title: Importance of the DNA "bond" in programmable nanoparticle crystallization.
abstract: If a solution of DNA-coated nanoparticles is allowed to crystallize, the thermodynamic structure can be predicted by a set of structural design rules analogous to Pauling's rules for ionic crystallization. The details of the crystallization process, however, have proved more difficult to characterize as they depend on a complex interplay of many factors. Here, we report that this crystallization process is dictated by the individual DNA bonds and that the effect of changing structural or environmental conditions can be understood by considering the effect of these parameters on free oligonucleotides. Specifically, we observed the reorganization of nanoparticle superlattices using time-resolved synchrotron small-angle X-ray scattering in systems with different DNA sequences, salt concentrations, and densities of DNA linkers on the surface of the nanoparticles. The agreement between bulk crystallization and the behavior of free oligonucleotides may bear important consequences for constructing novel classes of crystals and incorporating new interparticle bonds in a rational manner.
authors.affiliation: Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; and.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Macfarlane
authors.affiliation: Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; and.
authors.forename: Ryan V
authors.initials: RV
authors.lastname: Thaner
authors.affiliation: Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; and.
authors.forename: Keith A
authors.initials: KA
authors.lastname: Brown
authors.affiliation: Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; and.
authors.forename: Jian
authors.initials: J
authors.lastname: Zhang
authors.affiliation: X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439.
authors.forename: Byeongdu
authors.initials: B
authors.lastname: Lee
authors.affiliation: Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; and.
authors.forename: SonBinh T
authors.initials: ST
authors.lastname: Nguyen
authors.affiliation: Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL 60208; and chadnano@northwestern.edu.
authors.forename: Chad A
authors.initials: CA
authors.lastname: Mirkin
mesh_terms: D003460:Crystallization; D004247:DNA / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D053768:Metal Nanoparticles / Q000737:chemistry; D053758:Nanoparticles / Q000737:chemistry*; D036103:Nanotechnology / Q000379:methods; D009690:Nucleic Acid Conformation; D009841:Oligonucleotides / Q000737:chemistry; D012492:Salts / Q000737:chemistry; D012542:Scattering, Radiation; D017356:Synchrotrons; D013696:Temperature; D013816:Thermodynamics; D014965:X-Rays
chemical_list: D009841:Oligonucleotides; D012492:Salts; D006046:Gold; D004247:DNA
keywords: DNA materials; nanostructure; self assembly