Enzyme-Assisted Photoinitiated Polymerization-Induced Self-Assembly: An Oxygen-Tolerant Method for Preparing Block Copolymer Nano-Objects in Open Vessels and Multiwell Plates

Abstract

High-throughput synthesis of well-defined polymer nano-objects has long been an attractive yet challenging topic in the area of polymer chemistry and material science. Herein, we report an enzyme-assisted photoinitiated polymerizationinduced self-assembly (photo-PISA) approach to prepare well-defined AB diblock or ABC triblock copolymer nano-objects at room temperature in open vessels and multiwell plates. Kinetic studies indicated that the presence of glucose oxidase (GOx) endowed the polymerizations with excellent oxygen tolerance. Good control was maintained during the enzyme-assisted photo-PISA process. This method facilitates high-throughput PISA, allowing for the construction of a detailed phase diagram in a rather short time. We also demonstrate the potential bio-related application of this method by the successful encapsulation of horseradish peroxidase (HRP) and bovine serum albumin (BSA) into self-assembled polymer vesicles without compromising protein activities. This robust oxygen-tolerant PISA approach leads to unprecedented access to well-defined polymer nanoobjects for nonexperts.

Synthesis of Light‐Responsive Pyrene‐Based Polymer Nanoparticles via Polymerization‐Induced Self‐Assembly

“…PISA‐generated systems have gained interest in the field of nanomedicine because various shapes could be produced . Of the various living polymerization techniques that can be employed to drive the PISA process, reversible addition–fragmentation chain transfer (RAFT) polymerization which can be activated either thermally or by visible light has been the dominant technique due to its versatility to control a broad range of monomers . The RAFT‐derived PISA process is based on the chain extension of a soluble macromolecular chain transfer agent (macro‐CTA) with a solvophobic polymer to generate self‐assembled nanoparticles in situ .…”

A Breathing Atom‐Transfer Radical Polymerization: Fully Oxygen‐Tolerant Polymerization Inspired by Aerobic Respiration of Cells

“…[13,14] Thus,o xygen is the undesired radical scavenger in radical polymerizations.T oo vercome this,d eoxygenation with inert gasses,u se of ag love box or other techniques such as the freeze-pump-thaw method are used for effective removal of oxygen. [20,21] However,the generated hydrogen peroxide (from the glucose oxidase-catalyzed step between oxygen and d-glucose), [22][23][24] was not removed and its fate has not been addressed. [20,21] However,the generated hydrogen peroxide (from the glucose oxidase-catalyzed step between oxygen and d-glucose), [22][23][24] was not removed and its fate has not been addressed.…”

ICAR ATRP in PEG with Low Concentration of Cu(II) Catalyst: A Versatile Method for Synthesis of Block Copolymer Nanoassemblies under Dispersion Polymerization

“…This ICAR ATRP dispersion polymerization runs very fast and 92.1% monomer conversion is obtained in 5 h. Compared with the RAFT dispersion polymerization in PEG400 employing a macro‐RAFT agent of trithiocarbonate‐terminated poly(ethylene glycol) monomethyl ether (PEG 113 ‐TTC) under [St] 0 :[PEG 113 ‐TTC] 0 :[AIBN] 0 = 300:1:1/3 (seeing details) in the Supporting Information, the ICAR ATRP dispersion polymerization runs much fast. From Figure B and Figure S7 (Supporting Information), a two‐stage plot of ln([M] 0 /[M]) versus polymerization time is observed in either ICAR ATRP dispersion polymerization or RAFT dispersion polymerization, which is typically occurs in dispersion polymerization under PISA conditions . The PEG 113 ‐ b ‐PS block copolymers synthesized by ICAR ATRP dispersion polymerization were characterized by GPC (Figure C) and NMR (Figure S8, Supporting Information), and the results are summarized in Figure D.…”