Effects of Silicate, Phosphate, and Calcium on the Stability of Aldopentoses
Ribose is an important constituent of RNA: ribose connects RNA bases and forms a strand of sugar phosphates. Accumulation of ribose on prebiotic Earth was difficult because of its low stability. Improvement in the yield of ribose by the introduction of borate or silicate in a formose-like reaction has been proposed. The effects of borates have been further analyzed and confirmed in subsequent studies. Nonetheless, the effects of silicates and phosphates remain unclear. In the present study, we incubated aldopentoses in a highly alkaline aqueous solution at a moderate temperature to determine the effects of silicate or phosphate on the degradation rates of ribose and its isomeric aldopentoses. The formation of a complex of silicate (or phosphate) with ribose was also analyzed in experiments with 29Si and 31P nuclear magnetic resonance (NMR). We found that silicate or phosphate complexes of ribose were not detectable under our experimental conditions. The stability of ribose and lyxose improved after addition of 40-fold molar excess (relative to a pentose) of sodium silicate or sodium phosphate to the alkaline solution. The stability was not improved further when an 80-fold molar excess of sodium silicate or sodium phosphate was added. Calcium was removed from these solutions by precipitation of calcium salts. The drop in Ca2+ concentration might have improved the stability of ribose and lyxose, which are susceptible to aldol addition. The improvement of ribose stability by the removal of Ca2+ and by addition of silicate or phosphate was far smaller than the improvement by borate. Furthermore, all aldopentoses showed similar stability in silicate- and phosphate-containing solutions. These results clearly show that selective stabilization of ribose by borate cannot be replaced by the effects of silicate or phosphate; this finding points to the importance of borate in prebiotic RNA formation.
KeywordsRibose RNA Silicate Phosphate Borate
This work was supported by JSPS KAKENHI, grant numbers 23740402, 15H02144, and 24244084. The authors acknowledge S. A. Benner and H. J. Kim for the discussion on carbohydrate chemistry, F. W. Nara for ICP-AES analysis, and the staff of Tohoku University Research and Analytical Center for Giant Molecules for NMR analysis. We also appreciate an anonymous reviewer for helpful comments to improve the manuscript.
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