Work

Polyelectrolyte Copolymer Nanoreactors: From Colloidal Assembly to Photoredox Activity in Water

Year: 2026

Type: article

Abstract: Performing organic photoredox reactions in water remains challenging because most catalysts cannot simultaneously solubilize substrates, control nanoscale organization, and maintain activity under aqueous conditions. We report a photoredox-active polyelectrolyte based on a polydehydroalanine (PDha) backbone covalently functionalized with polypyridyl complexes to address some of these limitations. The copolymer undergoes substrate-triggered self-assembly in water, forming photocatalytically active spherical colloidal nanostructures (∼30 nm), as confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The assemblies efficiently catalyze the hydroxylation of arylboronic acids, a representative water-insoluble photoredox transformation. Mechanistic studies using UV-visible spectroscopy, Raman spectroscopy, time-resolved emission spectroscopy, electrochemistry, and density functional theory (DFT) indicate that dual hydrogen bonding between PDha carboxylates and arylboronic acids governs both self-assembly and catalytic performance. The nanostructures retain high activity over multiple cycles. These findings establish adaptive polymer self-assembly as a general strategy for creating enzyme-like, water-compatible photoredox systems and provide a platform for transferring organic photoredox chemistry into aqueous media.

Source: ACS Applied Materials & Interfaces

DOI: 10.1021/acsami.6c00473