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Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface

[Image: see text] Nanostructures that are inaccessible through spontaneous thermodynamic processes may be formed by supramolecular self-assembly under kinetic control. In the past decade, the dynamics of pathway complexity in self-assembly have been elucidated through kinetic models based on aggrega...

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Autores principales: Robayo-Molina, Iván, Molina-Osorio, Andrés F., Guinane, Luke, Tofail, Syed A. M., Scanlon, Micheál D.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8227452/
https://www.ncbi.nlm.nih.gov/pubmed/34115491
http://dx.doi.org/10.1021/jacs.1c02481
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author Robayo-Molina, Iván
Molina-Osorio, Andrés F.
Guinane, Luke
Tofail, Syed A. M.
Scanlon, Micheál D.
author_facet Robayo-Molina, Iván
Molina-Osorio, Andrés F.
Guinane, Luke
Tofail, Syed A. M.
Scanlon, Micheál D.
author_sort Robayo-Molina, Iván
collection PubMed
description [Image: see text] Nanostructures that are inaccessible through spontaneous thermodynamic processes may be formed by supramolecular self-assembly under kinetic control. In the past decade, the dynamics of pathway complexity in self-assembly have been elucidated through kinetic models based on aggregate growth by sequential monomer association and dissociation. Immiscible liquid–liquid interfaces are an attractive platform to develop well-ordered self-assembled nanostructures, unattainable in bulk solution, due to the templating interaction of the interface with adsorbed molecules. Here, we report time-resolved in situ UV–vis spectroscopic observations of the self-assembly of zinc(II) meso-tetrakis(4-carboxyphenyl)porphyrin (ZnTPPc) at an immiscible aqueous–organic interface. We show that the kinetically favored metastable J-type nanostructures form quickly, but then transform into stable thermodynamically favored H-type nanostructures. Numerical modeling revealed two parallel and competing cooperative pathways leading to the different porphyrin nanostructures. These insights demonstrate that pathway complexity is not unique to self-assembly processes in bulk solution and is equally valid for interfacial self-assembly. Subsequently, the interfacial electrostatic environment was tuned using a kosmotropic anion (citrate) in order to influence the pathway selection. At high concentrations, interfacial nanostructure formation was forced completely down the kinetically favored pathway, and only J-type nanostructures were obtained. Furthermore, we found by atomic force microscopy and scanning electron microscopy that the J- and H-type nanostructures obtained at low and high citric acid concentrations, respectively, are morphologically distinct, which illustrates the pathway-dependent material properties.
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spelling pubmed-82274522021-06-25 Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface Robayo-Molina, Iván Molina-Osorio, Andrés F. Guinane, Luke Tofail, Syed A. M. Scanlon, Micheál D. J Am Chem Soc [Image: see text] Nanostructures that are inaccessible through spontaneous thermodynamic processes may be formed by supramolecular self-assembly under kinetic control. In the past decade, the dynamics of pathway complexity in self-assembly have been elucidated through kinetic models based on aggregate growth by sequential monomer association and dissociation. Immiscible liquid–liquid interfaces are an attractive platform to develop well-ordered self-assembled nanostructures, unattainable in bulk solution, due to the templating interaction of the interface with adsorbed molecules. Here, we report time-resolved in situ UV–vis spectroscopic observations of the self-assembly of zinc(II) meso-tetrakis(4-carboxyphenyl)porphyrin (ZnTPPc) at an immiscible aqueous–organic interface. We show that the kinetically favored metastable J-type nanostructures form quickly, but then transform into stable thermodynamically favored H-type nanostructures. Numerical modeling revealed two parallel and competing cooperative pathways leading to the different porphyrin nanostructures. These insights demonstrate that pathway complexity is not unique to self-assembly processes in bulk solution and is equally valid for interfacial self-assembly. Subsequently, the interfacial electrostatic environment was tuned using a kosmotropic anion (citrate) in order to influence the pathway selection. At high concentrations, interfacial nanostructure formation was forced completely down the kinetically favored pathway, and only J-type nanostructures were obtained. Furthermore, we found by atomic force microscopy and scanning electron microscopy that the J- and H-type nanostructures obtained at low and high citric acid concentrations, respectively, are morphologically distinct, which illustrates the pathway-dependent material properties. American Chemical Society 2021-06-11 2021-06-23 /pmc/articles/PMC8227452/ /pubmed/34115491 http://dx.doi.org/10.1021/jacs.1c02481 Text en © 2021 The Authors. Published by American Chemical Society Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Robayo-Molina, Iván
Molina-Osorio, Andrés F.
Guinane, Luke
Tofail, Syed A. M.
Scanlon, Micheál D.
Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface
title Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface
title_full Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface
title_fullStr Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface
title_full_unstemmed Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface
title_short Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface
title_sort pathway complexity in supramolecular porphyrin self-assembly at an immiscible liquid–liquid interface
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8227452/
https://www.ncbi.nlm.nih.gov/pubmed/34115491
http://dx.doi.org/10.1021/jacs.1c02481
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