Entropy-Driven Crystallization Behavior in DNA-Mediated Nanoparticle Assembly

Thaner, Ryan V.; Kim, Youngeun; Li, Ting I. N. G.; Macfarlane, Robert J.; Nguyen, SonBinh T.; Olvera de la Cruz, Monica; Mirkin, Chad A.

doi:10.1021/acs.nanolett.5b02129

Entropy-Driven Crystallization Behavior in DNA-Mediated Nanoparticle Assembly

Journal Article · Tue Jun 30 00:00:00 EDT 2015 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.5b02129· OSTI ID:1370658

Thaner, Ryan V. ^[1]; Kim, Youngeun ^[1]; Li, Ting I. N. G. ^[1]; Macfarlane, Robert J. ^[1]; Nguyen, SonBinh T. ^[1]; Olvera de la Cruz, Monica ^[1]; Mirkin, Chad A. ^[1]

Northwestern Univ., Evanston, IL (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0000989

OSTI ID:: 1370658

Alternate ID(s):: OSTI ID: 1470463

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 8 Vol. 15; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Transitioning DNA-Engineered Nanoparticle Superlattices from Solution to the Solid State Auyeung, Evelyn; Macfarlane, Robert J.; Choi, Chung Hang J. Advanced Materials, Vol. 24, Issue 38 https://doi.org/10.1002/adma.201202069	journal	July 2012
Oligonucleotide Flexibility Dictates Crystal Quality in DNA-Programmable Nanoparticle Superlattices Senesi, Andrew J.; Eichelsdoerfer, Daniel J.; Brown, Keith A. Advanced Materials, Vol. 26, Issue 42 https://doi.org/10.1002/adma.201402548	journal	September 2014
Establishing the Design Rules for DNA-Mediated Programmable Colloidal Crystallization Macfarlane, Robert J.; Jones, Matthew R.; Senesi, Andrew J. Angewandte Chemie International Edition, Vol. 49, Issue 27 https://doi.org/10.1002/anie.201000633	journal	May 2010
Nucleic Acid-Modified Nanostructures as Programmable Atom Equivalents: Forging a New “Table of Elements” Macfarlane, Robert J.; O'Brien, Matthew N.; Petrosko, Sarah Hurst Angewandte Chemie International Edition, Vol. 52, Issue 22 https://doi.org/10.1002/anie.201209336	journal	May 2013
On the selection of FCC and BCC lattices in poly(styrene-b-isoprene) copolymer micelles Bang, Joona; Lodge, Timothy P. Macromolecular Research, Vol. 16, Issue 1 https://doi.org/10.1007/BF03218960	journal	January 2008
Materials design by DNA programmed self-assembly Knorowski, C.; Travesset, A. Current Opinion in Solid State and Materials Science, Vol. 15, Issue 6 https://doi.org/10.1016/j.cossms.2011.07.002	journal	December 2011
Rigid body constraints realized in massively-parallel molecular dynamics on graphics processing units Nguyen, Trung Dac; Phillips, Carolyn L.; Anderson, Joshua A. Computer Physics Communications, Vol. 182, Issue 11 https://doi.org/10.1016/j.cpc.2011.06.005	journal	November 2011
General purpose molecular dynamics simulations fully implemented on graphics processing units Anderson, Joshua A.; Lorenz, Chris D.; Travesset, A. Journal of Computational Physics, Vol. 227, Issue 10 https://doi.org/10.1016/j.jcp.2008.01.047	journal	May 2008
Maximizing DNA Loading on a Range of Gold Nanoparticle Sizes Hurst, Sarah J.; Lytton-Jean, Abigail K. R.; Mirkin, Chad A. Analytical Chemistry, Vol. 78, Issue 24 https://doi.org/10.1021/ac0613582	journal	December 2006
Spherical Nucleic Acids Cutler, Joshua I.; Auyeung, Evelyn; Mirkin, Chad A. Journal of the American Chemical Society, Vol. 134, Issue 3 https://doi.org/10.1021/ja209351u	journal	January 2012
