Toward Complete Resolution of DNA/Carbon Nanotube Hybrids by Aqueous Two-Phase Systems

Sequence-dependent interactions between DNA and single-wall carbon nanotubes (SWCNTs) are shown to provide resolution for the atomic-structure-based sorting of DNA-wrapped SWCNTs. Previous studies have demonstrated that aqueous two-phase (ATP) systems are very effective for sorting DNA-wrapped SWCNTs (DNA-SWCNTs). However, most separations have been carried out with a polyethylene glycol (PEG)/polyacrylamide (PAM) ATP system, which shows severe interfacial trapping for many DNA-SWCNT dispersions, resulting in significant material loss and limiting multistage extraction. Here, we report a study of several new ATP systems for sorting DNA-SWCNTs. We have developed a convenient method to explore these systems without knowledge of the corresponding phase diagram. We further show that the molecular weight of the polymer strongly affects the partition behavior and separation results for DNA-SWCNTs in PEG/dextran (DX) ATP systems. This leads to the identification of the PEG1.5kDa/DX250kDa ATP system as an effective vehicle for the chirality separation of DNA-SWCNTs. Additionally, this ATP system exhibits greatly reduced interfacial trapping, enabling for the first time continuous multistep sorting of four species of SWCNTs from a single dispersion. Enhanced stability of DNA-SWCNTs in the PEG1.5kDa/DX250kDa ATP system also allows us to investigate pH dependent sorting of SWCNTs wrapped by C-rich sequences. Our observations suggest that hydrogen bonding may form between the DNA bases at lower pH, enabling a more ordered wrapping structure on the SWCNTs and improvement in sorting (11,0). Together, these findings reveal that the new ATP system is suitable for searching DNA sequences leading toward more complete resolution of DNA-SWCNTs. A new concept of "resolving sequences", evolved from the old notion of "recognition sequences", is proposed to describe a broader range of behaviors of DNA/SWCNT interactions and sorting.