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Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer

As molecular self-assembled systems increase in complexity, due to a large number of participating entities and/or the establishment of multiple competing equilibria, their full understanding becomes likewise more complicated, and the use of diverse analytical techniques that can afford complementar...

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Autores principales: Mayoral, María J., Serrano-Molina, David, Camacho-García, Jorge, Magdalena-Estirado, Eva, Blanco-Lomas, Marina, Fadaei, Elham, González-Rodríguez, David
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6194488/
https://www.ncbi.nlm.nih.gov/pubmed/30429990
http://dx.doi.org/10.1039/c8sc03229g
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author Mayoral, María J.
Serrano-Molina, David
Camacho-García, Jorge
Magdalena-Estirado, Eva
Blanco-Lomas, Marina
Fadaei, Elham
González-Rodríguez, David
author_facet Mayoral, María J.
Serrano-Molina, David
Camacho-García, Jorge
Magdalena-Estirado, Eva
Blanco-Lomas, Marina
Fadaei, Elham
González-Rodríguez, David
author_sort Mayoral, María J.
collection PubMed
description As molecular self-assembled systems increase in complexity, due to a large number of participating entities and/or the establishment of multiple competing equilibria, their full understanding becomes likewise more complicated, and the use of diverse analytical techniques that can afford complementary information is required. We demonstrate in this work that resonance excitation energy transfer phenomena, measured by fluorescence spectroscopy in combination with other optical spectroscopies, can be a valuable tool to obtain supplementary thermodynamic data about complex supramolecular landscapes that other methods fail to provide. In particular, noncovalent macrocyclization processes of lipophilic dinucleosides are studied here by setting up a competition between intra- and intermolecular association processes of Watson–Crick H-bonding pairs. Multiwavelength analysis of the monomer emission changes allowed us to determine cyclotetramerization constants and to quantify chelate cooperativity, which was confirmed to be substantially larger for the G-C than for the A-U pair. Furthermore, when bithiophene-BODIPY donor–acceptor energy transfer probes are employed in these competition experiments, fluorescence and circular dichroism spectroscopy measurements in different regions of the visible spectrum additionally reveal intermolecular interactions occurring simultaneously at both sides of the macrocyclization reaction: the cyclic product, acting as a host for the competitor, and the monomer reactant, ultimately leading to macrocycle denaturation.
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spelling pubmed-61944882018-11-14 Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer Mayoral, María J. Serrano-Molina, David Camacho-García, Jorge Magdalena-Estirado, Eva Blanco-Lomas, Marina Fadaei, Elham González-Rodríguez, David Chem Sci Chemistry As molecular self-assembled systems increase in complexity, due to a large number of participating entities and/or the establishment of multiple competing equilibria, their full understanding becomes likewise more complicated, and the use of diverse analytical techniques that can afford complementary information is required. We demonstrate in this work that resonance excitation energy transfer phenomena, measured by fluorescence spectroscopy in combination with other optical spectroscopies, can be a valuable tool to obtain supplementary thermodynamic data about complex supramolecular landscapes that other methods fail to provide. In particular, noncovalent macrocyclization processes of lipophilic dinucleosides are studied here by setting up a competition between intra- and intermolecular association processes of Watson–Crick H-bonding pairs. Multiwavelength analysis of the monomer emission changes allowed us to determine cyclotetramerization constants and to quantify chelate cooperativity, which was confirmed to be substantially larger for the G-C than for the A-U pair. Furthermore, when bithiophene-BODIPY donor–acceptor energy transfer probes are employed in these competition experiments, fluorescence and circular dichroism spectroscopy measurements in different regions of the visible spectrum additionally reveal intermolecular interactions occurring simultaneously at both sides of the macrocyclization reaction: the cyclic product, acting as a host for the competitor, and the monomer reactant, ultimately leading to macrocycle denaturation. Royal Society of Chemistry 2018-08-20 /pmc/articles/PMC6194488/ /pubmed/30429990 http://dx.doi.org/10.1039/c8sc03229g Text en This journal is © The Royal Society of Chemistry 2018 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Mayoral, María J.
Serrano-Molina, David
Camacho-García, Jorge
Magdalena-Estirado, Eva
Blanco-Lomas, Marina
Fadaei, Elham
González-Rodríguez, David
Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
title Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
title_full Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
title_fullStr Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
title_full_unstemmed Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
title_short Understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
title_sort understanding complex supramolecular landscapes: non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6194488/
https://www.ncbi.nlm.nih.gov/pubmed/30429990
http://dx.doi.org/10.1039/c8sc03229g
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