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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...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2021
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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. |
format | Online Article Text |
id | pubmed-8227452 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
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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