Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase

Programming living and soft complex matter via primary structure and self-organization represents the key methodology employed to design functions in biological and synthetic nanoscience. Memory effects have been used to create commercial technologies including liquid crystal displays and biomedical...

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Autores principales:	Virgil Percec, Ning Huang, Qi Xiao, Benjamin E. Partridge, Dipankar Sahoo, Mohammad R. Imam, Mihai Peterca, Robert Graf, Hans-Wolfgang Spiess, Xiangbing Zeng, Goran Ungar
Formato:	article
Lenguaje:	EN
Publicado:	Elsevier 2022
Materias:	Fiber X-ray diffraction Epitaxial nucleation Supramolecular Self-assembly Soft matter Dendrimers Science (General) Q1-390
Acceso en línea:	https://doaj.org/article/d3d0f6dc2e574d4799530092278ada67
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spelling	oai:doaj.org-article:d3d0f6dc2e574d4799530092278ada672021-11-04T04:41:49ZSelf-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase2666-542510.1016/j.giant.2021.100084https://doaj.org/article/d3d0f6dc2e574d4799530092278ada672022-03-01T00:00:00Zhttp://www.sciencedirect.com/science/article/pii/S2666542521000382https://doaj.org/toc/2666-5425Programming living and soft complex matter via primary structure and self-organization represents the key methodology employed to design functions in biological and synthetic nanoscience. Memory effects have been used to create commercial technologies including liquid crystal displays and biomedical applications based on shape memory polymers. Supramolecular orientational memory (SOM), induced by an epitaxial nucleation mediated by the close contact spheres of cubic phases, emerged as a pathway to engineer complex nanoscale soft matter of helical columnar hexagonal arrays. SOM preserves the crystallographic directions of close contact supramolecular spheres from the 3D phase upon cooling to the columnar hexagonal periodic array. Despite the diversity of 3D periodic and quasiperiodic nanoarrays of supramolecular dendrimers, including Frank-Kasper and quasicrystal, all examples of SOM to date were mediated by Im3¯m (body-centered cubic, BCC) and Pm3¯n (Frank-Kasper A15) cubic phases. Expanding the scope of SOM to non-cubic arrays is expected to generate additional morphologies that were not yet available by any other methods. Here we demonstrate the SOM of a dendronized triphenylene that self-organizes into helical columnar hexagonal and tetragonal P42/mnm (Frank-Kasper σ) phases. Structural analysis of oriented fibers by X-ray diffraction reveals that helical columnar hexagonal domains self-organize an unusual rectangular bipyramidal morphology upon cooling from the σ phase. The discovery of SOM in a non-cubic Frank-Kasper phase indicates that this methodology may be expanded to other periodic and quasiperiodic nanoarrays organized from self-assembling dendrimers and, most probably, to other soft and living complex matter.Virgil PercecNing HuangQi XiaoBenjamin E. PartridgeDipankar SahooMohammad R. ImamMihai PetercaRobert GrafHans-Wolfgang SpiessXiangbing ZengGoran UngarElsevierarticleFiber X-ray diffractionEpitaxial nucleationSupramolecularSelf-assemblySoft matterDendrimersScience (General)Q1-390ENGiant, Vol 9, Iss , Pp 100084- (2022)
institution	DOAJ
collection	DOAJ
language	EN
topic	Fiber X-ray diffraction Epitaxial nucleation Supramolecular Self-assembly Soft matter Dendrimers Science (General) Q1-390
spellingShingle	Fiber X-ray diffraction Epitaxial nucleation Supramolecular Self-assembly Soft matter Dendrimers Science (General) Q1-390 Virgil Percec Ning Huang Qi Xiao Benjamin E. Partridge Dipankar Sahoo Mohammad R. Imam Mihai Peterca Robert Graf Hans-Wolfgang Spiess Xiangbing Zeng Goran Ungar Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase
description	Programming living and soft complex matter via primary structure and self-organization represents the key methodology employed to design functions in biological and synthetic nanoscience. Memory effects have been used to create commercial technologies including liquid crystal displays and biomedical applications based on shape memory polymers. Supramolecular orientational memory (SOM), induced by an epitaxial nucleation mediated by the close contact spheres of cubic phases, emerged as a pathway to engineer complex nanoscale soft matter of helical columnar hexagonal arrays. SOM preserves the crystallographic directions of close contact supramolecular spheres from the 3D phase upon cooling to the columnar hexagonal periodic array. Despite the diversity of 3D periodic and quasiperiodic nanoarrays of supramolecular dendrimers, including Frank-Kasper and quasicrystal, all examples of SOM to date were mediated by Im3¯m (body-centered cubic, BCC) and Pm3¯n (Frank-Kasper A15) cubic phases. Expanding the scope of SOM to non-cubic arrays is expected to generate additional morphologies that were not yet available by any other methods. Here we demonstrate the SOM of a dendronized triphenylene that self-organizes into helical columnar hexagonal and tetragonal P42/mnm (Frank-Kasper σ) phases. Structural analysis of oriented fibers by X-ray diffraction reveals that helical columnar hexagonal domains self-organize an unusual rectangular bipyramidal morphology upon cooling from the σ phase. The discovery of SOM in a non-cubic Frank-Kasper phase indicates that this methodology may be expanded to other periodic and quasiperiodic nanoarrays organized from self-assembling dendrimers and, most probably, to other soft and living complex matter.
format	article
author	Virgil Percec Ning Huang Qi Xiao Benjamin E. Partridge Dipankar Sahoo Mohammad R. Imam Mihai Peterca Robert Graf Hans-Wolfgang Spiess Xiangbing Zeng Goran Ungar
author_facet	Virgil Percec Ning Huang Qi Xiao Benjamin E. Partridge Dipankar Sahoo Mohammad R. Imam Mihai Peterca Robert Graf Hans-Wolfgang Spiess Xiangbing Zeng Goran Ungar
author_sort	Virgil Percec
title	Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase
title_short	Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase
title_full	Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase
title_fullStr	Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase
title_full_unstemmed	Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase
title_sort	self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a frank-kasper σ phase
publisher	Elsevier
publishDate	2022
url	https://doaj.org/article/d3d0f6dc2e574d4799530092278ada67
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Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase

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