Understanding complex supramolecular landscapes: Non-covalent macrocyclization equilibria examined by fluorescence resonance energy transfer
EntityUAM. Departamento de Química Orgánica; UAM. Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)
PublisherRoyal Society of Chemistry
10.1039/c8sc03229gChemical Science 9.40 (2018): 7809-7821
ISSN2041-6520 (print); 2041-6539 (online)
Funded byFunding from the European Research Council (ERC-Starting Grant 279548 PROGRAM-NANO) and MINECO (CTQ2014-57729 P and CTQ2017-84727 P) is gratefully acknowledged. E. F. would like to thank Sharif University of Technology of Iran for financial support. D. S.-M. would like to acknowledge Comunidad de Madrid for financial support through contract PEJ16/IND/AI-0849
Projectinfo:eu-repo/grantAgreement/EC/FP7/279548; Gobierno de España. CTQ2014- 57729 P; Gobierno de España. CTQ2017-84727 P; Comunidad de Madrid. PEJ16/IND/AI-0849
SubjectsMolecular self-assembled system; Analytical techniques; Excitation energy; Thermodynamic; Watson–Crick H-bonding pairs; Macrocyclization reaction; Química
Rights© The Royal Society of Chemistry
Esta obra está bajo una licencia de Creative Commons Reconocimiento-NoComercial 4.0 Internacional.
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
Google Scholar:Mayoral, María José - Serrano-Molina, David - Camacho-García, Jorge - Magdalena-Estirado, Eva - Blanco-Lomas, Marina - Fadaei, Elham - González Rodríguez, David
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