Dynamic Microcompartments Drive Adaptation, Catalysis, and Assembly Changes in Constitutional Dynamic Networks

The formation of microcompartments is a form of self-assembly that governs the transition from chaotic mixtures of molecules to complex systems with functional states. Despite recent advances in systems chemistry, how microcompartments favor the formation of their constituents and become functional remains largely unexplored. Here, we show that combinatorial libraries based on the dynamic covalent imine bond provide a suitable model to investigate selection mechanisms in micellar formation, leading to the emergence of catalysis and structural changes in the assembly toward more organized structures. Systematic studies reveal that micelles protect their imine-based surfactants from hydrolysis through the microenvironments they generate, thereby stabilizing their own components via a self-selection process. Remarkably, this mechanism also promotes the self-sorting of reaction networks, which further reinforces the robustness of the selection. Increasing the molecular diversity enables the emergence of complex behaviors within the assembly, such as mimicking hydrolase activity through the sorting of catalytic groups and changing the structure of the parent micelle itself. This study thus provides guidelines for probing the emergence of microcompartments by elucidating key selection rules that may be extended to a wider range of microcompartments.