Synthesis of One-Component Nanostructured Polyion Complexes via Polymerization-Induced Electrostatic Self-Assembly

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

Compartmentalization and Unidirectional Cross-Domain Molecule Shuttling of Organometallic Single-Chain Nanoparticles

Compartmentalization and unidirectional cross-domain molecule shuttling are omnipresent in proteins, and play key roles in molecular recognition, enzymatic reaction, and other living functions. Nanomachinery design emulating these biological functions is being considered as one of the most ambitious and challenging tasks in modern chemistry and nanoscience. Here, we present a biomimetic nanomachinery design using single-chain technology. Stepwise complex of the outer blocks of water-soluble linear ABC triblock terpolymer to copper ions yields dumbbell-shaped single-chain nanoparticle. A novel nanomachine capable of compartmentalization and unidirectional cross-domain molecule shuttling has been achieved upon ascorbic acid reduction, leading to synergistically donating/accepting copper centers between discrete double heads, overall dumbbell-to-tadpole configurational transition, and intake of oxidized ascorbic acid into reconstructed head. Subsequent air oxidation results in the inverse molecule shuttling and configurational transition processes. This is the first demonstration of biomimetic nanomachinery design that is capable of compartmentalization and unidirectional cross-domain molecule shuttling, exemplified simply using a new single-chain technology