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Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers

[Image: see text] Supramolecular block copolymers composed of discrete blocks have promising properties for nanotechnology resulting from their ability to combine well-defined morphologies with good bulk material properties. Here, we present the impact of a well-defined siloxane block in either the...

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Autores principales: Lamers, Brigitte A. G., van der Tol, Joost J. B., Vonk, Kasper M., de Waal, Bas F. M., Palmans, Anja R. A., Meijer, E. W., Vantomme, Ghislaine
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7690048/
https://www.ncbi.nlm.nih.gov/pubmed/33250525
http://dx.doi.org/10.1021/acs.macromol.0c02237
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author Lamers, Brigitte A. G.
van der Tol, Joost J. B.
Vonk, Kasper M.
de Waal, Bas F. M.
Palmans, Anja R. A.
Meijer, E. W.
Vantomme, Ghislaine
author_facet Lamers, Brigitte A. G.
van der Tol, Joost J. B.
Vonk, Kasper M.
de Waal, Bas F. M.
Palmans, Anja R. A.
Meijer, E. W.
Vantomme, Ghislaine
author_sort Lamers, Brigitte A. G.
collection PubMed
description [Image: see text] Supramolecular block copolymers composed of discrete blocks have promising properties for nanotechnology resulting from their ability to combine well-defined morphologies with good bulk material properties. Here, we present the impact of a well-defined siloxane block in either the main-chain or present as pendant grafts on the properties of supramolecular block copolymers that form ordered nanostructures with sub-5 nm domains. For this, two types of supramolecular block copolymers were synthesized based on the ureidopyrimidinone–urethane (UPy-UT) motif. In the first, oligodimethylsiloxanes (oDMS) of discrete length were end-capped with the UPy-UT motif, affording main-chain UPy-UT-Si(n). In the second, the UPy-UT motif was grafted with discrete oDMS affording grafted UPy-UT-g-Si(7). For the two systems, the compositions are similar; only the molecular architecture differs. In both cases, crystallization of the UPy-UT block is in synergy with phase segregation of the oDMS, resulting in the formation of lamellar morphologies. The grafted UPy-UT-g-Si(7) can form long-range ordered lamellae, resulting in the formation of micrometer-sized 2D sheets of supramolecular polymers which show brittle properties. In contrast, UPy-UT-Si(n) forms a ductile material. As the compositions of both BCOs are similar, the differences in morphology and mechanical properties are a direct consequence of the molecular architecture. These results showcase how molecular design of the building block capable of forming block copolymers translates into controlled nanostructures and material properties as a result of the supramolecular nature of the interactions.
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spelling pubmed-76900482020-11-27 Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers Lamers, Brigitte A. G. van der Tol, Joost J. B. Vonk, Kasper M. de Waal, Bas F. M. Palmans, Anja R. A. Meijer, E. W. Vantomme, Ghislaine Macromolecules [Image: see text] Supramolecular block copolymers composed of discrete blocks have promising properties for nanotechnology resulting from their ability to combine well-defined morphologies with good bulk material properties. Here, we present the impact of a well-defined siloxane block in either the main-chain or present as pendant grafts on the properties of supramolecular block copolymers that form ordered nanostructures with sub-5 nm domains. For this, two types of supramolecular block copolymers were synthesized based on the ureidopyrimidinone–urethane (UPy-UT) motif. In the first, oligodimethylsiloxanes (oDMS) of discrete length were end-capped with the UPy-UT motif, affording main-chain UPy-UT-Si(n). In the second, the UPy-UT motif was grafted with discrete oDMS affording grafted UPy-UT-g-Si(7). For the two systems, the compositions are similar; only the molecular architecture differs. In both cases, crystallization of the UPy-UT block is in synergy with phase segregation of the oDMS, resulting in the formation of lamellar morphologies. The grafted UPy-UT-g-Si(7) can form long-range ordered lamellae, resulting in the formation of micrometer-sized 2D sheets of supramolecular polymers which show brittle properties. In contrast, UPy-UT-Si(n) forms a ductile material. As the compositions of both BCOs are similar, the differences in morphology and mechanical properties are a direct consequence of the molecular architecture. These results showcase how molecular design of the building block capable of forming block copolymers translates into controlled nanostructures and material properties as a result of the supramolecular nature of the interactions. American Chemical Society 2020-11-11 2020-11-24 /pmc/articles/PMC7690048/ /pubmed/33250525 http://dx.doi.org/10.1021/acs.macromol.0c02237 Text en © 2020 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 Lamers, Brigitte A. G.
van der Tol, Joost J. B.
Vonk, Kasper M.
de Waal, Bas F. M.
Palmans, Anja R. A.
Meijer, E. W.
Vantomme, Ghislaine
Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers
title Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers
title_full Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers
title_fullStr Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers
title_full_unstemmed Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers
title_short Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers
title_sort consequences of molecular architecture on the supramolecular assembly of discrete block co-oligomers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7690048/
https://www.ncbi.nlm.nih.gov/pubmed/33250525
http://dx.doi.org/10.1021/acs.macromol.0c02237
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