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Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis

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Abstract

In this work the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyroside, isolated for the first time from Clitoria guianensis, were studied using the density functional theory. The frontier molecular orbitals and structural properties showed that the diastereoisomers exhibit the same energy gap 166.61 kcal mol−1 and structural properties different, where in the S diastereoisomer, the bond length between the chiral carbon and the phenolic group is greater (difference of 0.0126 Å). The HPLC data showed that the retention time of the S-diastereoisomer (16.7 min) is shorter than that of R, suggesting that the S compound is more polar than R. The HPLC results corroborates with the molecular electrostatic potential which showed that in the S configuration, the electronegative density was more intense overall, particularly in the glucose molecule. The reactivity indices showed that the diastereoisomers are good electrophiles and reactive species. Finally, the absolute configuration of the diastereoisomers were determined using electronic circular dichroism (ECD) spectroscopy and the theoretical spectra were similar to the experimental.

Methods

All calculations of Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TDDFT) were performed using the program Gaussian 09 and the structures of the diastereoisomers were generated and analyzed using the GaussView program. The optimization and vibrational frequency calculations were performed using the functional CAM-B3LYP and 6–311 +  + G(2d,2p) basis set. Conformational searches were performed for R configuration, by molecular mechanics using the MM + , MMFF, and OPLS05 force fields; the entire molecular mechanics simulation was performed using the Maestro/MacroModel software. The calculations for the simulations of the ECD spectra were performed for the eight lowest energy conformers obtained in the geometric optimization step, and the TDDFT at the CAM-B3LYP/6–311 +  + G(2d,2p) theory level used. The effects of methanol and chloroform were calculated using the SMD implicit solvent model.

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Funding

This study was supported by CAPES (Coordination of Improvement of Higher Education Personnel, Brazil, Funding Code 001 CAPES) and the PROPESQ/Federal University of Tocantins (Edital para tradução de artigos científicos da Universidade Federal do Tocantins, PROPESQ/UFT). Douglas H. Pereira acknowledge the Center for Computational Engineering and Sciences (financial support from FAPESP—Fundação de Amparo à Pesquisa, Grant 2013/08293–7, and Grant 2017/11485–6), the National Center for High Performance Processing (Centro Nacional de Processamento de Alto Desempenho – CENAPAD) in São Paulo for their computational resources and the FAPT (Fundação de Amparo à Pesquisa—Governo do Tocantins) for productivity grant. To Evam Stoll and Christina Moke of the Schrödinger Platform Science and Technology team, Inc. by the license provided.

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Authors and Affiliations

  1. Collegiate of Exact Sciences and Biotechnology, Universidade Federal do Tocantins, 77 402-970, Gurupi, Tocantins, Brazil

    Állefe Barbosa Cruz, Nicolas Nascimento Ciribelli, Juliana Cristina Holzbach & Douglas Henrique Pereira

  2. Graduate Program in Chemistry, Universidade Federal do Tocantins, 77 402-970, Gurupi, Tocantins, Brazil

    Douglas Henrique Pereira

  3. Institute of Chemistry, Universidade Estadual Paulista (Unesp), Araraquara, SP, 14800-060, Brazil

    Camila Luiza Cunha & Isabele Rodrigues Nascimento

Authors
  1. Állefe Barbosa Cruz
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  2. Nicolas Nascimento Ciribelli
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  4. Isabele Rodrigues Nascimento
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  5. Juliana Cristina Holzbach
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Contributions

A.B.C. and N.N.C. performed the simulations and analyzed the data. C.LC., J.C.H. and I.R.N. performed the experimental analyzes and analyzed the data. I.R.N. supervised the experiments. D.H.P. supervised the simulations. A.B.C, N.N.C. and C.L.C. wrote the first draft of the manuscript. J.C.H., I.R.N. and D.H.P. provided critical feedback and revised the draft the manuscript.

Corresponding author

Correspondence to Douglas Henrique Pereira.

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Cruz, Á.B., Ciribelli, N.N., Cunha, C.L. et al. Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis. J Mol Model 29, 77 (2023). https://doi.org/10.1007/s00894-023-05482-y

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