Aerobic Atom Transfer Radical Polymerization by Using Surfactant-GOx: Overcoming the Challenges of Hydrophobicity

Aerobic (or oxygen tolerant) reversible-deactivation radical polymerization (RDRP) techniques can enables efficient synthesis well-defined polymers and hybrid materials with novel complex architectures. However, most oxygen tolerant RDRP methods rely on glucose oxidase (GOx), and conventional GOx-mediated systems are restricted to hydrophilic monomers due to enzyme instability in hydrophobic media. Herein, we develop a novel surfactant-GOx complex (S-GOx), which unlike conventional deoxygenation approaches, the S-GOx complex not only scavenges oxygen via GOx-catalyzed but also acts as a surfactant to stabilize emulsion droplets, enabling one-pot aerobic ATRP of both hydrophilic and hydrophobic monomers in aqueous systems without glucose. This polymerization proceeds under mild conditions: a hydrophobic monomer, a S-GOx, a copper(II) bromide (CuBr2), a ligand (tris(2-pyridylmethyl)amine (TPMA)), and 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044) enables the synthesis of various polymers with good control over molecular weight and dispersity at 45 oC, and high monomer conversions (>90%) in less than12 hours with ultralow copper loading (2000 ppm) as well as excellent chain-end fidelity. In addition, circulardichroism (CD) and UV-Vis studies (205−260 nm) demonstrated that the activity of GOx modified by non-ionic surfactants still exists and the size of the polymer particles given by DLS and cryo-TEM is 379 nm, < 100 nm respectively. Meanwhile, the ATRP strategy assisted by S-GOx has essentially reduced the impact of chemical enterprises on the environment, and offers a sustainable pathway for synthesizing advanced polymeric materials.