Assembly‐driven protection from hydrolysis as key selective force during chemical evolution

The origins of biopolymers pose fascinating questions in prebiotic chemistry. The marvelous assembly proficiencies of biopolymers suggest they are winners of a competitive evolutionary process. Sophisticated molecular assembly is ubiquitous in life where it is often emergent upon polymerization. We focus on the influence of molecular assembly on hydrolysis rates in aqueous media and suggest that assembly was crucial for biopolymer selection. In this model, incremental enrichment of some molecular species during chemical evolution was partially driven by the interplay of kinetics of synthesis and hydrolysis. We document a general attenuation of hydrolysis by assembly (i.e., recalcitrance) for all universal biopolymers and highlight the likely role of assembly in the survival of the ‘fittest’ molecules during chemical evolution. The chemistry of the origins of life poses fascinating questions. The proficiencies of biopolymers in forming marvelous spatial arrangements (assemblies) suggests they are survivors of a competitive evolutionary process. As assembly slows down the degradation rates of biomolecules in water, we suggest that the evolution of biopolymers was driven partially by an interplay of their formation, assembly, and degradation.