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Title: Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants

Abstract

Frank–Kasper (F-K) and quasicrystal phases were originally identified in metal alloys and only sporadically reported in soft materials. These unconventional sphere-packing schemes open up possibilities to design materials with different properties. The challenge in soft materials is how to correlate complex phases built from spheres with the tunable parameters of chemical composition and molecular architecture. Here, we report a complete sequence of various highly ordered mesophases by the self-assembly of specifically designed and synthesized giant surfactants, which are conjugates of hydrophilic polyhedral oligomeric silsesquioxane cages tethered with hydrophobic polystyrene tails. We show that the occurrence of these mesophases results from nanophase separation between the heads and tails and thus is critically dependent on molecular geometry. Variations in molecular geometry achieved by changing the number of tails from one to four not only shift compositional phase boundaries but also stabilize F-K and quasicrystal phases in regions where simple phases of spheroidal micelles are typically observed. These complex self-assembled nanostructures have been identified by combining X-ray scattering techniques and real-space electron microscopy images. Brownian dynamics simulations based on a simplified molecular model confirm the architecture-induced sequence of phases. Our results demonstrate the critical role of molecular architecture in dictating the formation ofmore » supramolecular crystals with “soft” spheroidal motifs and provide guidelines to the design of unconventional self-assembled nanostructures.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ORCiD logo; ; ; ; ;
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1342238
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 50; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE

Citation Formats

Yue, Kan, Huang, Mingjun, Marson, Ryan L., He, Jinlin, Huang, Jiahao, Zhou, Zhe, Wang, Jing, Liu, Chang, Yan, Xuesheng, Wu, Kan, Guo, Zaihong, Liu, Hao, Zhang, Wei, Ni, Peihong, Wesdemiotis, Chrys, Zhang, Wen-Bin, Glotzer, Sharon C., and Cheng, Stephen Z. D. Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants. United States: N. p., 2016. Web. doi:10.1073/pnas.1609422113.
Yue, Kan, Huang, Mingjun, Marson, Ryan L., He, Jinlin, Huang, Jiahao, Zhou, Zhe, Wang, Jing, Liu, Chang, Yan, Xuesheng, Wu, Kan, Guo, Zaihong, Liu, Hao, Zhang, Wei, Ni, Peihong, Wesdemiotis, Chrys, Zhang, Wen-Bin, Glotzer, Sharon C., & Cheng, Stephen Z. D. Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants. United States. doi:10.1073/pnas.1609422113.
Yue, Kan, Huang, Mingjun, Marson, Ryan L., He, Jinlin, Huang, Jiahao, Zhou, Zhe, Wang, Jing, Liu, Chang, Yan, Xuesheng, Wu, Kan, Guo, Zaihong, Liu, Hao, Zhang, Wei, Ni, Peihong, Wesdemiotis, Chrys, Zhang, Wen-Bin, Glotzer, Sharon C., and Cheng, Stephen Z. D. Mon . "Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants". United States. doi:10.1073/pnas.1609422113.
@article{osti_1342238,
title = {Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants},
author = {Yue, Kan and Huang, Mingjun and Marson, Ryan L. and He, Jinlin and Huang, Jiahao and Zhou, Zhe and Wang, Jing and Liu, Chang and Yan, Xuesheng and Wu, Kan and Guo, Zaihong and Liu, Hao and Zhang, Wei and Ni, Peihong and Wesdemiotis, Chrys and Zhang, Wen-Bin and Glotzer, Sharon C. and Cheng, Stephen Z. D.},
abstractNote = {Frank–Kasper (F-K) and quasicrystal phases were originally identified in metal alloys and only sporadically reported in soft materials. These unconventional sphere-packing schemes open up possibilities to design materials with different properties. The challenge in soft materials is how to correlate complex phases built from spheres with the tunable parameters of chemical composition and molecular architecture. Here, we report a complete sequence of various highly ordered mesophases by the self-assembly of specifically designed and synthesized giant surfactants, which are conjugates of hydrophilic polyhedral oligomeric silsesquioxane cages tethered with hydrophobic polystyrene tails. We show that the occurrence of these mesophases results from nanophase separation between the heads and tails and thus is critically dependent on molecular geometry. Variations in molecular geometry achieved by changing the number of tails from one to four not only shift compositional phase boundaries but also stabilize F-K and quasicrystal phases in regions where simple phases of spheroidal micelles are typically observed. These complex self-assembled nanostructures have been identified by combining X-ray scattering techniques and real-space electron microscopy images. Brownian dynamics simulations based on a simplified molecular model confirm the architecture-induced sequence of phases. Our results demonstrate the critical role of molecular architecture in dictating the formation of supramolecular crystals with “soft” spheroidal motifs and provide guidelines to the design of unconventional self-assembled nanostructures.},
doi = {10.1073/pnas.1609422113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 50,
volume = 113,
place = {United States},
year = {2016},
month = {11}
}

Works referenced in this record:

Quasicrystals: A New Class of Ordered Structures
journal, December 1984


Metallic Phase with Long-Range Orientational Order and No Translational Symmetry
journal, November 1984


Structural diversity in binary nanoparticle superlattices
journal, January 2006

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