Thermal Behavior of d-Ribose Adsorbed on Silica: Effect of Inorganic Salt Coadsorption and Significance for Prebiotic Chemistry.
Understanding ribose reactivity is a crucial step in the "RNA world" scenario because this molecule is a component of all extant nucleotides that make up RNA. In solution, ribose is unstable and susceptible to thermal destruction. We examined how ribose behaves upon thermal activation when adsorbed on silica, either alone or with the coadsorption of inorganic salts (MgCl2, CaCl2, SrCl2, CuCl2, FeCl2, FeCl3, ZnCl2). A combination of13C NMR, in situ IR, and TGA analyses revealed a variety of phenomena. When adsorbed alone, ribose remains stable up to 150 °C, at which point ring opening is observed, together with minor oxidation to a lactone. All the metal salts studied showed specific interactions with ribose after dehydration, resulting in the formation of polydentate metal ion complexes. Anomeric equilibria were affected, generally favoring ribofuranoses. Zn2+stabilized ribose up to higher temperatures than bare silica (180 to 200 °C). Most other cations had an adverse effect on ribose stability, with ring opening already upon drying at 70 °C. In addition, alkaline earth cations catalyzed the dehydration of ribose to furfural and, to variable degrees, its further decarbonylation to furan. Transition-metal ions with open d-shells took part in redox reactions with ribose, either as reagents or as catalysts. These results allow the likelihood of prebiotic chemistry scenarios to be evaluated, and may also be of interest for the valorization of biomass-derived carbohydrates by heterogeneous catalysis.
Sorbonne Universités, UPMC Univ Paris 06 and CNRS UMR 7197, LRS case courrier 178, UPMC 4 Pl. Jussieu, 75252, PARIS CEDEX 05, France.
Mariame
M
Akouche
Sorbonne Universités, UPMC Univ Paris 06 and CNRS UMR 8220, LAMS, case courrier 225, UPMC 4 Pl. Jussieu, 75252, Paris CEDEX 05, France.
Maguy
M
Jaber
Sorbonne Universités, UPMC Univ Paris 06 and CNRS UMR 8233, MONARIS, case courrier, UPMC 4 Pl. Jussieu, 75252, Paris CEDEX 05, France.
Emilie-Laure
EL
Zins
UMR 7205- ISyEB, CNRS-MNHN-UPMC Univ Paris 06, 75005, Paris, France.
Marie-Christine
MC
Maurel
Sorbonne Universités, UPMC Univ Paris 06 and CNRS UMR 7197, LRS case courrier 178, UPMC 4 Pl. Jussieu, 75252, PARIS CEDEX 05, France. jean-francois.lambert@upmc.fr.
Jean-Francois
http://orcid.org/0000-0002-8124-5709
JF
Lambert
Sorbonne Universités, UPMC Univ Paris 06 and CNRS UMR 7197, LRS case courrier 178, UPMC 4 Pl. Jussieu, 75252, PARIS CEDEX 05, France. thomas.georgelin@upmc.fr.
Thomas
T
Georgelin
D002384:Catalysis; D008670:Metals / Q000737:chemistry*; D056692:Prebiotics; D012313:RNA / Q000737:chemistry*; D012266:Ribose / Q000737:chemistry*; D012492:Salts / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*
D008670:Metals; D056692:Prebiotics; D012492:Salts; D012313:RNA; D012266:Ribose; D012822:Silicon Dioxide
RNA; heterogeneous catalysis; silicon; surface analysis; surface chemistry