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Title: Entropy-Driven Crystallization Behavior in DNA-Mediated Nanoparticle Assembly

Abstract

Herein, we report an example of entropy-driven crystallization behavior in DNA-nanoparticle superlattice assembly, marking a divergence from the well-established enthalpic driving force of maximizing nearest-neighbor hybridization connections. Such behavior is manifested in the observation of a non-close-packed, body-centered cubic (bcc) superlattice when using a system with self-complementary DNA linkers that would be predicted to form a close-packed, face-centered cubic (fcc) structure based solely on enthalpic considerations and previous design rules for DNA-linked particle assembly. Notably, this unexpected phase behavior is only observed when employing long DNA linkers with unpaired “flexor” bases positioned along the length of the DNA linker that increase the number of microstates available to the DNA ligands. A range of design conditions are tested showing sudden onsets of this behavior, and these experiments are coupled with coarse-grained molecular dynamics simulations to show that this entropy-driven crystallization behavior is due to the accessibility of additional microstates afforded by using long and flexible linkers.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1370658
Grant/Contract Number:  
SC0000989; FA9550-11-1-0275; FA9550-12-1-0280; N00014-15-1-0043; DGE-1324585
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 15; Journal Issue: 8; Related Information: CBES partners with Northwestern University (lead); Harvard University; New York University; Pennsylvania State University; University of Michigan; University of Pittsburgh; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; catalysis (homogeneous); solar (photovoltaic); bio-inspired; charge transport; mesostructured aterials; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); DNA; nanoparticle superlattice; nanomaterials; colloidal crystals; self-assembly; crystallization; genetics; nanoparticles; lattices hybridization

Citation Formats

Thaner, Ryan V., Kim, Youngeun, Li, Ting I. N. G., Macfarlane, Robert J., Nguyen, SonBinh T., Olvera de la Cruz, Monica, and Mirkin, Chad A. Entropy-Driven Crystallization Behavior in DNA-Mediated Nanoparticle Assembly. United States: N. p., 2015. Web. doi:10.1021/acs.nanolett.5b02129.
Thaner, Ryan V., Kim, Youngeun, Li, Ting I. N. G., Macfarlane, Robert J., Nguyen, SonBinh T., Olvera de la Cruz, Monica, & Mirkin, Chad A. Entropy-Driven Crystallization Behavior in DNA-Mediated Nanoparticle Assembly. United States. doi:10.1021/acs.nanolett.5b02129.
Thaner, Ryan V., Kim, Youngeun, Li, Ting I. N. G., Macfarlane, Robert J., Nguyen, SonBinh T., Olvera de la Cruz, Monica, and Mirkin, Chad A. Tue . "Entropy-Driven Crystallization Behavior in DNA-Mediated Nanoparticle Assembly". United States. doi:10.1021/acs.nanolett.5b02129. https://www.osti.gov/servlets/purl/1370658.
@article{osti_1370658,
title = {Entropy-Driven Crystallization Behavior in DNA-Mediated Nanoparticle Assembly},
author = {Thaner, Ryan V. and Kim, Youngeun and Li, Ting I. N. G. and Macfarlane, Robert J. and Nguyen, SonBinh T. and Olvera de la Cruz, Monica and Mirkin, Chad A.},
abstractNote = {Herein, we report an example of entropy-driven crystallization behavior in DNA-nanoparticle superlattice assembly, marking a divergence from the well-established enthalpic driving force of maximizing nearest-neighbor hybridization connections. Such behavior is manifested in the observation of a non-close-packed, body-centered cubic (bcc) superlattice when using a system with self-complementary DNA linkers that would be predicted to form a close-packed, face-centered cubic (fcc) structure based solely on enthalpic considerations and previous design rules for DNA-linked particle assembly. Notably, this unexpected phase behavior is only observed when employing long DNA linkers with unpaired “flexor” bases positioned along the length of the DNA linker that increase the number of microstates available to the DNA ligands. A range of design conditions are tested showing sudden onsets of this behavior, and these experiments are coupled with coarse-grained molecular dynamics simulations to show that this entropy-driven crystallization behavior is due to the accessibility of additional microstates afforded by using long and flexible linkers.},
doi = {10.1021/acs.nanolett.5b02129},
journal = {Nano Letters},
issn = {1530-6984},
number = 8,
volume = 15,
place = {United States},
year = {2015},
month = {6}
}

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