Unveiling Polymerization Mechanism in pH-regulated Supramolecular Fibers in Aqueous Media

Nicolás M. Casellas; Lorenzo Albertazzi; Sílvia Pujals; Tomás Torres; Miguel García-Iglesias

doi:10.1002/chem.202101660

Unveiling Polymerization Mechanism in pH-regulated Supramolecular Fibers in Aqueous Media

Nicolás M. Casellas, Lorenzo Albertazzi, Sílvia Pujals (Corresponding author), Tomás Torres (Corresponding author), Miguel García-Iglesias (Corresponding author)

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Abstract

An amine functionalized C₃-symmetric benzotrithiophene (BTT) monomer has been designed and synthetized in order to form pH responsive one-dimensional supramolecular polymers in aqueous media. While most of the reported studies looked at the effect of pH on the size of the aggregates, herein, a detailed mechanistic study is reported, carried out upon modifying the pH to trigger the formation of positively charged ammonium groups. A dramatic and reversible change in the polymerization mechanism and size of the supramolecular fibers is observed and ascribed to the combination of Coulombic repulsive forces and higher monomer solubility. Furthermore, the induced frustrated growth of the fibers is further employed to finely control the one-dimensional supramolecular polymerisation and copolymerization processes.

Original language	English
Pages (from-to)	11056-11060
Number of pages	5
Journal	Chemistry - A European Journal
Volume	27
Issue number	43
Early online date	7 Jun 2021
DOIs	https://doi.org/10.1002/chem.202101660
Publication status	Published - 2 Aug 2021

Bibliographical note

Funding Information:
Financial support from MINECO (CTQ2017‐85393‐P) and ERA‐NET/European Commission/MINECO (EuroNanoMed2017‐191/PCIN‐2017‐042) is acknowledged by T.T. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016‐0686). M.G.I thanks Santander Talent Atraction Research (STAR2) for finantial support. This work was also financially supported by Spanish Ministry of Science and Innovation (PID2019‐109450RB‐I00/AEI/10.13039/501100011033), European Research Council/Horizon2020 (ERC‐StG‐757397), la Caixa Foundation (ID 100010434) and by the Generalitat de Catalunya (2017 SGR 01536) to S.P. and L.A.

Publisher Copyright:
© 2021 The Authors. Published by Wiley-VCH GmbH

Funding

Financial support from MINECO (CTQ2017‐85393‐P) and ERA‐NET/European Commission/MINECO (EuroNanoMed2017‐191/PCIN‐2017‐042) is acknowledged by T.T. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016‐0686). M.G.I thanks Santander Talent Atraction Research (STAR2) for finantial support. This work was also financially supported by Spanish Ministry of Science and Innovation (PID2019‐109450RB‐I00/AEI/10.13039/501100011033), European Research Council/Horizon2020 (ERC‐StG‐757397), la Caixa Foundation (ID 100010434) and by the Generalitat de Catalunya (2017 SGR 01536) to S.P. and L.A.

Funders	Funder number
European Union's Horizon 2020 - Research and Innovation Framework Programme	757397
Ministerio de Economía y Competitividad

Keywords

pH responsivity
polymerization mechanism
self-assembly
supramolecular chemistry
supramolecular polymers
Water
Polymerization
Polymers
Hydrogen-Ion Concentration
Macromolecular Substances

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10.1002/chem.202101660

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abstract = "An amine functionalized C3-symmetric benzotrithiophene (BTT) monomer has been designed and synthetized in order to form pH responsive one-dimensional supramolecular polymers in aqueous media. While most of the reported studies looked at the effect of pH on the size of the aggregates, herein, a detailed mechanistic study is reported, carried out upon modifying the pH to trigger the formation of positively charged ammonium groups. A dramatic and reversible change in the polymerization mechanism and size of the supramolecular fibers is observed and ascribed to the combination of Coulombic repulsive forces and higher monomer solubility. Furthermore, the induced frustrated growth of the fibers is further employed to finely control the one-dimensional supramolecular polymerisation and copolymerization processes.",

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note = "Funding Information: Financial support from MINECO (CTQ2017‐85393‐P) and ERA‐NET/European Commission/MINECO (EuroNanoMed2017‐191/PCIN‐2017‐042) is acknowledged by T.T. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R\&D (MINECO, Grant SEV2016‐0686). M.G.I thanks Santander Talent Atraction Research (STAR2) for finantial support. This work was also financially supported by Spanish Ministry of Science and Innovation (PID2019‐109450RB‐I00/AEI/10.13039/501100011033), European Research Council/Horizon2020 (ERC‐StG‐757397), la Caixa Foundation (ID 100010434) and by the Generalitat de Catalunya (2017 SGR 01536) to S.P. and L.A. Publisher Copyright: {\textcopyright} 2021 The Authors. Published by Wiley-VCH GmbH",

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Unveiling Polymerization Mechanism in pH-regulated Supramolecular Fibers in Aqueous Media

Abstract

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Keywords

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