High-Density DNA Coatings on Carboxylated Colloids by DMTMM- and Azide-Mediated Coupling Reactions.

DNA-mediated colloidal interactions provide a powerful strategy for the self-assembly of ordered superstructures. We report a practical and efficient two-step chemical method to graft DNA brushes onto carboxylated particles, which resolves the previously reported issues such as irreversible aggregation, inhomogeneous coating, and relatively low DNA density that can hinder colloidal crystallization. First, carboxylated particles are functionalized with heterobifunctional poly(ethylene glycol) (NH-PEG-N) by 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM)-activated esterification of carboxylic groups and amide coupling. Then, dibenzocyclooctyne (DBCO)-functionalized DNA strands are grafted onto the pegylated particles through strain-promoted alkyne-azide cycloaddition (SPAAC) on azide groups. The homogeneous PEG brushes provide dispersion stability to the particles and clickable functional groups, resulting in DNA coatings of 1 100 000 DNA per 1 μm particle or 1 DNA per 2.9 nm, about five times higher than previously reported. The DNA-coated particles exhibit a sharp association-dissociation transition and readily self-assemble into colloidal crystals upon annealing. In addition, fluorinated particles and lens-shaped particles with carboxylate groups are successfully grafted with DNA strands in this manner. Janus particles are also functionalized with DNA strands selectively on one of the two faces. Owing to the anisotropic attraction, the DNA-coated Janus particles self-assemble into self-limiting aggregates.