Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs

Lee, Sangmin; Teich, Erin G.; Engel, Michael; Glotzer, Sharon C.

doi:10.1073/pnas.1905929116

Title: Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs

Journal Article · 08 July 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1905929116 · OSTI ID:1610454

^[1]; Teich, Erin G. ^[2]; Engel, Michael ^[3]; Glotzer, Sharon C. ^[2]

Univ. of Michigan, Ann Arbor, MI (United States); DOE/OSTI
Univ. of Michigan, Ann Arbor, MI (United States)
Univ. of Michigan, Ann Arbor, MI (United States); Friedrich-Alexander Univ. Erlangen-Nurnberg (Germany)

Complex crystallization pathways are common in protein crystallization, tetrahedrally coordinated systems, and biomineralization, where single or multiple precursors temporarily appear before the formation of the crystal. The emergence of precursors is often explained by a unique property of the system, such as short-range attraction, directional bonding, or ion association. But, structural characteristics of the prenucleation phases found in multistep crystallization remain unclear, and models are needed for testing and expanding the understanding of fluid-to-solid ordering pathways. Here, we report 3 instances of 2-step crystallization of hard-particle fluids. Crystallization in these systems proceeds via a high-density precursor fluid phase with prenucleation motifs in the form of clusters, fibers and layers, and networks, respectively. The density and diffusivity change across the fluid–fluid phase transition increases with motif dimension. We observe crystal nucleation to be catalyzed by the interface between the 2 fluid phases. The crystals that form are complex, including, notably, a crystal with 432 particles in the cubic unit cell. Finally, our results establish the existence of complex crystallization pathways in entropic systems and reveal prenucleation motifs of various dimensions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: ACI-1053575; DGE 1256260; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0000989

OSTI ID:: 1610454

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 30 Vol. 116; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (42)

