Poly(8-methyladenylic acid): a single-stranded regular structure with alternating syn-anti conformations

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Abstract
Poly(8-methyladenylic acid) was prepared by chemical synthesis of 8-methyladenosine 5''-diphosphate and enzymatic polymerization with polynucleotide phosphorylase. The polymer exhibits a large hypochromism and cooperative melting in neutral solution. The transition temperature is independent of salt concentration at moderate ionic strength and decreases slightly at high salt. The adenine ring vibration at 1626 cm-1 is independent of temperature. A high-resolution NMR spectrum is observed near the bottom of the melting range. The chemical shift of the H2 proton exhibits a large upfield shift in the ordered form, and the temperature profile of H2 is cooperative and congruent with the UV melting curve. The CH3 proton signal, in striking contrast to H2, is independent of temperature. These results support a regular, single-stranded helix in the ordered form, in contrast to both poly(adenylic acid) and poly(8-bromoadenylic acid). The contrasting temperature dependence of the H2 and CH3 proton signals can be accounted for by regularly alternating syn and anti conformations of the 8-methyladenylic acid residues.