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Molecular insights into enantioselective separation of λ-cyhalothrin: a theoretical investigation

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Abstract

λ-Cyhalothrin (CLT), a widely employed pyrethroid insecticide for pest control, is typically marketed as a racemate, akin to many other pesticides. It has been recognized that optical isomers may exhibit distinct biological activity and toxicity, prompting the burgeoning demand for more efficient separation methods to isolate these isomers. In this study, we employed a theoretical approach to unravel the chiral recognition mechanisms governing the interaction between a polysaccharide-derived stationary phase and the λ-cyhalothrin. Density functional theory calculations were utilized to glean structural and energetic information, enabling the elucidation of the observed chiral discrimination and enantiomeric elution order from prior HPLC experiments. Our analysis pinpointed the critical role of hydrogen bonding and π-π stacking interactions in dictating the relative stability of the diastereomeric complexes formed between the λ-cyhalothrin enantiomers and the chiral selector.

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Funding

The authors would like to thank the Brazilian agencies CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), and FAPEMIG (Fundação de Amparo à Pesquisa do Estado de Minas Gerais) for financial support.

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Authors and Affiliations

  1. GPQCA: Grupo de Pesquisa em Química Computacional Aplicada, Departamento de Ciências Naturais (DCNAT), Universidade Federal de São João Del-Rei (UFSJ), Campus Dom Bosco, 36301-160, São João Del Rei, Minas Gerais, Brazil

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

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  1. Vitória S. Reis
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  2. Luciana Guimarães
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  3. Clebio S. Nascimento Jr.
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Contributions

A declaration of the role of each author is mentioned as follows: Prof. Clebio S. Nascimento Jr. participated in the supervision, validation, analysis of the results, writing—original draft preparation, writing—reviewing, and editing; Prof. Luciana Guimarães in the supervision; Miss Vitória S. Reis participated in the investigation, analysis of the results, data curation, and discussion; all authors read and approved the final manuscript.

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Correspondence to Clebio S. Nascimento Jr..

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Reis, V.S., Guimarães, L. & Nascimento, C.S. Molecular insights into enantioselective separation of λ-cyhalothrin: a theoretical investigation. Struct Chem (2024). https://doi.org/10.1007/s11224-024-02356-8

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