Selection of Order by the Formation of Self-Reproducing Microcompartments Drives Adaptation, Catalysis, and Chemical Evolution in Constitutional Dynamic Networks.

The lipid world hypothesis postulates that the formation of micro-compartments may represent the self-organisation process governing the transition from chaotic mixtures of molecules to complex systems. Although protocells have been reported to display biologically inspired functions in both systems chemistry and prebiotic contexts, the rules underlying lipid selection in competitive environments remain largely unexplored. Here we show that combinatorial libraries based on dynamic covalent imine bonds provide a suitable model to investigate selection mechanisms in micellar formation, leading to the emergence of enzyme-like catalysis and the chemical evolution toward bilayer structures. Systematic studies reveal that micelles protect their imine-based surfactants from hydrolysis through the micro-environments they generate, thereby stabilising their own components via a self-selection process. Remarkably, this mechanism also pro-motes the self-sorting of reaction networks, which in turn reinforces the robustness of selection. Increasing compositional diversity enables micelles to adopt complex behaviours, such as mimicking hydrolase activity through the incorporation of a catalytic triad, and affording sufficient stabilising interactions to drive the micelle-to-vesicle transition. Our findings suggest that micelles can act as dynamic attractors, selecting molecules of interest from mixtures and initiating chemical evolution towards function and higher levels of organisation. This study provides guidelines for probing the emergence of protocells by elucidating key selection rules that may be extended to a wide range of micro-compartments.