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Structure Elucidation of Menthol-Based Deep Eutectic Solvent using Experimental and Computational Techniques

  • Md Ackas Ali
    Md Ackas Ali
    Division of Quantum Chemistry, The Red-Green Research Center, BICCB, 16, Tejkunipara, Tejgaon, Dhaka 1215, Bangladesh
    Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
    More by Md Ackas Ali
  • Md Sajjadur Rahman
    Md Sajjadur Rahman
    Department of Chemistry and Biochemistry, South Dakota State University, Brookings 57007, South Dakota, United States
  • Ranen Roy
    Ranen Roy
    Department of Chemistry and Biochemistry, South Dakota State University, Brookings 57007, South Dakota, United States
    More by Ranen Roy
  • Paul Gambill
    Paul Gambill
    Department of Physical Sciences, University of Arkansas-Fort Smith, Fort Smith 72913-3649, Arkansas, United States
    More by Paul Gambill
  • Douglas E. Raynie
    Douglas E. Raynie
    Department of Chemistry and Biochemistry, South Dakota State University, Brookings 57007, South Dakota, United States
  • , and 
  • Mohammad A. Halim*
    Mohammad A. Halim
    Department of Physical Sciences, University of Arkansas-Fort Smith, Fort Smith 72913-3649, Arkansas, United States
    *Phone: 1-479-788-7741. Fax: +1-479-424-6741. Email: [email protected]
Cite this: J. Phys. Chem. A 2021, 125, 12, 2402–2412
Publication Date (Web):March 23, 2021
https://doi.org/10.1021/acs.jpca.0c10735
Copyright © 2021 American Chemical Society

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    Abstract

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    The structural properties and nonbonding interactions of a menthol-based deep eutectic solvent (DES) were investigated in detail employing experimental and computational methods. A mass spectrometry analysis confirmed the formation of 1:1 l-menthol/acetic acid. A molecular dynamics simulation was used to figure out energetically most favorable cluster conformers of the 1:1 l-menthol/acetic acid system. Density functional theory at the ωB97XD/6-311G (d,p) level of theory was employed to optimize the isolated structures and to calculate their thermochemical properties. Both experimental and computed IR spectra were analyzed for the samples. Additionally, vibrational circular dichroism (VCD) spectra of the samples were measured to prove the chirality transfer. Principal component analysis (PCA) was used to make the data interpretation more vivid. All the spectral data analyses and nanostructure elucidation proved the spontaneous formation of the DES through the formation of strong hydrogen bonding. Experimental solvatochromism and computed highest occupied molecular orbital–lowest unoccupied molecular orbital gaps validated the reasoning. Moreover, comparative VCD and IR spectral analyses clearly indicated a chirality transfer from the chiral menthol to achiral acetic acid. This study suggests that various techniques, such as mass spectrometry, IR, solvatochromism, and computed IR-VCD could be useful and important tools to elucidate nanostructure and nonbonding interactions of a DES. VCD could be used as an excellent complementary technique to IR spectroscopy for a chiral molecule-based DESs.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c10735.

    • IR and VCD wavenumbers and intensities, selected bond distances (Å) and bond angles (deg), images of the 5, 10, and 20 pairs of menthol–acetic acid MD simulations, van der Waals and Coulombic energies of the menthol–acetic acid simulations; schematic flowchart shows how the best conformers were selected, mass spectra of this DES when prepared at 50 °C, loading plot of the PCA analysis of IR and VCD spectra (PDF)

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    Cited By

    This article is cited by 14 publications.

