In situ biocatalytic ATP regulated, transient supramolecular polymerization

Area of Science:

• Supramolecular Chemistry
• Bioinspired Materials Science
• Enzyme Catalysis

Background:

• Biological systems exhibit exquisite temporal control over self-assembly, driven by enzymatic reactions.
• Synthetic materials lack adaptable control over self-assembly kinetics, limiting their functional applications.
• There is a need for bioinspired synthetic materials with tunable growth and decay profiles.

Purpose of the Study:

• To develop a general strategy for controlling the temporal aspects of synthetic self-assembly.
• To utilize enzymatically coupled reactions to govern the growth and decay of self-assembled systems.
• To create adaptive, bioinspired synthetic materials with programmed temporal behavior.

Main Methods:

• Coupling of phosphokinase/phosphatase enzymes with a bolaamphiphilic cationic chromophore (PDI).
• Self-assembly and disassembly of PDI mediated by adenosine triphosphate (ATP) and its hydrolysis.
• Controlled *in situ* generation and hydrolysis of ATP via enzymatic reactions to regulate self-assembly kinetics.

Main Results:

• Precise control over the self-assembly process was achieved by managing ATP-generating components.
• Self-assembled structures exhibited programmed temporal decay profiles through coupled enzymatic reactions.
• The system demonstrated dissipative self-assembly driven by enzymatic ATP generation and hydrolysis.

Conclusions:

• A novel strategy for reaction-coupled, one-dimensional nanostructure formation with controlled dimensions was introduced.
• Enzymatically controlled ATP dynamics provide a powerful mechanism for temporal regulation of synthetic self-assembly.
• This bioinspired approach offers a pathway to create dynamic and responsive synthetic materials.