Like-Charge PISA: Polymerization-Induced Like-Charge Electrostatic Self-Assembly

We report the use of l-asparticacid chiralionic hydrogenbonds to drive liquid-liquid phase separation (LLPS) and precisiontwo-dimensional electrostatic self-assembly in photo-RAFT aqueouspolymerization-induced self-assembly (photo-PISA). Homopolymerizationcan yield salt-resistant, 3 nm ultrafine fibril-structured 5 nm ultrathinlamellae via LLPS, a left-to-right-handed chiralitytransition, and a droplets-to-lamellae transition. Like-charge blockcopolymerization leads to supercharged yet identical fibril-structuredultrathin lamellae, also, via LLPS, the left-to-rightchirality transition and the droplets-to-lamellae transition. Ultrafinestructures maintain intactness upon the seeded polymerization of theoppositely charged monomer. This work demonstrates that amino acidchiral ionic hydrogen bonds are powerful for the precision synthesisof salt-resistant ultrathin membrane nanomaterials.

Automated summary

In this study, l-aspartic acid chiral ionic hydrogen bonds were used to drive liquid-liquid phase separation and precision 2D electrostatic self-assembly in photo-RAFT aqueous polymerization-induced self-assembly. Through the liquid-liquid phase separation, the polymerization reaction resulted in salt-resistant, 3nm ultrafine fibril-structured and 5nm ultrathin lamellae with a chirality transition and a droplets-to-lamellae transition. Block copolymerization of like-charged monomers led to supercharged yet identical fibril-structured ultrathin lamellae, also through liquid-liquid phase separation, with a chirality transition and a droplets-to-lamellae transition. The ultrafine structures remained intact during the seeded polymerization of the oppositely charged monomer. This work demonstrates the powerful precision synthesis capability of amino acid chiral ionic hydrogen bonds for salt-resistant ultrathin membrane nanomaterials.