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    2. Th.Gomti Devi, Th.Joymati Devi, P. Suraj Singh, L. Willingson. Vibrational and molecular properties of curcumin-natural deep eutectic solvent mixture using experimental and theoretical methods. Journal of Molecular Liquids 2024, 397 , 124055. https://doi.org/10.1016/j.molliq.2024.124055
    3. Pierre-Alann Cablé, Yann Le Brech, Fabrice Mutelet. Density functional theory investigation of interactions between phenolic compounds and water or hydrophobic deep eutectic solvent. Structural Chemistry 2024, 35 (1) , 321-339. https://doi.org/10.1007/s11224-023-02180-6
    4. Marharyta Cherniakova, Victoria Varchenko, Konstantin Belikov. Menthol‐Based (Deep) Eutectic Solvents: A Review on Properties and Application in Extraction. The Chemical Record 2024, 24 (2) https://doi.org/10.1002/tcr.202300267
    5. Xin Wen, Sifan Du, Li Zhang, Minghua Liu. Chiral Deep Eutectic Solvents Enable Full‐Color and White Circularly Polarized Luminescence from Achiral Luminophores. Angewandte Chemie 2023, 135 (46) https://doi.org/10.1002/ange.202311816
    6. Xin Wen, Sifan Du, Li Zhang, Minghua Liu. Chiral Deep Eutectic Solvents Enable Full‐Color and White Circularly Polarized Luminescence from Achiral Luminophores. Angewandte Chemie International Edition 2023, 62 (46) https://doi.org/10.1002/anie.202311816
    7. Farouq S. Mjalli, Mehdi Shakourian-Fard, Ganesh Kamath, Ghulam Murshid, Jamil Naser, Suhaib Al Ma'awali. Experimental and theoretical study of the physicochemical properties of the novel imidazole-based eutectic solvent. Journal of Molecular Graphics and Modelling 2023, 118 , 108319. https://doi.org/10.1016/j.jmgm.2022.108319
    8. Salvatore Marullo, Matteo Tiecco, Raimondo Germani, Francesca D'Anna. Highly recyclable surfactant-based supramolecular eutectogels for iodine removal. Journal of Molecular Liquids 2022, 362 , 119712. https://doi.org/10.1016/j.molliq.2022.119712
    9. Md Sajjadur Rahman, Ranen Roy, Cynthia Montoya, Mohammad A. Halim, Douglas E. Raynie. Acidic and basic amino acid-based novel deep eutectic solvents and their role in depolymerization of lignin. Journal of Molecular Liquids 2022, 362 , 119751. https://doi.org/10.1016/j.molliq.2022.119751
    10. Loknath Dhar, Md Sajjadur Rahman, Saddam Hossain, Shamshad B. Quraishi, Koushik Saha, Farzana Rahman, Uttam Kumar Sarker, Mir Tamzid Rahman. Mechanistic insights of the adsorption of Eriochrome Black T by the formulated Mg–Al LDH-graphene oxide composite. Journal of the Iranian Chemical Society 2022, 19 (4) , 1319-1328. https://doi.org/10.1007/s13738-021-02380-z
    11. Md Sajjadur Rahman, Jennifer Kyeremateng, Mousumi Saha, Sampson Asare, Nizam Uddin, Mohammad A. Halim, Douglas E. Raynie. Evaluation of the experimental and computed properties of choline chloride-water formulated deep eutectic solvents. Journal of Molecular Liquids 2022, 350 , 118520. https://doi.org/10.1016/j.molliq.2022.118520
    12. Dmitry Tolmachev, Natalia Lukasheva, Ruslan Ramazanov, Victor Nazarychev, Natalia Borzdun, Igor Volgin, Maria Andreeva, Artyom Glova, Sofia Melnikova, Alexey Dobrovskiy, Steven A. Silber, Sergey Larin, Rafael Maglia de Souza, Mauro Carlos Costa Ribeiro, Sergey Lyulin, Mikko Karttunen. Computer Simulations of Deep Eutectic Solvents: Challenges, Solutions, and Perspectives. International Journal of Molecular Sciences 2022, 23 (2) , 645. https://doi.org/10.3390/ijms23020645
    13. Philippe-Henri Secretan, Olivier Thirion, Hassane Sadou Yayé, Thibaud Damy, Alain Astier, Muriel Paul, Bernard Do. Simple Approach to Enhance Green Tea Epigallocatechin Gallate Stability in Aqueous Solutions and Bioavailability: Experimental and Theoretical Characterizations. Pharmaceuticals 2021, 14 (12) , 1242. https://doi.org/10.3390/ph14121242
    14. Mahmudul Islam Rain, Humayun Iqbal, Mousumi Saha, Md Ackas Ali, Harmeet Kaur Chohan, Md Sajjadur Rahman, Mohammad A. Halim. A comprehensive computational and principal component analysis on various choline chloride-based deep eutectic solvents to reveal their structural and spectroscopic properties. The Journal of Chemical Physics 2021, 155 (4) https://doi.org/10.1063/5.0052569

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