S. Pitsch et al., PYRANOSYL-RNA (P-RNA) - BASE-PAIRING SELECTIVITY AND POTENTIAL TO REPLICATE - PRELIMINARY COMMUNICATION, Helvetica Chimica Acta, 78(7), 1995, pp. 1621-1635
Base pairing in p-RNA (beta-D-ribopyranosyl-(4'--> 2')-oligonucleotide
s) is not only stronger than in DNA and RNA, but also more selective i
n the sense that it is strictly confined to the Watson-Crick mode. Hom
opurine sequences (tested up to decamers) exist as single strands unde
r conditions where they undergo reverse-Hoogsteen self-pairing in homo
-DNA or Hoogsteen seif-pairing in DNA. This exceptional pairing select
ivity is rationalized as hinging on two structural features of p-RNA:
the large inclination between backbone axis and base-pair axes in p-RN
A duplexes, and the higher rigidity of the p-RNA backbone compared wit
h RNA, DNA, and homo-DNA. The most important consequence of the pairin
g selectivity refers to the potential of p-RNA to replicate. Replicati
ve copying of sequence information by nonenzymatic template-controlled
ligation is not hampered by self-pairing of guanine-rich templates, a
s it is known to be the case in the RNA series. We have demonstrated t
wo replicative cycles in which G-rich p-RNA-octamer templates induce s
equence-selective ligation of tetramer-2'-phosphate derivatives to com
plementary C-rich octamer sequences, and in which the latter, with com
parable efficiency, induce corresponding ligation reactions back to th
e original G-rich octamers. Ligation is most satisfactorily achieved a
fter pre-activation of the 2'-phosphate groups as 2',3'-cyclophosphate
derivatives; in this version, the process does not proceed as oligoco
ndensation, but as a genuine oligomerization. This is of considerable
promise for the search for potentially natural conditions under which
homochiral p-RNA strands might self-assemble and self-replicate.