Thermodynamics of molecular recognition by cyclodextrins. 1. Calorimetric titration of inclusion complexation of naphthalenesulfonates with .alpha.-, .beta.-, and .gamma.-cyclodextrins: enthalpy-entropy compensation

Inoue, Yoshihisa; Hakushi, Tadao; Liu, Yu; Tong, Lin-Hui; Shen, Baojian; Jin, Dandan

doi:10.1021/ja00055a017

Cited by 406 publications

(234 citation statements)

References 3 publications

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“…14 A possible explanation for our observations considers that the inclusion of ferrocene units inside the cyclodextrin cavity is mainly controlled by a positive entropic change ( Sº) for the water molecules which, 1,35 upon inclusion, are transferred from the hydrophobic basket-like cavity (S (12) Comparison of equations 11 and 12 allows to predict that the stability constants K for the interfacial Fc CD complexes (see Table 2) must be lower 36 than those observed in solution, 14 . This condition holds when we note that the dielectric constants, H2O , for interfacial and bulk water regions (related to water structure rigidity or entropy), are 6 and 80 respectively.…”

Section: Binding Of CD With Fc Tethered To the Dendrimer Filmsmentioning

confidence: 88%

Electrochemical study of β-Cyclodextrin binding with ferrocene tethered onto a gold surface via PAMAM dendrimers

Bustos¹,

Manríquez²,

Juaristi³

et al. 2008

J. Braz. Chem. Soc.

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Este artigo descreve a fixação de ferrocenos (Fc) sobre eletrodos policristalinos de ouro, por filmes dendrímeros de poliamidoamina (PAMAM). A superfície eletroativa fornece uma rota viável para investigar quantitativamente a ligação do ferroceno com a ciclodextrina (CD). Em particular, as medidas eletroquímicas, revelam o efeito das interações adsorção-adsorção sobre a constante de associação K, na interface eletrodo-eletrólito, durante a formação do complexo de 1:1 Os resultados obtidos a partir da investigação da isoterma de adsorção de Frumkin indicam que as interações podem ter um forte impacto na afinidade do CD com as superfícies do ferrocenil modificado, estudadas aqui. A técnica apresentada pode ser útil para investigar outras reações de ligação entre hóspede-hospedeiro. This paper describes the tethering of ferrocene (Fc) onto polycrystalline gold electrodes by immobilized polyamidoamine (PAMAM) dendrimers films. The resulting electroactive surface provides a viable route for investigating quantitatively the host-guest binding of ferrocene with cyclodextrin (CD). In particular, electrochemical measurements reveal the effect of adsorbateadsorbate interactions on the association constant K for the formation of the 1:1 CD Fc complex at the electrode-electrolyte interface. The results obtained from fitting the Frumkin isotherm to the adsorption data indicate that adsorbate-adsorbate interactions can have a strong impact on the CD affinity for the ferrocenyl-modified surfaces studied here. The technique presented may be useful for investigating other host-guest binding reactions.

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Section: Binding Of CD With Fc Tethered To the Dendrimer Filmsmentioning

confidence: 88%

Electrochemical study of β-Cyclodextrin binding with ferrocene tethered onto a gold surface via PAMAM dendrimers

Bustos¹,

Manríquez²,

Juaristi³

et al. 2008

J. Braz. Chem. Soc.

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“…The change in entropy is therefore a combination of entropic loss by complex formation with concomitant restriction of the degrees of freedom and the entropic gain by desolvation. 40 The altered solubility of the salt can also be considered an entropic gain. Due to the complex formation, the alkali metal salt is no longer restricted to the aqueous phase and the entropy of the total system increases.…”

Section: Gibbs Free Energy Of Cation Complexation In B15c5 and Poly15c5mentioning

confidence: 99%

Thermodynamic analysis of alkali metal complex formation of polymer-bonded crown ether

Bey

Dreyer

Abetz

2017

Phys. Chem. Chem. Phys.

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The complex formation of two crown ethers with colored alkali metal salts was investigated by UV/Vis spectroscopy. Complexation was accomplished with free benzo-15-crown-5 (B15C5) and 15-crown-5 bonded to a diblock copolymer (Poly15C5). The diblock copolymer was synthesized by two controlled polymerization techniques and copper(I)-catalyzed azide-alkyne cycloaddition. Depending on the inserted cation, 1 : 1-or 1 : 2-complexes are formed. A significant difference of the stability constants was determined by concentration dependence solvent extraction with sodium or potassium salt. For Poly15C5 the stability constants increase for both salts compared to the stability constants of B15C5, which suggests a more effective complexation. Evaluation of the thermodynamics (DH, DS, DG) of cation complexation was achieved by temperature dependence phase extraction on the basis of established thermodynamic equations. Remarkably, in all cases the entropic gain seems to be the major propulsion facilitating the complexation between alkali metal salts and crown ethers. Indeed, by using Poly15C5 a more pronounced dependency of enthalpy and entropy on the complex formation is calculated.

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“…[29][30][31] Cyclodextrins known as a typical kind of host compounds in molecular recognition, owing to the coexistence of hydrophobic cavity and hydrophilic surface in them, have showed good performance and already been widely used in drug delivery, 32,33 separation, 34,35 catalysis, 36 as well as desulfurization. [37][38][39] However, cyclodextrins have rather small binding constants with substrates, 40 and the binding abilities for them couldn't be improved effectively by functionalization and modication, 41 limitating the application of them in molecular recognition. Fortunately, these problems have been solved by the bridged cyclodextrin in some degree.…”

Section: -8mentioning

confidence: 99%

Molecular recognition with cyclodextrin polymer: a novel method for removing sulfides efficiently

Duan

Chen

et al. 2017

RSC Adv.

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A series of cyclodextrin polymers (CDPs) were synthesized and they were used for removing different sulfides by molecular recognition. Different CDPs showed a higher desulfurization efficiency for sulfides with an aromatic ring structure than those with an aliphatic chain structure. For different cyclodextrin polymers, b-CDP has a more suitable cavity size for removing DBT. Moreover, it has a good synergetic effect of adjacent cyclodextrin cavities and good electronic interactions with DBT.For these reasons, b-CDP showed the best desulfurization performance, in particular it has good performance for deep desulfurization by forming inclusion complexes and excellent selectivity for removing DBT. Meanwhile, the b-CDP showed good regeneration performance. Various characterization measurements were used to characterize the b-CDP before and after desulfurization of DBT, the results of which showed that it had advantages of wide application temperature range and good structure stability before and after desulfurization. Finally, a molecular recognition mechanism for removing sulfides efficiently was proposed.

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Thermodynamics of molecular recognition by cyclodextrins. 1. Calorimetric titration of inclusion complexation of naphthalenesulfonates with .alpha.-, .beta.-, and .gamma.-cyclodextrins: enthalpy-entropy compensation

Cited by 406 publications

References 3 publications

Electrochemical study of β-Cyclodextrin binding with ferrocene tethered onto a gold surface via PAMAM dendrimers

Electrochemical study of β-Cyclodextrin binding with ferrocene tethered onto a gold surface via PAMAM dendrimers

Thermodynamic analysis of alkali metal complex formation of polymer-bonded crown ether

Molecular recognition with cyclodextrin polymer: a novel method for removing sulfides efficiently

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