Dimerization in highly concentrated solutions of phosphoimidazolide activated mononucleotides.
Phosphoimidazolide activated ribomononucleotides (*pN) are useful substrates for the non-enzymatic synthesis of polynucleotides. However, dilute neutral aqueous solutions of *pN typically yield small amounts of dimers and traces of polymers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate. Here we report the self-condensation of nucleoside 5'-phosphate 2-methylimidazolide (2-MeImpN with N = cytidine, uridine or guanosine) in the presence of Mg2+ in concentrated solutions, such as might have been found in an evaporating lagoon on prebiotic Earth. The product distribution indicates that oligomerization is favored at the expense of hydrolysis. At 1.0 M, 2-MeImpU and 2-MeImpC produce about 65% of oligomers including 4% of the 3',5'-linked dimer. Examination of the product distribution of the three isomeric dimers in a self-condensation allows identification of reaction pathways that lead to dimer formation. Condensations in a concentrated mixture of all three nucleotides (U,C,G mixtures) is made possible by the enhanced solubility of 2-MeImpG in such mixtures. Although percent yield of internucleotide linked dimers is enhanced as a function of initial monomer concentration, pyrophosphate dimer yields remain practically unchanged at about 20% for 2-MeImpU, 16% for 2-MeImpC and 25% of the total pyrophosphate in the U,C,G mixtures. The efficiency by which oligomers are produced in these concentrated solutions makes the evaporating lagoon scenario a potentially interesting medium for the prebiotic synthesis of dimers and short RNAs.
Kanavarioti
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Department of Chemistry and Biochemistry, University of California, Santa Cruz 95064, USA.
D003568:Cytidine Monophosphate / Q000031:analogs & derivatives* / Q000737:chemistry; D019281:Dimerization; D011756:Diphosphates / Q000138:chemical synthesis*; D019020:Directed Molecular Evolution; D019143:Evolution, Molecular; D006157:Guanosine Monophosphate / Q000031:analogs & derivatives* / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007536:Isomerism; D013997:Time Factors; D014542:Uridine Monophosphate / Q000031:analogs & derivatives* / Q000737:chemistry
D011756:Diphosphates; C036896:guanosine 5'-phospho-2-methylimidazolide; D006157:Guanosine Monophosphate; C057426:uridine 5'-phospho-2-methylimidazolide; C043331:cytidine 5'-phospho-2-methylimidazolide; D014542:Uridine Monophosphate; D003568:Cytidine Monophosphate