Biocatalytic "Oxygen-Fueled" Atom Transfer Radical Polymerization

Area of Science:

• Polymer Chemistry
• Biocatalysis
• Organic Synthesis

Background:

• Atom transfer radical polymerization (ATRP) typically requires stringent conditions to avoid oxygen inhibition.
• Developing controlled polymerization methods that are tolerant to air and utilize sustainable catalysts is an ongoing challenge.

Purpose of the Study:

• To develop an air-tolerant, enzyme-catalyzed system for atom transfer radical polymerization (ATRP).
• To achieve controlled polymerization of oligo(ethylene oxide) methyl ether methacrylate (OEOMA500) using a biocatalytic approach.
• To demonstrate the synthesis of protein and DNA bioconjugates via this enzymatic polymerization method.

Main Methods:

• Utilized a biocatalytic system comprising glucose oxidase (GOx) and horseradish peroxidase (HRP) with a copper catalyst for ATRP.
• Conducted polymerization in a flask open to air, controlling oxygen supply to regulate radical generation.
• Synthesized protein-b-POEOMA and DNA-b-POEOMA bioconjugates using initiators functionalized with biomolecules.

Main Results:

• Achieved excellent control over OEOMA500 polymerization, yielding polymers with high molecular weight (Mn >70,000) and low dispersities (1.13 ≤ Đ ≤ 1.27) within an hour.
• Demonstrated the necessity of continuous oxygen supply for radical generation and polymer growth through temporal control and hypoxic condition experiments.
• Successfully synthesized protein-b-POEOMA and DNA-b-POEOMA bioconjugates, showcasing the versatility of the enzymatic cascade polymerization.

Conclusions:

• The developed enzyme-catalyzed ATRP system offers a robust and air-tolerant alternative for controlled polymerization.
• This biocatalytic approach enables efficient synthesis of well-defined polymers and functional bioconjugates under mild conditions.
• The method highlights the potential of enzymatic cascades in advanced polymer synthesis and bioconjugation strategies.