From Mineral Surfaces to Peptides: Hydroxyapatite-Based Platforms for Surface-Mediated Prebiotic Synthesis.

The formation of peptide bonds under prebiotic conditions represents a major challenge due to both thermodynamic and kinetic constraints, particularly in aqueous environments where condensation reactions are disfavored. Mineral surfaces have long been proposed as key contributors to overcoming these limitations by providing structured and reactive interfaces that promote molecular organization and facilitate chemical transformations. In this context, hydroxyapatite emerges as a particularly promising system due to its structural versatility, surface heterogeneity, and ability to interact with a wide range of organic molecules. Its capacity to support adsorption, interfacial organization, and dynamic interactions makes it a promising platform for surface-mediated prebiotic chemistry. Furthermore, the incorporation of metal centers, especially zirconium-based species, introduces additional catalytic functionalities that can enhance bond activation and enable cooperative reaction mechanisms. The combination of mineral surfaces and metal-based catalysis thus provides a framework for understanding how complex chemical processes could have emerged under prebiotic conditions. Particular attention is given to hybrid hydroxyapatite-zirconium systems as multifunctional catalytic platforms integrating adsorption, activation, and spatial organization. Finally, the role of dynamic environmental regimes, including gradients, cyclic processes, and non-equilibrium conditions, is considered as a critical factor in sustaining chemical reactivity and promoting increasing levels of molecular complexity. Together, these elements support a scenario in which surface-mediated processes played a central role in the emergence of peptide-like structures and early protometabolic systems.