Prebiotic Chemistry Assemblies of L-Cysteine on Defect-Free Pyrite Terraces

Abstract

Wächtershäuser's theory proposes iron-sulfur minerals as key platforms for molecular synthesis and supramolecular organization in prebiotic environments. However, defects have been traditionally considered at the center of such assemblies, thereby underestimating the contributions of regular and pristine interfaces. Here, we combine scanning tunneling microscopy and spectroscopy (STM/STS) with density functional theory (DFT) to investigate the fundamental prebiotic chemistry system of L-Cysteine (L-Cys) on defectless FeS$_2$(100) terraces. To do so, we first achieved atomically ordered, defect-free terraces that act as support of two distinct supramolecular phases of L-Cys: one compact, highly ordered supramolecular network and another less packed, labile supramolecular network. We unveil trimer-based intermolecular interactions to be at the origin of these pattern formations. These results demonstrate that L-Cys self-assemblies can be hosted on flawless FeS$_2$ terraces due to the cooperative interplay between substrate electronic structure and intermolecular interactions, without the participation of dominant defects. Therefore, the autocatalytic activity of pyrite could have triggered the on-surface polymerization process of these non-static self-assembled structures under primordial conditions, thereby endorsing Wächtershäuser's postulates on the origin of life.