Comprehensive Characterization of the Self-Folding Cavitand Dynamics
dc.contributor.author
dc.date.accessioned
2021-07-02T08:41:47Z
dc.date.available
2021-07-02T08:41:47Z
dc.date.issued
2021-07-12
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
The conformational equilibria and guest exchange process of a resorcin[4]arene derived self-folding cavitand receptor have been characterized in detail by molecular dynamics simulations (MD) and 1H EXSY NMR experiments. A multi-timescale strategy for exploring the fluxional behaviour of this system has been constructed, exploiting conventional MD and accelerated MD (aMD) techniques. The use of aMD allows the reconstruction of the folding/unfolding process of the receptor by sampling high-energy barrier processes unattainable by conventional MD simulations. We obtained MD trajectories sampling events occurring at different timescales from ns to s: 1) rearrangement of the directional hydrogen bond seam stabilizing the receptor, 2) folding/unfolding of the structure transiting partially open intermediates, and 3) guest departure from different folding stages. Most remarkably, reweighing of the biased aMD simulations provided kinetic barriers that are in very good agreement with those determined experimentally by 1H NMR. These results constitute the first comprehensive characterization of the complex dynamic features of cavitand receptors. Our approach emerges as a valuable rational design tool for synthetic host-guest systems
dc.description.sponsorship
We are grateful for financial support from the Spanish government (“Ramón y Cajal” contract RYC2012-11112 and grant CTQ2017-83587-P to A.L.; grant RTI2018-101032-J00 to F.F), the European Community (MSCA-IF-2014-EF-661160-MetAccembly grant to F.F), and the Generalitat de Catalunya (projects 2017-SGR-39 and 2017-SGR-1707). We thank the Spanish Supercomputing Network (RES) for access to supercomputing resources (projects QCM-2018-3-0036, QCM-2019-1-0022, and QSB-2020-1-0008)
Open Access funding provided thanks to the CRUE-CSIC agreement with Wiley
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation.isformatof
Reproducció digital del document publicat a: https://doi.org/10.1002/chem.202100563
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Chemistry - A European Journal, 2021, vol. 27, núm. 39, p.10099-10106
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Articles publicats (D-Q)
dc.rights
Attribution-NonCommercial-NoDerivatives 4.0 International
dc.rights.uri
dc.title
Comprehensive Characterization of the Self-Folding Cavitand Dynamics
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-83587-P/ES/CATALISIS BIOMIMETICA DE CICLACIONES CARBOCATIONICAS CON RECEPTORES SINTETICOS/
info:eu-repo/grantAgreement/EC/H2020/661160/EU/Accelerating metal-directed assembly, recognition and catalysis with computational methods/MetAccembly
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765