Incorporation of porphyrinacetylides into duplexes of the simplified nucleic acidGNA

Abstract

A porphyrin-acetylide-modified GNA (glycol nucleic acid) phosphoramidite building block was synthesized in an economical fashion starting from (S)-glycidyl-4,4′- dimethoxytrityl ether in just 4 steps with an overall yield of 48%. The porphyrin acetylide nucleotide was incorporated into GNA duplexes opposite ethylene glycol abasic sites and the duplexes were analyzed by UV-melting, UV-vis, fluorescence spectroscopy, and circular dichroism. The modified GNA duplexes display lower thermal stabilities, however, the stabilities of the duplexes can be modulated by the incorporation of Zn²⁺ (further destabilization) or Ni²⁺ (stabilization relative to the uncomplexed porphyrin). Uncomplexed as well as Ni²⁺-coordinated porphyrins intercalate into the GNA duplex whereas Zn²⁺-coordinated porphyrins are most likely located outside the base stack. Adjacent porphyrins in opposite strands of GNA duplexes show an electronic interaction with each other which might be exploited in the future for the design of photoelectrical devices.