A molecular modelling study of the distortion of α-cyclo-dextrin (cyclomaltohexaose) in complexes with guest molecules

Helden, Steven P. van; Drooge, Marc J. van; Claessens, A. J.; Jansen, A. C. A.; Janssen, Lambert H.M.

doi:10.1016/0008-6215(91)84025-a

Cited by 18 publications

(8 citation statements)

References 19 publications

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“…The glucose units which show the largest deviation from these equations have an absolute torsion angle between C1, 04, 04' and C4 atoms which is larger than 5 °. Similar correlations have been found in the case of ~-cyclodextrin molecules [10]. …”

Section: Conformation Of Fl-cyclodextrin In Fl-cyclodextrin Complexessupporting

confidence: 72%

Modeling and conformation analysis of β-cyclodextrin complexes

Kostense¹,

Helden²,

Janssen³

1991

J Computer-Aided Mol Des

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A series of beta-cyclodextrin complexes containing various guest molecules was studied using computer-aided molecular modeling and conformation analysis techniques. The geometry of each complex was studied using crystallographic data. The positions of the glycosidic O4 atoms indicate that the beta-cyclodextrin molecules are elliptically distorted. This distortion can be related to the van der Waals volume of the guest molecules. This correlation is different for aromatic and non-aromatic guest compounds. Rigid body docking experiments demonstrated that in crystal structures the guest molecule occupies a position in the cavity of nearly minimum interaction energy when there are no other molecules having interactions with the guest molecule. From the crystallographic data several rules could be deduced which seem to determine the conformation of beta-cyclodextrin molecules in complexes. A procedure was developed to construct beta-cyclodextrin molecules that are able to encompass guest molecules having a given van der Waals volume.

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Section: Conformation Of Fl-cyclodextrin In Fl-cyclodextrin Complexessupporting

confidence: 72%

Modeling and conformation analysis of β-cyclodextrin complexes

Kostense¹,

Helden²,

Janssen³

1991

J Computer-Aided Mol Des

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“…This suggests that, to some degree, the interaction between the guest enantiomers and permethylated P-cyclodextrin may be considered an induce fit, where the conformation of the host changes to produce a better fit. The importance of induced-fit behavior in cyclodextrin complexation has been previously demonstrated experimentally and the~retically.~~, 40 Docking of a-pinene into a-cyclodextrin yields a AAG of 0.2 kcal mol-', as shown in Table 11. Experimentally, S-a-pinene is observed to elute last when separated on a-cyclodextrin and thus should be bound more tightly.…”

Section: Minimizationsmentioning

confidence: 83%

Enantioselective binding of α-pinene and of some cyclohexanetriol derivatives by cyclodextrin hosts: A molecular modeling study

et al. 1996

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We have used molecular modeling to investigate the enantioselective separation of the monoterpene α‐pinene on permethylated β‐cyclodextrin and on α‐cyclodextrin and the enantioselective separation of three cyclohexanetriol derivatives on permethylated β‐cyclodextrin. Using the Consistent Valence Force Field (CVFF) from Insight/Discover, we have carried out systematic rigid‐body docking grid searches on each of the optical antipodes of the organic guest molecules interacting with the cyclodextrins, followed by minimizations of the low‐energy docked structures. A statistical mechanical analysis of the minimized energies yields data that agree in four out of five cases with the experimental elution order of enantiomers. The computed energies of the rigid‐body docking before minimizations do not agree with the experimental results, suggesting that a conformational induced fit of the cyclodextrins upon binding of the organic guests may be involved in the mechanism of the chiral recognition. © 1996 by John Wiley & Sons, Inc.

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“…This issue was addressed in an earlier paper where we found the induced fit changes for type I CSPs to be small and inconsequential with regards to the computed free energy differences we felt less confident that such a sampling protocol would work because it has been speculated that induced fit structural changes are especially important when cyclodextrins bind guest molecules and, consequently, that an alternative methodology accounting for such changes, like molecular dynamics, would be better suited for this task (see below) …”

Section: Resultsmentioning

confidence: 99%

Explanation of Where and How Enantioselective Binding Takes Place on Permethylated β-Cyclodextrin, a Chiral Stationary Phase Used in Gas Chromatography

et al. 1997

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A computational study was undertaken to discern where and how chiral alkanes, alcohols, and acetates enantioselectively bind to permethyated -cyclodextrin, the most commonly used chiral stationary phase in gas chromatography. We found that enantioselective binding data could be reproduced with standard molecular dynamics techniques if averages are taken over multiple trajectories of nanosecond simulation times each, while Metropolis Monte Carlo simulations using rigid body molecules are unable to reproduce chromatographic retention orders. Data extracted from the molecular simulations revealed the preferred binding site for small analytes to be the interior of the macrocycle, with rapid shuttling between the primary and secondary rims and low-energy excursions into and out of the host cavity. The dominant forces holding the host-guest complexes together are the short range dispersion forces. The enantiodiscriminating forces responsible for chiral recognition are also the short range van der Waals forces and these enantiodifferentiating forces are typically 1-2 orders of magnitude smaller than the binding forces. An assessment of the number of hydrogen bonds for the diastereomeric complexes is presented along with the locations of dominant hydrogen-bonding sites on the macrocycle. A comparison is made between analytes capable of intramolecular hydrogen bonding with those that can not. It is pointed out that the 3-point binding description of chiral discrimination can be used, but it loses its appeal at such high temperatures due to ill-defined structures.

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A molecular modelling study of the distortion of α-cyclo-dextrin (cyclomaltohexaose) in complexes with guest molecules

Cited by 18 publications

References 19 publications

Modeling and conformation analysis of β-cyclodextrin complexes

Modeling and conformation analysis of β-cyclodextrin complexes

Enantioselective binding of α-pinene and of some cyclohexanetriol derivatives by cyclodextrin hosts: A molecular modeling study

Explanation of Where and How Enantioselective Binding Takes Place on Permethylated β-Cyclodextrin, a Chiral Stationary Phase Used in Gas Chromatography

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