Switchable pH-Responsive Morphologies of Coassembled Nucleobase Copolymers

• Published in: Biomacromolecules 2024-11, Vol.25 (11), p.7225-7236
• Main Authors: Arsenie, Laura Vasilica, Semsarilar, Mona, Benkhaled, Belkacem Tarek, Geneste, Amine, Prélot, Benedicte, Colombani, Olivier, Nicol, Erwan, Lacroix-Desmazes, Patrick, Ladmiral, Vincent, Catrouillet, Sylvain
• Format: Article
• Language: English
• Subjects: Adenine - chemistry; Chemical Sciences; Hydrogen Bonding; Hydrogen-Ion Concentration; Hydrophobic and Hydrophilic Interactions; Nanostructures - chemistry; Polymerization; Polymers; Polymers - chemistry; Uracil - chemistry
• ISSN: 1525-7797; 1526-4602; 1526-4602
• DOI: 10.1021/acs.biomac.4c00901

This work presents supramolecular coassembled nucleobase copolymers with transitional morphologies upon pH changes (from 7.4 to 10). Uracil- and adenine-containing copolymers were prepared by RAFT, which allowed us to finely tailor the polymerization degree and the composition. The coassembled formulations prepared in an aqueous buffer at two distinct pH (7.4 and 10) formed spherical morphologies at physiological pH. The increase of the pH induced the apparition of various large, irreversible anisotropic supramolecular architectures. Isothermal titration calorimetry revealed that the coassembly at pH 7.4 was mainly guided by H-bonds between complementary nucleobases, while the experiments conducted at pH 10 showed that the assemblies were mainly driven by hydrophobic interactions. These results highlight that the nature of supramolecular interactions (H-bonds or hydrophobic interactions) has a great influence on the morphology of nucleobase-containing coassemblies when changing the pH. These findings may provide further perspectives in the field of advanced nanomaterials.