title: Sequence- and regio-selectivity in the montmorillonite-catalyzed synthesis of RNA.
abstract: The six binary montmorillonite clay-catalyzed reactions of the 5'-phosphorimidazolides of adenosine, cytidine, guanosine and uridine were performed and the eight dimers from each reaction were separated and analyzed by HPLC. A 16-51-fold higher yield of the 5'-purine-pyrimidine dimers over that of the 5'-pyrimidine-purines was observed. The total yield of the 5'-purine-pyrimidine dimers was in the 50-70% range while that of the 5'-pyrimidine-purine dimers was 1.3-7.0%. Less sequence selectivity was observed in the homodimers formed. Regioselectivity for the formation of 3', 5'-phosphodiester bonds over that found in the absence of clay was observed. The 5'-purine-pyrimidine, 5'-pyrimidine-pyrimidine and 5'-purine-purine dimers had 3', 5'-links in about half of their phosphodiester bonds. The percent phosphodiester links in the 5'-pyrimidine-pyrimidine dimers was 18%, a value close to that observed in the absence of the montmorillonite catalyst. The montmorillonite-catalyzed reaction of all four activated nucleotides was performed and the 24 products were separated and analyzed. The trends observed in the binary reactions were confirmed and the results also showed that the relative reactivity of the activated monomers was A > G > C > U in the ratio 8.2:4.8:1.3:1 respectively. No 5'-pyrimidine-purines with a 5'-U and pG3' pU, pC3' pA and pC3' pG were detected. These studies suggest that a limited population of RNAs would have formed in catalyzed prebiotic reactions.
authors.affiliation: Department of Chemistry, Rensselaer Polytechnic Institute, Troy, NY 12180, USA.
authors.forename: G
authors.initials: G
authors.lastname: Ertem
authors.forename: J P
authors.initials: JP
authors.lastname: Ferris
mesh_terms: D000241:Adenosine / Q000737:chemistry; D000538:Aluminum Silicates; D001546:Bentonite; D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D000077215:Clay; D003562:Cytidine / Q000737:chemistry; D019281:Dimerization; D015226:Dinucleoside Phosphates / Q000138:chemical synthesis*; D006151:Guanosine / Q000737:chemistry; D007093:Imidazoles / Q000737:chemistry*; D012313:RNA / Q000138:chemical synthesis*; D014529:Uridine / Q000737:chemistry
chemical_list: D000538:Aluminum Silicates; D015226:Dinucleoside Phosphates; D007093:Imidazoles; D006151:Guanosine; D001546:Bentonite; D003562:Cytidine; D012313:RNA; D000241:Adenosine; D000077215:Clay; D014529:Uridine