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Title: Unique Symmetry-Breaking Phenomenon during the Self-assembly of Macroions Elucidated by Simulation

Abstract

Various soluble hydrophilic macroions can self-assemble into hollow, spherical, monolayered supramolecular “blackberry”-type structures, despite their like-charged nature. However, how the 3-D symmetrical macroions prefer to form 2-D monolayers in bulk solution, especially for the highly symmetrical “Keplerate” polyoxometalates and functionalized C 60 macroions has been a mystery. Through molecular dynamics simulations, using a model specifically designed for macroions in solution, the mechanism of this intriguing symmetry-breaking process is found to be related to the apparently asymmetric charge distribution on the surface of macroions in the equatorial belt area (the area which can be effectively involved in the counterion-mediated attraction). As a result, the electric field lines around macroions during the self-assembly process clearly show that the symmetry-breaking happens at the dimer level effectively defining the plane of the self-assembly. These findings are expected to contribute to our fundamental knowledge of complex solution systems that are found in many fields from materials science to biological phenomena.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Univ. of Akron, OH (United States). Dept. of Polymer Science
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Akron, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1499997
Grant/Contract Number:  
SC0001089; DMR-1665284; CHE-1607138
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; coarse-grained models; self-assembly

Citation Formats

Liu, Zhuonan, Liu, Tianbo, and Tsige, Mesfin. Unique Symmetry-Breaking Phenomenon during the Self-assembly of Macroions Elucidated by Simulation. United States: N. p., 2018. Web. doi:10.1038/s41598-018-31533-z.
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Liu, Zhuonan, Liu, Tianbo, & Tsige, Mesfin. Unique Symmetry-Breaking Phenomenon during the Self-assembly of Macroions Elucidated by Simulation. United States. doi:10.1038/s41598-018-31533-z.
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Liu, Zhuonan, Liu, Tianbo, and Tsige, Mesfin. Thu . "Unique Symmetry-Breaking Phenomenon during the Self-assembly of Macroions Elucidated by Simulation". United States. doi:10.1038/s41598-018-31533-z. https://www.osti.gov/servlets/purl/1499997.
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@article{osti_1499997,
title = {Unique Symmetry-Breaking Phenomenon during the Self-assembly of Macroions Elucidated by Simulation},
author = {Liu, Zhuonan and Liu, Tianbo and Tsige, Mesfin},
abstractNote = {Various soluble hydrophilic macroions can self-assemble into hollow, spherical, monolayered supramolecular “blackberry”-type structures, despite their like-charged nature. However, how the 3-D symmetrical macroions prefer to form 2-D monolayers in bulk solution, especially for the highly symmetrical “Keplerate” polyoxometalates and functionalized C60 macroions has been a mystery. Through molecular dynamics simulations, using a model specifically designed for macroions in solution, the mechanism of this intriguing symmetry-breaking process is found to be related to the apparently asymmetric charge distribution on the surface of macroions in the equatorial belt area (the area which can be effectively involved in the counterion-mediated attraction). As a result, the electric field lines around macroions during the self-assembly process clearly show that the symmetry-breaking happens at the dimer level effectively defining the plane of the self-assembly. These findings are expected to contribute to our fundamental knowledge of complex solution systems that are found in many fields from materials science to biological phenomena.},
doi = {10.1038/s41598-018-31533-z},
journal = {Scientific Reports},
number = ,
volume = 8,
place = {United States},
year = {2018},
month = {8}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1038/s41598-018-31533-z
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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Coarse-graining of various macroions that form blackberry structures. (a) Examples of different kinds of macroions, including inorganic metal-oxide molecular clusters (1, 2)8–13, metal-organic nanocages (3)18–21, functionalized fullerenes (4)15, cyclodextrins (5)14 and dendrimers (6)17. (b) A typical blackberry structure self-assembled from metal-oxide molecular clusters (a1), which is a monolayermore » hollow sphere. (c) A coarse-grained model designed for general spherical macroions. In this model, the cyan beads have only VDW interactions while the yellow beads have both VDW and electrostatic interactions.« less
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