Glucose oxidase deoxygenation−redox initiation for RAFT polymerization in air

Abstract

A new methodology based on glucose oxidase (GOx) deoxygenation and hydrogen peroxide/vitamin C (H 2 O 2 / Vc) redox initiation for conducting RAFT polymerization at low temperature in air is reported. GOx catalyzes reduction of oxygen in the presence of glucose to generate hydrogen peroxide, which is directly used to constitute a redox pair with Vc for the efficient generation of hydroxyl radicals to initiate RAFT polymerization in air. Various experimental parameters including temperature, stirring speed, prepolymerization incubation time, and concentrations of Vc, glucose, and GOx were evaluated with respect to monomer conversion, molecular weight, and dispersity. Efficient removal of oxygen is typically realized within 10 min before polymerization is initiated by addition of Vc, and high conversions are achieved within 5 h. Well-defined homopolymers and block copolymers have been efficiently synthesized with high monomer conversions and low dispersities (< 1.2). Using this new methodology, it is possible to conduct controlled RAFT polymerizations in both open and sealed vessels, though lower conversions but less termination by oxygen are typically observed for the sealed systems.

Synthesis of ultra‐high molecular weight polymers by controlled production of initiating radicals

“…Enzymes accelerate biochemical reactions with unrivaled rate enhancement and orthogonality under mild aqueous conditions, and offer excellent inspiration as catalysts in RDRP processes . Among them, glucose oxidase (GOx) shows significant promise as both an industrial catalyst and for mediating RDRP reactions . In the presence of molecular oxygen, GOx catalyzes the production of hydrogen peroxide (H 2 O 2 ) while oxidizing β‐D‐glucose to gluconic acid (Supporting Information Fig.…”

“…17 Among them, glucose oxidase (GOx) shows significant promise as both an industrial catalyst and for mediating RDRP reactions. [18][19][20][21] In the presence of molecular oxygen, GOx catalyzes the production of hydrogen peroxide (H 2 O 2 ) while oxidizing β-D-glucose to gluconic acid (Supporting Information Fig. S1, ESI).…”

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.…”

Photochemistry for Well‐Defined Polymers in Aqueous Media: From Fundamentals to Polymer Nanoparticles to Bioconjugates

“…While aqueous polymerizations present challenges to troubleshoot, they are uniquely biocompatible. Enzyme degassing for aqueous RAFT has been reported as early as 2014, and several systems have been developed expanding on this idea . They all employ the enzyme glucose oxidase (GOx), which consumes glucose to reduce O 2 to hydrogen peroxide, allowing for RAFT polymerizations to be performed in open‐air vessels.…”

“…Enzyme degassing for aqueous RAFT has been reported as early as 2014, [104] and several systems have been developed expanding on this idea. [105][106][107][108][109] They all employ the enzyme glucose oxidase (GOx), which consumes glucose to reduce O 2 to hydrogen peroxide, Macromol. Rapid Commun.…”