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Title: Directionally Interacting Spheres and Rods Form Ordered Phases

Abstract

The structures formed by mixtures of dissimilarly shaped nanoscale objects can significantly enhance our ability to produce nanoscale architectures. However, understanding their formation is a complex problem due to the interplay of geometric effects (entropy) and energetic interactions at the nanoscale. Spheres and rods are perhaps the most basic geometrical shapes and serve as convenient models of such dissimilar objects. The ordered phases formed by each of these individual shapes have already been explored, but, when mixed, spheres and rods have demonstrated only limited structural organization to date. We show using experiments and theory that the introduction of directional attractions between rod ends and isotropically interacting spherical nanoparticles (NPs) through DNA base pairing leads to the formation of ordered three-dimensional lattices. The spheres and rods arrange themselves in a complex alternating manner, where the spheres can form either a face-centered cubic (FCC) or hexagonal close-packed (HCP) lattice, or a disordered phase, as observed by in situ X-ray scattering. Increasing NP diameter at fixed rod length yields an initial transition from a disordered phase to the HCP crystal, energetically stabilized by rod-rod attraction across alternating crystal layers, as revealed by theory. In the limit of large NPs, the FCC structure ismore » instead stabilized over the HCP by rod entropy. Thus, we propose that directionally specific attractions in mixtures of anisotropic and isotropic objects offer insight into unexplored self-assembly behavior of noncomplementary shaped particles.« less

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [4]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  2. Princeton Univ., NJ (United States). Dept. of Chemical and Biological Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering, Dept. of Applied Physics and Applied Mathematics
  4. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1399671
Report Number(s):
BNL-114380-2017-JA
Journal ID: ISSN 1936-0851; KC0403020
Grant/Contract Number:
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 5; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; anisotropic colloids; colloidal crystals; DNA nanotechnology; nanoparticles; polymorphism; self-assembly; Center for Functional Nanomaterials

Citation Formats

Liu, Wenyan, Mahynski, Nathan A., Gang, Oleg, Panagiotopoulos, Athanassios Z., and Kumar, Sanat K. Directionally Interacting Spheres and Rods Form Ordered Phases. United States: N. p., 2017. Web. doi:10.1021/acsnano.7b01592.
Liu, Wenyan, Mahynski, Nathan A., Gang, Oleg, Panagiotopoulos, Athanassios Z., & Kumar, Sanat K. Directionally Interacting Spheres and Rods Form Ordered Phases. United States. doi:10.1021/acsnano.7b01592.
Liu, Wenyan, Mahynski, Nathan A., Gang, Oleg, Panagiotopoulos, Athanassios Z., and Kumar, Sanat K. Wed . "Directionally Interacting Spheres and Rods Form Ordered Phases". United States. doi:10.1021/acsnano.7b01592. https://www.osti.gov/servlets/purl/1399671.
@article{osti_1399671,
title = {Directionally Interacting Spheres and Rods Form Ordered Phases},
author = {Liu, Wenyan and Mahynski, Nathan A. and Gang, Oleg and Panagiotopoulos, Athanassios Z. and Kumar, Sanat K.},
abstractNote = {The structures formed by mixtures of dissimilarly shaped nanoscale objects can significantly enhance our ability to produce nanoscale architectures. However, understanding their formation is a complex problem due to the interplay of geometric effects (entropy) and energetic interactions at the nanoscale. Spheres and rods are perhaps the most basic geometrical shapes and serve as convenient models of such dissimilar objects. The ordered phases formed by each of these individual shapes have already been explored, but, when mixed, spheres and rods have demonstrated only limited structural organization to date. We show using experiments and theory that the introduction of directional attractions between rod ends and isotropically interacting spherical nanoparticles (NPs) through DNA base pairing leads to the formation of ordered three-dimensional lattices. The spheres and rods arrange themselves in a complex alternating manner, where the spheres can form either a face-centered cubic (FCC) or hexagonal close-packed (HCP) lattice, or a disordered phase, as observed by in situ X-ray scattering. Increasing NP diameter at fixed rod length yields an initial transition from a disordered phase to the HCP crystal, energetically stabilized by rod-rod attraction across alternating crystal layers, as revealed by theory. In the limit of large NPs, the FCC structure is instead stabilized over the HCP by rod entropy. Thus, we propose that directionally specific attractions in mixtures of anisotropic and isotropic objects offer insight into unexplored self-assembly behavior of noncomplementary shaped particles.},
doi = {10.1021/acsnano.7b01592},
journal = {ACS Nano},
number = 5,
volume = 11,
place = {United States},
year = {Wed May 10 00:00:00 EDT 2017},
month = {Wed May 10 00:00:00 EDT 2017}
}

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