TY - JOUR
T1 - Symmetry-Breaking Dendrimer Synthons in Colloidal Crystal Engineering with DNA
AU - Distler, Max E.
AU - Landy, Kaitlin M.
AU - Gibson, Kyle J.
AU - Lee, Byeongdu
AU - Weigand, Steven
AU - Mirkin, Chad A.
N1 - Funding Information:
This material is based upon work supported by the Air Force Office of Scientific Research under awards FA9550-17-1-0348 and FA9550-22-1-0300. The authors thank E. W. Roth (Northwestern University) for ultramicotomy of many of the crystal samples. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). This research used resources of the Advanced Photon Source (Sector 5, the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT), and the beamline 12-ID-B), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. DND-CAT is supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. Data collected in Sector 5 made use of an instrument funded by the National Science Foundation under Award No. 0960140. Some representations were made using BioRender.com.
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/1/18
Y1 - 2023/1/18
N2 - Breaking symmetry in colloidal crystals is challenging due to the inherent chemical and structural isotropy of many nanoscale building blocks. If a non-particle component could be used to anisotropically encode such building blocks with orthogonal recognition properties, one could expand the scope of structural and compositional possibilities of colloidal crystals beyond what is thus far possible with purely particle-based systems. Herein, we report the synthesis and characterization of novel DNA dendrimers that function as symmetry-breaking synthons, capable of programming anisotropic and orthogonal interactions within colloidal crystals. When the DNA dendrimers have identical sticky ends, they hybridize with DNA-functionalized nanoparticles to yield three distinct colloidal crystals, dictated by dendrimer size, including a structure not previously reported in the field of colloidal crystal engineering, Si2Sr. When used as symmetry-breaking synthons (when the sticky ends deliberately consist of orthogonal sequences), the synthesis of binary and ternary colloidal alloys with structures that can only be realized through directional interactions is possible. Furthermore, by modulating the extent of shape anisotropy within the DNA dendrimers, the local distribution of the nanoparticles within the crystals can be directed.
AB - Breaking symmetry in colloidal crystals is challenging due to the inherent chemical and structural isotropy of many nanoscale building blocks. If a non-particle component could be used to anisotropically encode such building blocks with orthogonal recognition properties, one could expand the scope of structural and compositional possibilities of colloidal crystals beyond what is thus far possible with purely particle-based systems. Herein, we report the synthesis and characterization of novel DNA dendrimers that function as symmetry-breaking synthons, capable of programming anisotropic and orthogonal interactions within colloidal crystals. When the DNA dendrimers have identical sticky ends, they hybridize with DNA-functionalized nanoparticles to yield three distinct colloidal crystals, dictated by dendrimer size, including a structure not previously reported in the field of colloidal crystal engineering, Si2Sr. When used as symmetry-breaking synthons (when the sticky ends deliberately consist of orthogonal sequences), the synthesis of binary and ternary colloidal alloys with structures that can only be realized through directional interactions is possible. Furthermore, by modulating the extent of shape anisotropy within the DNA dendrimers, the local distribution of the nanoparticles within the crystals can be directed.
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U2 - 10.1021/jacs.2c08599
DO - 10.1021/jacs.2c08599
M3 - Article
C2 - 36607135
AN - SCOPUS:85146001849
SN - 0002-7863
VL - 145
SP - 841
EP - 850
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 2
ER -