Thermally Active Hybridization Drives the Crystallization of DNA-Functionalized Nanoparticles Li, Ting I. N. G.; Sknepnek, Rastko; Olvera de la Cruz, Monica Journal of the American Chemical Society, Vol. 135, Issue 23 https://doi.org/10.1021/ja312644h	journal	May 2013
Dynamically Interchangeable Nanoparticle Superlattices Through the Use of Nucleic Acid-Based Allosteric Effectors Kim, Youngeun; Macfarlane, Robert J.; Mirkin, Chad A. Journal of the American Chemical Society, Vol. 135, Issue 28 https://doi.org/10.1021/ja405988r	journal	May 2013
Maximizing Entropy by Minimizing Area: Towards a New Principle of Self-Organization Ziherl, P.; Kamien, Randall D. The Journal of Physical Chemistry B, Vol. 105, Issue 42 https://doi.org/10.1021/jp010944q	journal	October 2001
Ordered packing arrangements of spherical micelles of diblock copolymers in two and three dimensions Thomas, Edwin L.; Kinning, David J.; Alward, David B. Macromolecules, Vol. 20, Issue 11 https://doi.org/10.1021/ma00177a049	journal	November 1987
Modeling the Crystallization of Spherical Nucleic Acid Nanoparticle Conjugates with Molecular Dynamics Simulations Li, Ting I. N. G.; Sknepnek, Rastko; Macfarlane, Robert J. Nano Letters, Vol. 12, Issue 5 https://doi.org/10.1021/nl300679e	journal	April 2012
A DNA-based method for rationally assembling nanoparticles into macroscopic materials Mirkin, Chad A.; Letsinger, Robert L.; Mucic, Robert C. Nature, Vol. 382, Issue 6592, p. 607-609 https://doi.org/10.1038/382607a0	journal	August 1996
Structural diversity in binary nanoparticle superlattices Shevchenko, Elena V.; Talapin, Dmitri V.; Kotov, Nicholas A. Nature, Vol. 439, Issue 7072, p. 55-59 https://doi.org/10.1038/nature04414	journal	January 2006
DNA-programmable nanoparticle crystallization Park, Sung Yong; Lytton-Jean, Abigail K. R.; Lee, Byeongdu Nature, Vol. 451, Issue 7178, p. 553-556 https://doi.org/10.1038/nature06508	journal	January 2008
DNA-guided crystallization of colloidal nanoparticles Nykypanchuk, Dmytro; Maye, Mathew M.; van der Lelie, Daniel Nature, Vol. 451, Issue 7178, p. 549-552 https://doi.org/10.1038/nature06560	journal	January 2008
DNA-mediated nanoparticle crystallization into Wulff polyhedra Auyeung, Evelyn; Li, Ting I. N. G.; Senesi, Andrew J. Nature, Vol. 505, Issue 7481 https://doi.org/10.1038/nature12739	journal	November 2013
A general approach to DNA-programmable atom equivalents Zhang, Chuan; Macfarlane, Robert J.; Young, Kaylie L. Nature Materials, Vol. 12, Issue 8 https://doi.org/10.1038/nmat3647	journal	May 2013
Synthetically programmable nanoparticle superlattices using a hollow three-dimensional spacer approach Auyeung, Evelyn; Cutler, Joshua I.; Macfarlane, Robert J. Nature Nanotechnology, Vol. 7, Issue 1 https://doi.org/10.1038/nnano.2011.222	journal	December 2011
Building plasmonic nanostructures with DNA Tan, Shawn J.; Campolongo, Michael J.; Luo, Dan Nature Nanotechnology, Vol. 6, Issue 5 https://doi.org/10.1038/nnano.2011.49	journal	April 2011
Dynamics of DNA-programmable nanoparticle crystallization: gelation, nucleation and topological defects Knorowski, Christopher; Travesset, Alex Soft Matter, Vol. 8, Issue 48 https://doi.org/10.1039/c2sm26832a	journal	January 2012
