Transient Compartmentalization in Coacervates Driven by Chemically Fueled Autocatalysis and Interfacial Remodeling

Area of Science:

• Soft Matter Chemistry
• Chemical Systems Biology
• Supramolecular Chemistry

Background:

• Membraneless organelles (MLOs) possess complex, dynamic structures crucial for cellular functions.
• Synthetically recreating the hierarchical architecture of MLOs presents a significant scientific challenge.
• Understanding dissipative processes in self-assembly is key to developing adaptive materials.

Purpose of the Study:

• To develop a chemically driven system that programs the hierarchical evolution of coacervate droplets.
• To integrate autocatalysis, liquid-liquid phase separation (LLPS), and interfacial remodeling for spatiotemporal control.
• To establish a minimal, programmable platform for creating life-like organizational complexity in soft materials.

Main Methods:

• A dissipative reaction network based on thiol-thioester exchange was employed.
• Autocatalytic generation of surfactant micelles and subsequent coacervate formation.
• Thiol-disulfide cascade to produce asymmetric aromatic surfactants for interfacial modification.

Main Results:

• The system successfully programmed hierarchical evolution of coacervate droplets.
• Interfacial enrichment of surfactants triggered symmetry breaking and cavity nucleation.
• Achieved stable multicompartmental architectures through fusion, reorganization, and kinetic trapping.
• Hydrolysis-mediated dissipation ensured system reversibility.

Conclusions:

• A minimal yet programmable chemical platform was established, integrating key self-assembly and reaction processes.
• Demonstrated spatiotemporal control over condensate morphology, mimicking MLOs.
• The study provides a versatile strategy for coupling reaction networks with self-assembly, advancing adaptive soft materials.