Exploring the zone of anisotropy and broken symmetries in DNA-mediated nanoparticle crystallization.
In this work, we present a joint experimental and molecular dynamics simulations effort to understand and map the crystallization behavior of polyhedral nanoparticles assembled via the interaction of DNA surface ligands. In these systems, we systematically investigated the interplay between the effects of particle core (via the particle symmetry and particle size) and ligands (via the ligand length) on crystallization behavior. This investigation revealed rich phase diagrams, previously unobserved phase transitions in polyhedral crystallization behavior, and an unexpected symmetry breaking in the ligand distribution on a particle surface. To understand these results, we introduce the concept of a zone of anisotropy, or the portion of the phase space where the anisotropy of the particle is preserved in the crystallization behavior. Through comparison of the zone of anisotropy for each particle we develop a foundational roadmap to guide future investigations.
Department of Chemistry, Northwestern University, Evanston, IL 60208; International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208;
Matthew N
0000-0002-1721-0464
MN
O'Brien
Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208;
Martin
M
Girard
Department of Chemistry, Northwestern University, Evanston, IL 60208; International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208;
Hai-Xin
HX
Lin
Department of Chemistry, Northwestern University, Evanston, IL 60208; International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208;
Jaime A
JA
Millan
Department of Chemistry, Northwestern University, Evanston, IL 60208; International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208;
Monica
M
Olvera de la Cruz
X-Ray Science Division, Argonne National Laboratory, Argonne, IL 60439.
Byeongdu
B
Lee
Department of Chemistry, Northwestern University, Evanston, IL 60208; International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208; chadnano@northwestern.edu.
Chad A
CA
Mirkin
D016880:Anisotropy; D003460:Crystallization; D004247:DNA / Q000737:chemistry* / Q000187:drug effects; D008024:Ligands; D056004:Molecular Dynamics Simulation; D053758:Nanoparticles / Q000737:chemistry*; D010316:Particle Size; D013499:Surface Properties; D014961:X-Ray Diffraction
D008024:Ligands; D004247:DNA
DNA; anisotropic nanoparticles; broken symmetry; colloidal crystallization; nanomaterials