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Supramolecular Block Copolymers under Thermodynamic Control

[Image: see text] Supramolecular block copolymers are becoming attractive materials in nascent optoelectronic and catalytic technologies. However, their dynamic nature precludes the straightforward tuning and analysis of the polymer’s structure. Here we report the elucidation on the microstructure o...

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Autores principales: Adelizzi, Beatrice, Aloi, Antonio, Markvoort, Albert J., Ten Eikelder, Huub M. M., Voets, Ilja K., Palmans, Anja R. A., Meijer, E. W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6002778/
https://www.ncbi.nlm.nih.gov/pubmed/29733207
http://dx.doi.org/10.1021/jacs.8b02706
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author Adelizzi, Beatrice
Aloi, Antonio
Markvoort, Albert J.
Ten Eikelder, Huub M. M.
Voets, Ilja K.
Palmans, Anja R. A.
Meijer, E. W.
author_facet Adelizzi, Beatrice
Aloi, Antonio
Markvoort, Albert J.
Ten Eikelder, Huub M. M.
Voets, Ilja K.
Palmans, Anja R. A.
Meijer, E. W.
author_sort Adelizzi, Beatrice
collection PubMed
description [Image: see text] Supramolecular block copolymers are becoming attractive materials in nascent optoelectronic and catalytic technologies. However, their dynamic nature precludes the straightforward tuning and analysis of the polymer’s structure. Here we report the elucidation on the microstructure of triarylamine triamide-based supramolecular block copolymers through a comprehensive battery of spectroscopic, theoretical, and super-resolution microscopic techniques. Via spectroscopic analysis we demonstrate that the direct mixing of preassembled homopolymers and the copolymerization induced by slow cooling of monomers lead to the formation of the same copolymer’s architecture. The small but pronounced deviation of the experimental spectra from the linear combination of the homopolymers’ spectra hints at the formation of block copolymers. A mass balance model is introduced to further unravel the microstructure of the copolymers formed, and it confirms that stable multiblock supramolecular copolymers can be accessed from different routes. The multiblock structure of the supramolecular copolymers originates from the fine balance between favorable hydrogen-bonding interactions and a small mismatch penalty between two different monomers. Finally, we visualized the formation of the supramolecular block copolymers by adapting a recently developed super-resolution microscopy technique, interface point accumulation for imaging in nanoscale topography (iPAINT), for visualizing the architectures formed in organic media. Combining multiple techniques was crucial to unveil the microstructure of these complex dynamic supramolecular systems.
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spelling pubmed-60027782018-06-19 Supramolecular Block Copolymers under Thermodynamic Control Adelizzi, Beatrice Aloi, Antonio Markvoort, Albert J. Ten Eikelder, Huub M. M. Voets, Ilja K. Palmans, Anja R. A. Meijer, E. W. J Am Chem Soc [Image: see text] Supramolecular block copolymers are becoming attractive materials in nascent optoelectronic and catalytic technologies. However, their dynamic nature precludes the straightforward tuning and analysis of the polymer’s structure. Here we report the elucidation on the microstructure of triarylamine triamide-based supramolecular block copolymers through a comprehensive battery of spectroscopic, theoretical, and super-resolution microscopic techniques. Via spectroscopic analysis we demonstrate that the direct mixing of preassembled homopolymers and the copolymerization induced by slow cooling of monomers lead to the formation of the same copolymer’s architecture. The small but pronounced deviation of the experimental spectra from the linear combination of the homopolymers’ spectra hints at the formation of block copolymers. A mass balance model is introduced to further unravel the microstructure of the copolymers formed, and it confirms that stable multiblock supramolecular copolymers can be accessed from different routes. The multiblock structure of the supramolecular copolymers originates from the fine balance between favorable hydrogen-bonding interactions and a small mismatch penalty between two different monomers. Finally, we visualized the formation of the supramolecular block copolymers by adapting a recently developed super-resolution microscopy technique, interface point accumulation for imaging in nanoscale topography (iPAINT), for visualizing the architectures formed in organic media. Combining multiple techniques was crucial to unveil the microstructure of these complex dynamic supramolecular systems. American Chemical Society 2018-05-07 2018-06-13 /pmc/articles/PMC6002778/ /pubmed/29733207 http://dx.doi.org/10.1021/jacs.8b02706 Text en Copyright © 2018 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Adelizzi, Beatrice
Aloi, Antonio
Markvoort, Albert J.
Ten Eikelder, Huub M. M.
Voets, Ilja K.
Palmans, Anja R. A.
Meijer, E. W.
Supramolecular Block Copolymers under Thermodynamic Control
title Supramolecular Block Copolymers under Thermodynamic Control
title_full Supramolecular Block Copolymers under Thermodynamic Control
title_fullStr Supramolecular Block Copolymers under Thermodynamic Control
title_full_unstemmed Supramolecular Block Copolymers under Thermodynamic Control
title_short Supramolecular Block Copolymers under Thermodynamic Control
title_sort supramolecular block copolymers under thermodynamic control
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6002778/
https://www.ncbi.nlm.nih.gov/pubmed/29733207
http://dx.doi.org/10.1021/jacs.8b02706
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