DyNAs: Constitutional Dynamic Nucleic Acid Analogues

Dynamic cationic polymers were generated in aqueous media from functionally complementary monomers bearing nucleobase groups. 1H NMR spectroscopy was used to follow the polycondensation reaction of the nucleobase‐appended dihydrazides 1 and 2 with the dialdehydes B and C. The reversibility of these polymers was established by proton NMR spectroscopy through exchange of the dihydrazide 2 with polymer 1 B. The polymers 1 B, 2 B, 1 C, and 2 C represent dynamic biopolymers of nucleic acid type, DyNAs. Electrostatic interaction of these polymers with polyanionic entities, such as polyphosphates, polynucleotides, and polyaspartic acid, was shown to take place. It induces a change in size of the dynamic polymer, as it responds by an increase in degree of polymerization to an increase of the overall anionic charge introduced, that is, to the total electrostatic interaction. Nucleic acid analogues get dynamic! Components bearing functional groups capable of undergoing reversible connections and appended with nucleobase groups generate reversible covalent polymers that represent dynamic biopolymers, “biodynamers” (see scheme). Such entities display component exchange and undergo modification upon binding of external effectors.