Borate-Guanosine Hydrogels and Their Hypothetical Participation in the Prebiological Selection of Ribonucleoside...

The prebiological anomeric selectivity of ribonucleosides is a key phenomenon in the understanding of the RNA world hypothesis and the origin of life. While each ribonucleoside can have two anomers (α or β), ribonucleosides naturally occur in the β form, while α anomers are extremely rare. Guanosine, a canonical ribonucleoside, binds to borate and self-assembles into G4-quartets, enabling the formation of borate-guanosine hydrogels. These macrostructures, exhibiting elevated thermal robustness and self-healing properties, have been suggested as plausible frameworks for the syntheses of prebiological molecules. Moreover, their external layers could have prevented degradation of compounds by aggressive primitive radiation and reduced molecular dispersion. Herein it is proposed that anomeric selectivity may have occurred due to the different 3D organization and stereochemical environment formed by each borate-guanosine anomer and subsequent formation of borate-guanosine hydrogels. DFT was applied to the optimization of α and β anomeric structures in four steps, from borate-guanosine diesters to G4 structures. The results obtained suggest that β-syn-guanosine (the most stable structure) is the only anomer that forms a planar G4-quartet with borate, capable of self-assembling into a hydrogel. Given the properties of borate-guanosine hydrogels, this could explain why β-guanosine is currently the sole anomer present in living organisms.