Bi-directional feedback controlled transience in Cucurbituril based tandem nanozyme

Area of Science:

• Biomimetic Chemistry
• Supramolecular Chemistry
• Nanozyme Catalysis

Background:

• Biological systems utilize multi-enzymatic processes with high efficiency due to compartmentalization and out-of-equilibrium dynamics.
• Artificial catalytic systems aim to replicate these natural efficiencies.
• Vesicular nanozymes offer a platform for confined enzymatic reactions.

Purpose of the Study:

• To design a chemoenzymatic pH clock for transient assembly of a vesicular nanozyme.
• To achieve temporally controlled tandem catalysis mimicking biological systems.
• To investigate the role of feedback mechanisms in regulating nanozyme activity and stability.

Main Methods:

• Utilized alkaline TRIS buffer and glucose oxidase (GOx) to create a pH clock.
• Employed imine-linked Supramolecular Peptide Amphiphiles (SPAs) for vesicle formation.
• Integrated histidine and hemin within the vesicle structure for hydrolase-peroxidase catalysis.

Main Results:

• Successfully assembled transient vesicular nanozymes with distinct catalytic compartments.
• Demonstrated temporally controlled hydrolase-peroxidase tandem catalysis.
• Showcased bi-directional feedback from glucose oxidation regulating nanozyme assembly and activity, ensuring stability and reproducibility.

Conclusions:

• The developed pH clock system enables transient assembly and controlled function of vesicular nanozymes.
• This approach successfully mimics natural enzyme efficiency and compartmentalization.
• The nanozyme exhibits substrate specificity, catalytic reproducibility, and protected catalytic unit activity.