TY - JOUR
T1 - High-Density DNA Coatings on Carboxylated Colloids by DMTMM- And Azide-Mediated Coupling Reactions
AU - Oh, Joon Suk
AU - He, Mingxin
AU - Yi, Gi Ra
AU - Pine, David J.
N1 - Funding Information:
J.S.O. and D.P. were supported by the US Department of Energy (DOE) grant no. DE-SC0007991. MH was supported by the US National Science Foundation under Award Number DMR-1610788. G.-R.Y. acknowledges support from the NRF (Korea) under award nos. 2017M3A7B8065528 and 2017R1A5A1070259.
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/4/7
Y1 - 2020/4/7
N2 - 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) (NH2-PEGn-N3) 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 nm2, 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.
AB - 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) (NH2-PEGn-N3) 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 nm2, 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.
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U2 - 10.1021/acs.langmuir.9b03386
DO - 10.1021/acs.langmuir.9b03386
M3 - Article
C2 - 32054262
AN - SCOPUS:85082877039
VL - 36
SP - 3583
EP - 3589
JO - Langmuir
JF - Langmuir
SN - 0743-7463
IS - 13
ER -