Fuel-Driven Enzymatic Reaction Networks to Program Autonomous Thiol/Disulfide Redox Systems

Area of Science:

• Materials Science
• Biochemistry
• Polymer Chemistry

Background:

• Dissipative formation of disulfide bonds offers a versatile route for autonomous materials design.
• Directly combining oxidative and reductive agents for disulfide bond formation is challenging due to self-annihilation.
• Existing methods lack precise control over material lifetime and broad applicability to various thiol types.

Purpose of the Study:

• To develop a robust and autonomous method for dissipative disulfide bond formation.
• To enable programmable hydrogel lifetimes using a redox-based enzymatic reaction network (ERN).
• To demonstrate the broad applicability of the ERN for different types of thiols.

Main Methods:

• Introduction of a redox-based enzymatic reaction network (ERN) to mediate disulfide bond formation.
• Utilizing thiol-terminated star polymers (sPEG-SH) to control hydrogel network dynamics.
• Customizing the ERN to accommodate both aliphatic and aromatic thiols.

Main Results:

• Successfully achieved dissipative disulfide bond formation in a fully autonomous manner using the ERN.
• Demonstrated precise programming of hydrogel lifetimes through the ERN and sPEG-SH.
• Confirmed the ERN's versatility with both aliphatic and aromatic thiols, indicating broad functional applicability.

Conclusions:

• The developed ERN provides a powerful and autonomous strategy for disulfide bond formation in materials science.
• This approach allows for tunable hydrogel lifetimes, crucial for advanced autonomous materials.
• The ERN's adaptability to various thiols signifies its potential for widespread application in functional materials development.