vesicles show outstanding shape/size stability and high reversibility in the solution-adaptive electrostatic hierarchical self-assembly and disassembly upon adding ethanol into aqueous dispersion and subsequent dialysis.
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 report an updated polymerization-induced thermal self-assembly (PITSA) [Figg, C. A.; et al. Chem. Sci. 2015, 6, 1230]. The concept is validated using visible light initiated RAFT aqueous dispersion polymerization of diacetone acrylamide monomer at 25 – 70 °C. This PITSA formulation produces block copolymer lamellae at 25 °C while the copolymer morphology evolves from spheres to worms to vesicles during polymerization at 60 °C, which is above the lower critical solution chain length (LCSCL) of the core-forming block. Particle shape and size uniformity can be controlled by reaction temperature using a single photo-PISA formulation. Vesicles-to-lamellae and vesicles-to-worms transitions are achieved in situ upon cooling reaction dispersions (70 °C) to 25 °C, leading to the transformation of initially free-flowing liquids to physical hydrogels. Moreover, reversible thermoresponsive lamellae-to-vesicles-to-lamellae and worms-to-vesicles-to-worms transitions of as-synthesized nanoparticles are achieved in dilution in a heating–cooling cycle. This thermoresponsive photo-PISA formulation updates Figg’s PITSA protocol mainly in three aspects: (1) the absence of LCST limitation, (2) user-friendly control of particle shape and size uniformity by reaction temperature using a single photo-PISA formulation, and (3) reversible thermoresponsive transition of the ketone-functionalized vesicles to customer-guided lamellae or worms.
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