High Pressure Synthesis and Structure of a Novel Clathrate-Type Compound: Te7+xSi20-x (x ≈ 2.5). Jaussaud, Nicolas; Pouchard, Michel; Goglio, Graziella ChemInform, Vol. 34, Issue 50 https://doi.org/10.1002/chin.200350004	journal	December 2003
Thermodynamics and Kinetics of Prenucleation Clusters, Classical and Non-Classical Nucleation Zahn, Dirk ChemPhysChem, Vol. 16, Issue 10 https://doi.org/10.1002/cphc.201500231	journal	April 2015
The liquid protein phase in crystallization: a case study—intact immunoglobulins Kuznetsov, Yurii G.; Malkin, Alexander J.; McPherson, Alexander Journal of Crystal Growth, Vol. 232, Issue 1-4 https://doi.org/10.1016/S0022-0248(01)01058-2	journal	November 2001
High pressure synthesis and structure of a novel clathrate-type compound: Te7+xSi20−x (x∼2.5) Jaussaud, Nicolas; Pouchard, Michel; Goglio, Graziella Solid State Sciences, Vol. 5, Issue 9 https://doi.org/10.1016/S1293-2558(03)00172-9	journal	September 2003
Strong scaling of general-purpose molecular dynamics simulations on GPUs Glaser, Jens; Nguyen, Trung Dac; Anderson, Joshua A. Computer Physics Communications, Vol. 192 https://doi.org/10.1016/j.cpc.2015.02.028	journal	July 2015
Scalable Metropolis Monte Carlo for simulation of hard shapes Anderson, Joshua A.; Eric Irrgang, M.; Glotzer, Sharon C. Computer Physics Communications, Vol. 204 https://doi.org/10.1016/j.cpc.2016.02.024	journal	July 2016
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
A Diversity of Assembly Mechanisms of a Generic Amyloid Fold Eichner, Timo; Radford, Sheena E. Molecular Cell, Vol. 43, Issue 1 https://doi.org/10.1016/j.molcel.2011.05.012	journal	July 2011
Dense Liquid Precursor for the Nucleation of Ordered Solid Phases from Solution Vekilov, Peter G. Crystal Growth & Design, Vol. 4, Issue 4 https://doi.org/10.1021/cg049977w	journal	July 2004
Amorphous Precursors in the Nucleation of Clathrate Hydrates Jacobson, Liam C.; Hujo, Waldemar; Molinero, Valeria Journal of the American Chemical Society, Vol. 132, Issue 33 https://doi.org/10.1021/ja1051445	journal	July 2010
Role of Liquid Polymorphism during the Crystallization of Silicon Desgranges, Caroline; Delhommelle, Jerome Journal of the American Chemical Society, Vol. 133, Issue 9 https://doi.org/10.1021/ja1117478	journal	March 2011
Methane Clathrate Hydrate Nucleation Mechanism by Advanced Molecular Simulations Lauricella, Marco; Meloni, Simone; English, Niall J. The Journal of Physical Chemistry C, Vol. 118, Issue 40 https://doi.org/10.1021/jp5052479	journal	September 2014
Self-Assembly in Two Dimensions: Surface Micelles and Domain Formation in Monolayers Israelachvili, Jacob Langmuir, Vol. 10, Issue 10 https://doi.org/10.1021/la00022a062	journal	October 1994
Crystalline Assemblies and Densest Packings of a Family of Truncated Tetrahedra and the Role of Directional Entropic Forces Damasceno, Pablo F.; Engel, Michael; Glotzer, Sharon C. ACS Nano, Vol. 6, Issue 1 https://doi.org/10.1021/nn204012y	journal	November 2011
The relationship between liquid, supercooled and glassy water Mishima, Osamu; Stanley, H. Eugene Nature, Vol. 396, Issue 6709 https://doi.org/10.1038/24540	journal	November 1998
Generic mechanism for generating a liquid–liquid phase transition Franzese, Giancarlo; Malescio, Gianpietro; Skibinsky, Anna Nature, Vol. 409, Issue 6821 https://doi.org/10.1038/35055514	journal	February 2001
Prediction of absolute crystal-nucleation rate in hard-sphere colloids Auer, Stefan; Frenkel, Daan Nature, Vol. 409, Issue 6823 https://doi.org/10.1038/35059035	journal	February 2001
Metastable liquid–liquid transition in a molecular model of water Palmer, Jeremy C.; Martelli, Fausto; Liu, Yang Nature, Vol. 510, Issue 7505 https://doi.org/10.1038/nature13405	journal	June 2014
Surface-induced crystallization in supercooled tetrahedral liquids Li, Tianshu; Donadio, Davide; Ghiringhelli, Luca M. Nature Materials, Vol. 8, Issue 9 https://doi.org/10.1038/nmat2508	journal	August 2009
The role of prenucleation clusters in surface-induced calcium phosphate crystallization Dey, Archan; Bomans, Paul H. H.; Müller, Frank A. Nature Materials, Vol. 9, Issue 12 https://doi.org/10.1038/nmat2900	journal	November 2010
Order through entropy Frenkel, Daan Nature Materials, Vol. 14, Issue 1 https://doi.org/10.1038/nmat4178	journal	December 2014
Liquid–liquid phase transition in supercooled silicon Sastry, Srikanth; Austen Angell, C. Nature Materials, Vol. 2, Issue 11 https://doi.org/10.1038/nmat994	journal	October 2003
Erasing no-man’s land by thermodynamically stabilizing the liquid–liquid transition in tetrahedral particles Smallenburg, Frank; Filion, Laura; Sciortino, Francesco Nature Physics, Vol. 10, Issue 9 https://doi.org/10.1038/nphys3030	journal	July 2014
Geometrical frustration yields fibre formation in self-assembly Lenz, Martin; Witten, Thomas A. Nature Physics, Vol. 13, Issue 11 https://doi.org/10.1038/nphys4184	journal	July 2017
