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Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory

The induction of supramolecular chirality from achiral polymers has been widely investigated in composite systems consisting of a chiral guest, achiral host, and solvents. To further study and understand the process of chirality transfer from a chiral solvent or chiral molecules to an achiral polyme...

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Autores principales: Miao, Tengfei, Yin, Lu, Cheng, Xiaoxiao, Zhao, Yin, Hou, Wenjie, Zhang, Wei, Zhu, Xiulin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6404070/
https://www.ncbi.nlm.nih.gov/pubmed/30966646
http://dx.doi.org/10.3390/polym10060612
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author Miao, Tengfei
Yin, Lu
Cheng, Xiaoxiao
Zhao, Yin
Hou, Wenjie
Zhang, Wei
Zhu, Xiulin
author_facet Miao, Tengfei
Yin, Lu
Cheng, Xiaoxiao
Zhao, Yin
Hou, Wenjie
Zhang, Wei
Zhu, Xiulin
author_sort Miao, Tengfei
collection PubMed
description The induction of supramolecular chirality from achiral polymers has been widely investigated in composite systems consisting of a chiral guest, achiral host, and solvents. To further study and understand the process of chirality transfer from a chiral solvent or chiral molecules to an achiral polymer backbone or side-chain units, an alternative is to reduce the components in the supramolecular assembled systems. Herein, achiral side-chain azobenzene (Azo)-containing polymers, poly(6-[4-(4-methoxyphenylazo) phenoxy] hexyl methacrylate) (PAzoMA), with different M(n)s, were synthesized by atom transfer radical polymerization (ATRP). Preferred chirality from supramolecular assembled trans-Azo units of PAzoMAs is successfully induced solely by the neat limonene. These aggregates of the polymers in limonene solution were characterized by circular dichroism (CD), UV-vis spectra, and dynamic light scattering (DLS) under different temperatures. The temperature plays an important role in the course of chiral induction. Meanwhile, supramolecular chirality can be constructed in the solid films of the achiral side-chain Azo-containing polymers that were triggered by limonene vapors. Also, it can be erased after heated above the glass transition temperature (T(g)) of the polymer, and recovered after cooling down in the limonene vapors. A chiroptical switch can be built by alternately changing the temperature. The solid films show good chiral memory behaviors. The current results will facilitate studying the mechanism of chirality transfer induced by chiral solvent and improve potential application possibilities in chiral film materials.
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spelling pubmed-64040702019-04-02 Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory Miao, Tengfei Yin, Lu Cheng, Xiaoxiao Zhao, Yin Hou, Wenjie Zhang, Wei Zhu, Xiulin Polymers (Basel) Article The induction of supramolecular chirality from achiral polymers has been widely investigated in composite systems consisting of a chiral guest, achiral host, and solvents. To further study and understand the process of chirality transfer from a chiral solvent or chiral molecules to an achiral polymer backbone or side-chain units, an alternative is to reduce the components in the supramolecular assembled systems. Herein, achiral side-chain azobenzene (Azo)-containing polymers, poly(6-[4-(4-methoxyphenylazo) phenoxy] hexyl methacrylate) (PAzoMA), with different M(n)s, were synthesized by atom transfer radical polymerization (ATRP). Preferred chirality from supramolecular assembled trans-Azo units of PAzoMAs is successfully induced solely by the neat limonene. These aggregates of the polymers in limonene solution were characterized by circular dichroism (CD), UV-vis spectra, and dynamic light scattering (DLS) under different temperatures. The temperature plays an important role in the course of chiral induction. Meanwhile, supramolecular chirality can be constructed in the solid films of the achiral side-chain Azo-containing polymers that were triggered by limonene vapors. Also, it can be erased after heated above the glass transition temperature (T(g)) of the polymer, and recovered after cooling down in the limonene vapors. A chiroptical switch can be built by alternately changing the temperature. The solid films show good chiral memory behaviors. The current results will facilitate studying the mechanism of chirality transfer induced by chiral solvent and improve potential application possibilities in chiral film materials. MDPI 2018-06-04 /pmc/articles/PMC6404070/ /pubmed/30966646 http://dx.doi.org/10.3390/polym10060612 Text en © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Miao, Tengfei
Yin, Lu
Cheng, Xiaoxiao
Zhao, Yin
Hou, Wenjie
Zhang, Wei
Zhu, Xiulin
Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory
title Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory
title_full Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory
title_fullStr Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory
title_full_unstemmed Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory
title_short Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory
title_sort chirality construction from preferred π-π stacks of achiral azobenzene units in polymer: chiral induction, transfer and memory
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6404070/
https://www.ncbi.nlm.nih.gov/pubmed/30966646
http://dx.doi.org/10.3390/polym10060612
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