A computational study on the enantioselective separation of cyhalothrin enantiomers by β-cyclodextrins

IF 2.5 4区化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Molecular Modeling Pub Date : 2025-08-11 DOI:10.1007/s00894-025-06469-7

Vitória S. Reis, Luciana Guimarães, Clebio S. Nascimento Jr.

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引用次数: 0

Abstract

Context

This computational study investigates the enantioselective separation of λ-cyhalothrin (CLT) enantiomers, ( +)-[S]-CLT and ( −)-[R]-CLT, using native β-cyclodextrin (β-CD) and its sulfated derivative (S-β-CD) as chiral selectors. Our calculations, employing B97D/6-31G(d,p)//PM3 and B97X-D3/6-31G(d,p)//GFN2-xTB methodologies, consistently demonstrate that the ( −)-[R]-CLT enantiomer forms more stable inclusion complexes with both selectors, predicting a longer migration time compared to ( +)-[S]-CLT. This enhanced stability is primarily due to favorable hydrophobic interactions, with additional hydrogen bonding contributing in the case of S-β-CD. S-β-CD exhibited superior separation efficiency, as evidenced by higher ΔΔG values, likely due to structural modifications induced by sulfate groups that optimize steric fitting and van der Waals interactions within the cyclodextrin cavity. These findings highlight the potential of S-β-CD for efficient enantiomeric separation of CLT and underscore the utility of computational chemistry in understanding chiral recognition mechanisms.

Methods

Two distinct theoretical methodologies, B97D/6-31G(d,p)//PM3 and ωB97X-D3/6-31G(d,p)//GFN2-xTB, were employed to elucidate the structural and energetic properties of these diastereomeric complexes. The calculations were performed on Gaussian 09 and ORCA 5.0 software packages.

Abstract Image

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β-环糊精对氟氯氰菊酯对映体选择性分离的计算研究

本研究利用天然β-环糊精（β-CD）及其硫酸化衍生物（S-β-CD）作为手性选择剂，研究了λ-氯氟氰菊酯（CLT）对映体(+)-[S]-CLT和(−)-[R]-CLT的对映选择性分离。我们的计算采用B97D/6-31G(d,p)//PM3和B97X-D3/6-31G(d,p)//GFN2-xTB方法，一致表明(−)-[R]- clt对映体与两种选择器形成更稳定的包合物，预测与(+)-[S]- clt相比迁移时间更长。这种增强的稳定性主要是由于有利的疏水相互作用，在S-β-CD的情况下，额外的氢键有助于。S-β-CD表现出优异的分离效率，ΔΔG值较高，这可能是由于硫酸盐基团诱导的结构修饰优化了环糊精腔内的空间拟合和范德华相互作用。这些发现突出了S-β-CD在高效分离CLT对映体方面的潜力，并强调了计算化学在理解手性识别机制方面的实用性。方法采用B97D/6-31G(d,p)//PM3和ωB97X-D3/6-31G(d,p)//GFN2-xTB两种不同的理论方法来解释这些非对映体配合物的结构和能量性质。计算采用Gaussian 09和ORCA 5.0软件包。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Molecular Modeling 化学-化学综合

CiteScore

3.50

自引率

4.50%

发文量

362

审稿时长

2.9 months

期刊介绍： The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling. Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry. Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.