Kinetics and thermodynamics of β-cyclodextrin-NH2/β-carotene complexation: how much energy is required to include a hydrophobic group in the macrocycle cavity?
Yara Luiza Coelho, Hauster Maximiler Campos de Paula, Lívia Neves Santa Rosa, Isabela Araujo Marques, Nícolas Glanzmann, Camilla Fonseca Silva, Adilson David da Silva, Clebio Soares Nascimento Jr., Ana Clarissa dos Santos Pires, Luis Henrique Mendes da Silva
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引用次数: 0
Abstract
To improve the efficiency of cyclodextrins as carotenoid carriers, the kinetics and thermodynamics of the inclusion complex formation between modified β-cyclodextrin (βCD-NH2) and β-carotene (βCT) were studied using surface plasmon resonance (SPR) at pH 7.4 and theoretical calculations. The observed dissociation rate of the [βCD-NH2/βCT]° inclusion complex is small \((2.59\times 1{0}^{-1} {\text{s}}^{-1}\)), indicating that βCD-NH2 only interacted with the βCT ionone group to form inclusion complex. The βCD-NH2/βCT binding constant is \(2.80\times 1{0}^{4} \text{L} {\text{m}\text{o}\text{l}}^{-1}\) (at 298.15 K), and its temperature dependence indicates that the [βCD-NH2/βCT]° formation is driven by hydrophobic interactions (\({\Delta }H^\circ = 28.83 \text{k}\text{J} \text{m}\text{o}{\text{l}}^{-1}\) and \(T{\Delta }S^\circ = 54.21 \text{k}\text{J} \text{m}\text{o}{\text{l}}^{-1}\)) caused mainly by the βCT end group desolvation. In contrast, the formation of the [βCD-NH2/βCT]‡ activated complex via association between free molecules and dissociation of [βCD-NH2/βCT]° occurred with the overcoming of an energy barrier (\(E_{a}^{\ddag } = 40.77~{\text{kJ mol}}^{{ - 1}} ~\) and \({E}_{d}^{\ddag}=11.94 \text{k}\text{J} \text{m}\text{o}{\text{l}}^{-1}\)) and decrease in entropy (\(T{\varDelta S}_{a}^{\ddag}=-11.70 \text{k}\text{J} \text{m}\text{o}{\text{l}}^{-1}\) and \(T{\varDelta S}_{d}^{\ddag}=- 65.92 \text{k}\text{J} \text{m}\text{o}{\text{l}}^{-1}\)).
期刊介绍:
The Journal of Inclusion Phenomena and Macrocyclic Chemistry is the premier interdisciplinary publication reporting on original research into all aspects of host-guest systems. Examples of specific areas of interest are: the preparation and characterization of new hosts and new host-guest systems, especially those involving macrocyclic ligands; crystallographic, spectroscopic, thermodynamic and theoretical studies; applications in chromatography and inclusion polymerization; enzyme modelling; molecular recognition and catalysis by inclusion compounds; intercalates in biological and non-biological systems, cyclodextrin complexes and their applications in the agriculture, flavoring, food and pharmaceutical industries; synthesis, characterization and applications of zeolites.
The journal publishes primarily reports of original research and preliminary communications, provided the latter represent a significant advance in the understanding of inclusion science. Critical reviews dealing with recent advances in the field are a periodic feature of the journal.