DNA block copolymers are hybrid materials that contain both DNA and synthetic polymer linked into a blocky chain structure. They also represent a special class of charged-neutral block copolymers that can potentially interact with cationic molecules to form polyelectrolyte complexes. Ionic liquids (ILs) are green solvents consisting of tunable cationic and anionic constituents, and their interaction with biomolecules including DNA have been reported. In this study, we synthesize DNA-b-poly(ethylene glycol) (DNA-b-PEG) block copolymer and investigate its complexation with a number of biocompatible ILs. DNA-b-PEG is prepared by coupling chemistry between amine-functionalized DNA and N-hydroxysuccinimide ester activated PEG. Thermal annealing is employed to induce complex micelle formation, and the micelle morphology is investigated by varying DNA hybridization state, IL type, and charge ratio. The hybridization state of the DNA plays an important role in determining the complex formation. While ssDNA-b-PEG does not complex well with IL, dsDNA-b-PEG complexes with IL to form vesicle-like micelles. Moreover, the charge ratio and IL type also affect complex morphology, and the micelle size and stability are systematically examined by varying the IL concentration and the cation/anion type. Collectively, our study illustrates the utilization of ILs as novel solvents that can interact with DNA block copolymers to form complex micelles with rich morphology.

Complex micelle morphology of DNA block copolymer and ionic liquid

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