Drastic Stabilization of Junction Nodes in Supramolecular Structures Based on Host–Guest Complexes

Tânia F. G. G. Cova; Bruce F. Milne; Sandra C. C. Nunes; Alberto A. C. C. Pais

doi:10.1021/acs.macromol.8b00154

Drastic Stabilization of Junction Nodes in Supramolecular Structures Based on Host–Guest Complexes

Tânia F. G. G. Cova^* (Corresponding Author), Bruce F. Milne, Sandra C. C. Nunes, Alberto A. C. C. Pais

^*Corresponding author for this work

Chemistry

University of Coimbra

Research output: Contribution to journal › Article › peer-review

Abstract

The critical roles of solvent, enthalpic, and entropic contributions in complexes between different hyaluronic acid derivatives bearing monomeric β-cyclodextrin and adamantene moieties are assessed combining our previously designed free energy oriented method and a recently proposed density-based noncovalent interaction analysis. This establishes the relevant thermodynamics signatures and identifies the stabilizing/destabilizing noncovalent interactions within the complexes used as models for the junction points. It is observed that structural variations promote major changes in the thermodynamic variables. The presence of the amphiphilic chains emphasizes inclusion and drastically increases the binding constant (to ca. 1028). A comprehensive thermodynamic scheme is thus provided, in which host–guest interactions, host conformation, and solvation play the leading roles. These results have direct implications for the rational design of supramolecular materials with specific properties based on these host–guest systems.

Original language	English
Pages (from-to)	2732-2741
Number of pages	10
Journal	Macromolecules
Volume	51
DOIs	https://doi.org/10.1021/acs.macromol.8b00154
Publication status	Published - 30 Mar 2018

Bibliographical note

Acknowledgements
The authors acknowledge the Fundação para a Ciência e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the Projects n. 016648 POCI-01-0145-FEDER-016648 and COMPETE POCI-01-0145-FEDER-007440. The Coimbra Chemistry Centre is also supported by FCT through the Projects PEst-OE/QUI/UI0313/2014 and POCI-01-0145-FEDER-007630. Tânia F. G. G. Cova and S. C. C. Nunes also acknowledge respectively the PhD and postdoctoral research Grants SFRH/BD/95459/2013 and SFRH/BPD/71683/2010, assigned by FCT. B.F.M. thanks the FCT (project CENTRO-01-0145-FEDER-000014, 2017-2020) and the Donostia International Physics Centre for financial support. The authors also thank the Laboratory for Advanced Computing (LCA) of the University of Coimbra for the provision of computer time and support.

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title = "Drastic Stabilization of Junction Nodes in Supramolecular Structures Based on Host–Guest Complexes",

abstract = "The critical roles of solvent, enthalpic, and entropic contributions in complexes between different hyaluronic acid derivatives bearing monomeric β-cyclodextrin and adamantene moieties are assessed combining our previously designed free energy oriented method and a recently proposed density-based noncovalent interaction analysis. This establishes the relevant thermodynamics signatures and identifies the stabilizing/destabilizing noncovalent interactions within the complexes used as models for the junction points. It is observed that structural variations promote major changes in the thermodynamic variables. The presence of the amphiphilic chains emphasizes inclusion and drastically increases the binding constant (to ca. 1028). A comprehensive thermodynamic scheme is thus provided, in which host–guest interactions, host conformation, and solvation play the leading roles. These results have direct implications for the rational design of supramolecular materials with specific properties based on these host–guest systems.",

author = "Cova, {T{\^a}nia F. G. G.} and Milne, {Bruce F.} and Nunes, {Sandra C. C.} and Pais, {Alberto A. C. C.}",

note = "Acknowledgements The authors acknowledge the Funda{\c c}{\~a}o para a Ci{\^e}ncia e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the Projects n. 016648 POCI-01-0145-FEDER-016648 and COMPETE POCI-01-0145-FEDER-007440. The Coimbra Chemistry Centre is also supported by FCT through the Projects PEst-OE/QUI/UI0313/2014 and POCI-01-0145-FEDER-007630. T{\^a}nia F. G. G. Cova and S. C. C. Nunes also acknowledge respectively the PhD and postdoctoral research Grants SFRH/BD/95459/2013 and SFRH/BPD/71683/2010, assigned by FCT. B.F.M. thanks the FCT (project CENTRO-01-0145-FEDER-000014, 2017-2020) and the Donostia International Physics Centre for financial support. The authors also thank the Laboratory for Advanced Computing (LCA) of the University of Coimbra for the provision of computer time and support.",

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doi = "10.1021/acs.macromol.8b00154",

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AU - Cova, Tânia F. G. G.

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AU - Pais, Alberto A. C. C.

N1 - Acknowledgements The authors acknowledge the Fundação para a Ciência e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the Projects n. 016648 POCI-01-0145-FEDER-016648 and COMPETE POCI-01-0145-FEDER-007440. The Coimbra Chemistry Centre is also supported by FCT through the Projects PEst-OE/QUI/UI0313/2014 and POCI-01-0145-FEDER-007630. Tânia F. G. G. Cova and S. C. C. Nunes also acknowledge respectively the PhD and postdoctoral research Grants SFRH/BD/95459/2013 and SFRH/BPD/71683/2010, assigned by FCT. B.F.M. thanks the FCT (project CENTRO-01-0145-FEDER-000014, 2017-2020) and the Donostia International Physics Centre for financial support. The authors also thank the Laboratory for Advanced Computing (LCA) of the University of Coimbra for the provision of computer time and support.

PY - 2018/3/30

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N2 - The critical roles of solvent, enthalpic, and entropic contributions in complexes between different hyaluronic acid derivatives bearing monomeric β-cyclodextrin and adamantene moieties are assessed combining our previously designed free energy oriented method and a recently proposed density-based noncovalent interaction analysis. This establishes the relevant thermodynamics signatures and identifies the stabilizing/destabilizing noncovalent interactions within the complexes used as models for the junction points. It is observed that structural variations promote major changes in the thermodynamic variables. The presence of the amphiphilic chains emphasizes inclusion and drastically increases the binding constant (to ca. 1028). A comprehensive thermodynamic scheme is thus provided, in which host–guest interactions, host conformation, and solvation play the leading roles. These results have direct implications for the rational design of supramolecular materials with specific properties based on these host–guest systems.

AB - The critical roles of solvent, enthalpic, and entropic contributions in complexes between different hyaluronic acid derivatives bearing monomeric β-cyclodextrin and adamantene moieties are assessed combining our previously designed free energy oriented method and a recently proposed density-based noncovalent interaction analysis. This establishes the relevant thermodynamics signatures and identifies the stabilizing/destabilizing noncovalent interactions within the complexes used as models for the junction points. It is observed that structural variations promote major changes in the thermodynamic variables. The presence of the amphiphilic chains emphasizes inclusion and drastically increases the binding constant (to ca. 1028). A comprehensive thermodynamic scheme is thus provided, in which host–guest interactions, host conformation, and solvation play the leading roles. These results have direct implications for the rational design of supramolecular materials with specific properties based on these host–guest systems.

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DO - 10.1021/acs.macromol.8b00154

M3 - Article

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SP - 2732

EP - 2741

JO - Macromolecules

JF - Macromolecules

ER -

Drastic Stabilization of Junction Nodes in Supramolecular Structures Based on Host–Guest Complexes

Abstract

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