Cooperative binding of cyclodextrin dimers to isoflavone analogues elucidated by free energy calculations

Haiyang Zhang, Tianwei Tan, Csaba Hetényi, Yongqin Lv, David Van Der Spoel

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Dimerization of cyclodextrin (CD) molecules is an elementary step in the construction of CD-based nanostructured materials. Cooperative binding of CD cavities to guest molecules facilitates the dimerization process and, consequently, the overall stability and assembly of CD nanostructures. In the present study, all three dimerization modes (head-to-head, head-to-tail, and tail-to-tail) of β-CD molecules and their binding to three isoflavone drug analogues (puerarin, daidzin, and daidzein) were investigated in explicit water surrounding using molecular dynamics simulations. Total and individual contributions from the binding partners and solvent environment to the thermodynamics of these binding reactions are quantified in detail using free energy calculations. Cooperative drug binding to two CD cavities gives an enhanced binding strength for daidzin and daidzein, whereas for puerarin no obvious enhancement is observed. Head-to-head dimerization yields the most stable complexes for inclusion of the tested isoflavones (templates) and may be a promising building block for construction of template-stabilized CD nanostructures. Compared to the case of CD monomers, the desolvation of CD dimers and entropy changes upon complexation prove to be influential factors of cooperative binding. Our results shed light on key points of the design of CD-based supramolecular assemblies. We also show that structure-based calculation of binding thermodynamics can quantify stabilization caused by cooperative effects in building blocks of nanostructured materials.

Original languageEnglish
Pages (from-to)7163-7173
Number of pages11
JournalJournal of Physical Chemistry C
Volume118
Issue number13
DOIs
Publication statusPublished - Apr 3 2014

Fingerprint

Isoflavones
Cyclodextrins
Dimers
Free energy
free energy
dimers
analogs
dimerization
Dimerization
drugs
templates
Nanostructured materials
Molecules
Nanostructures
molecules
thermodynamics
cavities
Thermodynamics
assemblies
Complexation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Cooperative binding of cyclodextrin dimers to isoflavone analogues elucidated by free energy calculations. / Zhang, Haiyang; Tan, Tianwei; Hetényi, Csaba; Lv, Yongqin; Van Der Spoel, David.

In: Journal of Physical Chemistry C, Vol. 118, No. 13, 03.04.2014, p. 7163-7173.

Research output: Contribution to journalArticle

Zhang, Haiyang ; Tan, Tianwei ; Hetényi, Csaba ; Lv, Yongqin ; Van Der Spoel, David. / Cooperative binding of cyclodextrin dimers to isoflavone analogues elucidated by free energy calculations. In: Journal of Physical Chemistry C. 2014 ; Vol. 118, No. 13. pp. 7163-7173.
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