Preference for internucleotide linkages as a function of the number of constituents in a mixture.
Phosphoimidazolide-activated ribomononucleotides (*pN; see Scheme I) are useful substrates for the nonenzymatic synthesis of oligonucleotides. In the presence of metal ions dilute neutral aqueous solutions of *pN (0.01 M) typically yield only small amounts of dimers and traces of oligomers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate (5'NMP). An earlier investigation of *pN reactions in highly concentrated aqueous solutions (up to 1.4 M) showed, as expected, that the percentage yield of the condensation products increases and the yield of the hydrolysis product correspondingly decreases with *pN concentration (Kanavarioti 1997). Here we report product distributions in reactions with one, two, or three reactive components at the same total nucleotide concentration. *pN used as substrates were the nucleoside 5'-phosphate 2-methylimidazolides, 2-MeImpN, with N = cytidine (C), uridine (U), or guanosine (G). Reactions were conducted as self-condensations, i. e., one nucleotide only, with two components in the three binary U,C, U,G, and C,G mixtures, and with three components in the ternary U,C, G mixture. The products are 5'NMP, 5',5'-pyrophosphate-, 2',5'-, 3', 5'-linked dimers, cyclic dimers, and a small percentage of longer oligomers. The surprising finding was that, under identical conditions, including the same total monomer concentration, the product distribution differs substantially from one reaction to another, most likely due to changing intermolecular interactions depending on the constituents. Even more unexpected was the observed trend according to which reactions of the U,C,G mixture produce the highest yield of internucleotide-linked dimers, whereas the self-condensations produce the least and the reactions with the binary mixtures produce yields that fall in between. What is remarkable is that the approximately two-fold increase in the percentage yield of internucleotide-linked dimers is not due to a concentration effect or a catalyst, but to the increased complexity of the system from a single to two and three components. These observations, perhaps, provide an example of how increased complexity in relatively simple chemical systems leads to organization of the material and consequently to chemical evolution. A possible link between prebiotic chemistry and the postulated RNA world is discussed.
Kanavarioti
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Department of Chemistry and Biochemistry, University of California, Santa Cruz, CA 95064, USA. tessi@hydrogen.ucsc.edu
D002851:Chromatography, High Pressure Liquid; D003568:Cytidine Monophosphate / Q000031:analogs & derivatives / Q000737:chemistry; D003596:Cytosine / Q000737:chemistry; D019281:Dimerization; D019418:Evolution, Chemical; D006147:Guanine / Q000737:chemistry; D006157:Guanosine Monophosphate / Q000031:analogs & derivatives / Q000737:chemistry; D006868:Hydrolysis; D009711:Nucleotides / Q000737:chemistry*; D012996:Solutions; D014498:Uracil / Q000737:chemistry; D014542:Uridine Monophosphate / Q000031:analogs & derivatives / Q000737:chemistry
D009711:Nucleotides; D012996:Solutions; D014498:Uracil; D006147:Guanine; C036896:guanosine 5'-phospho-2-methylimidazolide; D006157:Guanosine Monophosphate; C057426:uridine 5'-phospho-2-methylimidazolide; C043331:cytidine 5'-phospho-2-methylimidazolide; D003596:Cytosine; D014542:Uridine Monophosphate; D003568:Cytidine Monophosphate