Temperature-dependent micellar structures in poly(styrene-b-isoprene) diblock copolymer solutions near the critical micelle temperature Bang, Joona; Viswanathan, Karthik; Lodge, Timothy P. The Journal of Chemical Physics, Vol. 121, Issue 22 https://doi.org/10.1063/1.1812753	journal	January 2004
Importance of the DNA “bond” in programmable nanoparticle crystallization Macfarlane, Robert J.; Thaner, Ryan V.; Brown, Keith A. Proceedings of the National Academy of Sciences, Vol. 111, Issue 42 https://doi.org/10.1073/pnas.1416489111	journal	October 2014
DNA-mediated engineering of multicomponent enzyme crystals Brodin, Jeffrey D.; Auyeung, Evelyn; Mirkin, Chad A. Proceedings of the National Academy of Sciences, Vol. 112, Issue 15 https://doi.org/10.1073/pnas.1503533112	journal	March 2015
Small-angle x-ray-scattering study of silver-nanocrystal disorder-order phase transitions Korgel, Brian A.; Fitzmaurice, Donald Physical Review B, Vol. 59, Issue 22 https://doi.org/10.1103/PhysRevB.59.14191	journal	June 1999
Dynamics and Statics of DNA-Programmable Nanoparticle Self-Assembly and Crystallization Knorowski, C.; Burleigh, S.; Travesset, A. Physical Review Letters, Vol. 106, Issue 21 https://doi.org/10.1103/PhysRevLett.106.215501	journal	May 2011
Molecular Origins of DNA Flexibility: Sequence Effects on Conformational and Mechanical Properties Ortiz, Vanessa; de Pablo, Juan J. Physical Review Letters, Vol. 106, Issue 23 https://doi.org/10.1103/PhysRevLett.106.238107	journal	June 2011
Theory of Programmable Hierarchic Self-Assembly Tkachenko, Alexei V. Physical Review Letters, Vol. 106, Issue 25 https://doi.org/10.1103/PhysRevLett.106.255501	journal	June 2011
Origin of the Thermoreversible fcc-bcc Transition in Block Copolymer Solutions Lodge, Timothy P.; Bang, Joona; Park, Moon Jeong Physical Review Letters, Vol. 92, Issue 14 https://doi.org/10.1103/PhysRevLett.92.145501	journal	April 2004
Long-Lived Metastable bcc Phase during Ordering of Micelles Bang, Joona; Lodge, Timothy P. Physical Review Letters, Vol. 93, Issue 24 https://doi.org/10.1103/PhysRevLett.93.245701	journal	December 2004
Nanoparticle Superlattice Engineering with DNA Macfarlane, R. J.; Lee, B.; Jones, M. R. Science, Vol. 334, Issue 6053, p. 204-208 https://doi.org/10.1126/science.1210493	journal	October 2011
On Side-Chain Conformational Entropy of Proteins Zhang, Jinfeng; Liu, Jun S. PLoS Computational Biology, Vol. 2, Issue 12 https://doi.org/10.1371/journal.pcbi.0020168	journal	January 2006

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Using DNA to program the self-assembly of colloidal nanoparticles and microparticles Rogers, W. Benjamin; Shih, William M.; Manoharan, Vinothan N. Nature Reviews Materials, Vol. 1, Issue 3 https://doi.org/10.1038/natrevmats.2016.8	journal	March 2016
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Exploring the zone of anisotropy and broken symmetries in DNA-mediated nanoparticle crystallization O’Brien, Matthew N.; Girard, Martin; Lin, Hai-Xin Proceedings of the National Academy of Sciences, Vol. 113, Issue 38 https://doi.org/10.1073/pnas.1611808113	journal	September 2016

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