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3829159 
Journal Article 
Highly Controlled Open Vessel RAFT Polymerizations by Enzyme Degassing 
Chapman, R; Gormley, AJ; Herpoldt, KL; Stevens, MM 
2014 
1 
Macromolecules
ISSN: 0024-9297
EISSN: 1520-5835 
47 
24 
8541-8547 
WOS:000347138300008 
Intolerance to oxygen is a key limitation in many reactions and particularly in controlled radical polymerizations. Here we introduce the use of enzymes such as glucose oxidase (GOx) to deoxygenate reversible additionfragmentation chain transfer polymerizations (Enz-RAFT), facilitating the preparation of highly controlled polymers in vessels open to ambient oxygen. Because the removal of oxygen is so efficient, very low concentrations of GOx and initiator can be used, enabling excellent control which is demonstrated by pseudoliving polymerization kinetics and the preparation of multiblock copolymers with narrow molecular weight distributions (M-w/M-n < 1.15). GOx retains sufficient activity to facilitate polymerization not only in aqueous solutions but also in a range of water/organic solvent mixtures, and we demonstrate the use of this technique to perform open vessel Enz-RAFT polymerizations in various methanol and dioxane/water mixtures. 
aqueous solutions; composite polymers; dioxane; glucose oxidase; methanol; molecular weight; polymerization; solvents