Chemically Fueled Dissipative Self-Assembly that Exploits Cooperative Catalysis

Area of Science:

• Chemical self-assembly
• Catalysis
• Supramolecular chemistry

Background:

• Living systems utilize energy from chemical fuel hydrolysis for dissipative processes.
• Nucleoside triphosphates are common chemical fuels in biological systems.
• Understanding transient self-assembly is key to mimicking life-like behaviors.

Purpose of the Study:

• To develop a simple model system for transient self-assembly.
• To investigate the catalytic role of histidine in ester bond formation and breakage.
• To mimic the dynamic structural changes observed in biological systems like microtubule formation.

Main Methods:

• Utilized histidine as a catalyst for ester bond formation and hydrolysis.
• Observed the co-assembly of molecules into a self-supporting gel.
• Investigated cooperative catalytic effects of proximal histidines in the assembled state.
• Analyzed the disassembly process from gel to sol.

Main Results:

• Histidine successfully facilitated ester bond formation, leading to gelation.
• Cooperative catalysis by assembled histidines drove disassembly to a sol state.
• Achieved a transient, out-of-equilibrium self-assembled state.
• Demonstrated a model system mimicking microtubule dynamic instability.

Conclusions:

• Histidine's dual catalytic role (nucleophile and proton donor) enables transient self-assembly.
• This model system provides insights into the fundamental principles of dynamic structural organization in living systems.
• The study highlights the importance of cooperative effects in driving non-equilibrium processes.