Observation of two-step nucleation in methane hydrates Vatamanu, Jenel; Kusalik, Peter G. Physical Chemistry Chemical Physics, Vol. 12, Issue 45 https://doi.org/10.1039/c0cp00551g	journal	January 2010
Monte Carlo simulations of amphiphilic nanoparticle self-assembly Davis, Jonathan R.; Panagiotopoulos, Athanassios Z. The Journal of Chemical Physics, Vol. 129, Issue 19 https://doi.org/10.1063/1.3009183	journal	November 2008
Spinodal decomposition of a symmetric critical mixture of deuterated and protonated polymer Bates, Frank S.; Wiltzius, Pierre The Journal of Chemical Physics, Vol. 91, Issue 5 https://doi.org/10.1063/1.456901	journal	September 1989
Phase transitions in fluctuations and their role in two-step nucleation James, Daniella; Beairsto, Seamus; Hartt, Carmen The Journal of Chemical Physics, Vol. 150, Issue 7 https://doi.org/10.1063/1.5057429	journal	February 2019
Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal Jiang, Hao; Debenedetti, Pablo G.; Panagiotopoulos, Athanassios Z. The Journal of Chemical Physics, Vol. 150, Issue 12 https://doi.org/10.1063/1.5084248	journal	March 2019
Molecular dynamics simulations of spontaneous fibril formation by random-coil peptides Nguyen, H. D.; Hall, C. K. Proceedings of the National Academy of Sciences, Vol. 101, Issue 46 https://doi.org/10.1073/pnas.0407273101	journal	November 2004
Understanding shape entropy through local dense packing van Anders, Greg; Klotsa, Daphne; Ahmed, N. Khalid Proceedings of the National Academy of Sciences, Vol. 111, Issue 45 https://doi.org/10.1073/pnas.1418159111	journal	October 2014
Computational investigation of surface freezing in a molecular model of water Haji-Akbari, Amir; Debenedetti, Pablo G. Proceedings of the National Academy of Sciences, Vol. 114, Issue 13 https://doi.org/10.1073/pnas.1620999114	journal	March 2017
Tuning the Liquid-Liquid Transition by Modulating the Hydrogen-Bond Angular Flexibility in a Model for Water Smallenburg, Frank; Sciortino, Francesco Physical Review Letters, Vol. 115, Issue 1 https://doi.org/10.1103/PhysRevLett.115.015701	journal	July 2015
The crystal structure of the metallic phase Mg32(Al, Zn)49 Bergman, G.; Waugh, J. L. T.; Pauling, L. Acta Crystallographica, Vol. 10, Issue 4 https://doi.org/10.1107/S0365110X57000808	journal	April 1957
Real-Space Imaging of Nucleation and Growth in Colloidal Crystallization Gasser, U. Science, Vol. 292, Issue 5515 https://doi.org/10.1126/science.1058457	journal	April 2001
Stable Prenucleation Calcium Carbonate Clusters Gebauer, Denis; Völkel, Antje; Cölfen, Helmut Science, Vol. 322, Issue 5909 https://doi.org/10.1126/science.1164271	journal	December 2008
Predictive Self-Assembly of Polyhedra into Complex Structures Damasceno, P. F.; Engel, M.; Glotzer, S. C. Science, Vol. 337, Issue 6093 https://doi.org/10.1126/science.1220869	journal	July 2012
Microscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 Solutions Wallace, A. F.; Hedges, L. O.; Fernandez-Martinez, A. Science, Vol. 341, Issue 6148 https://doi.org/10.1126/science.1230915	journal	August 2013
Enhancement of Protein Crystal Nucleation by Critical Density Fluctuations Wolde, Pieter Rein ten; Frenkel, Daan Science, Vol. 277, Issue 5334, p. 1975-1978 https://doi.org/10.1126/science.277.5334.1975	journal	September 1997
Crystallization by particle attachment in synthetic, biogenic, and geologic environments De Yoreo, J. J.; Gilbert, P. U. P. A.; Sommerdijk, N. A. J. M. Science, Vol. 349, Issue 6247 https://doi.org/10.1126/science.aaa6760	journal	July 2015
Clathrate colloidal crystals Lin, Haixin; Lee, Sangmin; Sun, Lin Science, Vol. 355, Issue 6328 https://doi.org/10.1126/science.aal3919	journal	March 2017
Understanding shape entropy through local dense packing van Anders, Greg; Klotsa, Daphne; Ahmed, N. Khalid arXiv https://doi.org/10.48550/arxiv.1309.1187	text	January 2013

Cited By (1)

Two-step crystallization and solid–solid transitions in binary colloidal mixtures Fang, Huang; Hagan, Michael F.; Rogers, W. Benjamin Proceedings of the National Academy of Sciences, Vol. 117, Issue 45 https://doi.org/10.1073/pnas.2008561117	journal	October 2020

Similar Records

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Journal Article · 2022 · Nature Communications · OSTI ID:2419558

Lee, Sangmin; Glotzer, Sharon C.

Quantifying Energetic and Entropic Pathways in Molecular Systems

Journal Article · 2022 · Journal of Physical Chemistry. B · OSTI ID:1991216

Beyerle, Eric R.; Mehdi, Shams; Tiwary, Pratyush

In-situ imaging of nucleation and growth of superlattices from nanoscale colloidal nanoparticles

Journal Article · 2022 · Journal of Crystal Growth · OSTI ID:2421639

Wang, Zuochen; Liu, Chang; Chen, Qian

Related Subjects

2-step crystallization
59 BASIC BIOLOGICAL SCIENCES
colloidal crystallization
entropic crystallization
fluid-fluid phase transitions
liquid-liquid phase
transition

Title: Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs

Citation Formats

References (42)

Cited By (1)

Similar Records

Related Subjects