Substitution of nucleobases within duplexes of natural or synthetic nucleic acids with ligands has been used in the last decade and a half as a method for the precise positioning of transition metal ions in the duplexes.  The metal ion incorporation can greatly expand the properties of the duplexes or higher order structures to include electronic, magnetic and catalytic properties different from those of organic molecules and materials.  While metal incorporation in duplexes was the focus of many published studies, their incorporation in triplexes was not. As a larger variety of coordination environments can be created by ligand incorporation in triplexes, we have examined the coordination ability of bis- and tris-ligand sites created in triplexes upon hybridization of ligand-containing, homo-purine and –pyrimidine peptide nucleic acid (PNA) strands.  The quantitative evaluation of the factors that govern the incorporation of metal ions at specific locations in the PNA triplexes shows that the supramolecular chelate effect exerted by nucleic acid hybridization on metal coordination to ligands built in the nucleic acid is modulated by steric interactions between the metal-ligand complex and the triplex.  These findings are of value in the design of functional hybrid inorganic-nucleic acid architectures.

Metal ion incorporation in peptide nucleic acid triplexes

249th National Meeting (2015)

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