Izvestiya of Saratov University.

Physics

ISSN 1817-3020 (Print)
ISSN 2542-193X (Online)

For citation:

Berezin K. V., Stepanovich E. Y., Dvoretsky K. N., Antonova E. M., Likhter A. M., Yanina I. Y. Hydrogen bonding in saturated acids triglyceride monohydrates: MD and DFT modeling. Izvestiya of Saratov University. Physics , 2025, vol. 25, iss. 4, pp. 425-437. DOI: 10.18500/1817-3020-2025-25-4-425-437, EDN: LXEQFE

This is an open access article distributed under the terms of Creative Commons Attribution 4.0 International License (CC-BY 4.0).
Published online: 
28.11.2025
Full text:
download
(downloads: 8)
Language: 
Russian
Heading: 
Optics and spectroscopy. Laser physics
Article type: 
Article
UDC: 
544.18:577.32
DOI: 
10.18500/1817-3020-2025-25-4-425-437
EDN: 
LXEQFE

Hydrogen bonding in saturated acids triglyceride monohydrates: MD and DFT modeling

Autors: 
Berezin Kirill Valentinovich, Saratov State University
Stepanovich Ekaterina Yu., Astrakhan Tatishchev State University
Dvoretsky Konstantin Nikolaevich, Saratov State Medical University named after V. I. Razumovsky
Antonova Ekaterina M., Astrakhan State Medical University
Likhter Anatoly M., Astrakhan Tatishchev State University
Yanina Irina Yu., Saratov State University
Abstract: 

Background and Objectives: Triglycerides, as the primary components of fats and oils, play a crucial role in various scientific and industrial fields, including food production, energy, and pharmaceuticals. Their interaction with water molecules is particularly significant, yet many aspects of these interactions remain poorly understood. This study aims to investigate hydrogen bonding in monohydrates of saturated fatty acid triglycerides using molecular dynamics (MD) and density functional theory (DFT) simulations. The objectives include determining the thermodynamic parameters of association, analyzing the influence of hydrocarbon chain length on hydration, and identifying the most stable hydration configurations. Materials and Methods: The study employed classical molecular dynamics (GROMACS) with the AMBER-03 force field and DFT calculations (B3LYP/6-31+G(d) and wB97XD/6-311+G(d,p)) to model hydrogen bonds in monohydrates of triglycerides ranging from triacetin to tristearin (chain lengths of 0 to 16 methylene groups). The MD simulations involved a 4×4×4 nm periodic boundary cell with a triglyceride molecule surrounded by water, run for 500 ps at 300 K and 1 bar. Hydrogen bonds were identified using geometric criteria (distance ≤ 3.5 Å, angle ≤ 30°). DFT calculations optimized molecular structures and calculated thermodynamic parameters, including association energies, enthalpies, and equilibrium constants. Results: The results have revealed that carbonyl groups of the central ester chain are the primary sites for hydrogen bond formation. Monohydrates involving the central chain (Type 1) have exhibited a greater stability than those involving side chains (Type 2). The association energy for Type 1 monohydrates has saturated starting from tricaprylin (chain length of 6). A linear relationship has been observed between the thermodynamic parameter TΔS and the equilibrium constant Kα for Type 1 monohydrates, attributed to the loss of conformational entropy upon hydration. Non-classical hydrogen bonds (C-H···O) have also contributed to the stability of monohydrates, influencing their spatial structure. The study has found that hydration of longer chains requires higher energy to overcome entropy losses. Conclusion: The study has demonstrated that the central carbonyl group of triglycerides is the primary hydration site, with Type 1 monohydrates being more stable than Type 2. The association energy and enthalpy reach saturation for chains longer than tricaprylin, while linear dependencies of TΔS and Kα on chain length highlight the role of conformational entropy in hydration. These findings enhance the understanding of triglyceridewater interactions, providing insights relevant to food science, pharmaceuticals, and the development of lipid-based delivery systems. The combined use of MD and DFT has proved effective for analyzing these complex molecular interactions.

Key words: 
triglycerides
hydrogen bonds
molecular dynamics
density functional theory
hydration
thermodynamics
Acknowledgments: 
This work was supported by the Russian Science Foundation (project No. 24-44-00082, https://rscf.ru/project/24-44-00082/).
Reference: 
  1. McClements D. J. Food Emulsions: Principles, Practices, and Techniques. 3rd edition. Boca Raton, CRC Press, 2015. 714 p. https://doi.org/10.1201/b18868
  2. Ravotti R., Worlitschek J., Pulham C., Stamatiou A. Triglycerides as novel phase-change materials: A review and asessment of their thermal properties. Molecules, 2020, vol. 25, iss. 23, art. 5572. https://doi.org/10.3390/molecules25235572
  3. Tascini A. S., Noro M. G., Chen R., Seddon J. M., Bresme F. Understanding the interactions between sebum triglycerides and water: A molecular dynamics simulation study. Phys. Chem. Chem. Phys., 2018, vol. 20, iss. 3, pp. 1848–1860. https://doi.org/10.1039/C7CP06889A
  4. Chumpitaz L. D. A., Coutinho L. F., Meirelles A. J. A. Surface tension of fatty acids and triglycerides. J. Amer. Oil Chem. Soc., 1999, vol. 76, iss. 3, pp. 379–382. https://doi.org/10.1007/s11746-999-0245-6
  5. Javadi A., Dowlati S., Shourni S., Rusli S., Eckert K., Miller R., Kraume M. Enzymatic hydrolysis of triglycerides at the water–oil interface studied via interfacial rheology analysis of lipase adsorption layers. Langmuir, 2021, vol. 37, iss. 44, pp. 12919–12928. https://doi.org/10.1021/acs.langmuir.1c01963
  6. Caruso B., Wilke N., Perillo M. A. Triglyceride lenses at the air–water interface as a model system for studying the initial stage in the biogenesis of lipid droplets. Langmuir, 2021, vol. 37, iss. 37, pp. 10958–10970. https://doi.org/10.1021/acs.langmuir.1c01359
  7. Kinard T. C., Wrenn S. P. Triglycerides stabilize water/organic interfaces of changing area via conformational flexibility. Langmuir, 2024, vol. 40, iss. 5, pp. 2500–2509. https://doi.org/10.1021/acs.langmuir.3c02473
  8. Cao Y., Marra M., Anderson B. D. Predictive relationships for the effects of triglyceride ester concentration and water uptake on solubility and partitioning of small molecules into lipid vehicles. J. Pharm Sci., 2004, vol. 93, iss. 11, pp. 2768–2779. https://doi.org/10.1002/jps.20126
  9. Benedikt T., Briesen K. H. Water–triglyceride interfaces limit permeability and diffusion of aromamolecules in butter. Eur. J. Lipid Sci. Technol., 2024. vol. 126, iss. 12, art. 2300248. https://doi.org/10.1002/ejlt.202300248
  10. Groot C. C. M., Velikov K. P., Bakker H .J. Structure and dynamics of water molecules confined in triglyceride oils. Phys. Chem. Chem. Phys., 2016, vol. 18, iss. 42, pp. 29361–29368. https://doi.org/10.1039/C6CP05883C
  11. Papageorgiou D. G., Demetropoulos I. N., Lagaris I. E., Papadimitriou P. T. How many conformers of the 1,2,3-propanetriol triacetate are pin gas phase and in aqueous solution? Tetrahedron, 1996, vol. 52, iss. 2, pp. 677–686. https://doi.org/10.1016/0040-4020(95)00918-3
  12. Berezin K. V., Dvoretskii K. N., Chernavina M. L., Novoselova A. V., Nechaev V. V., Likhter A. M., Shagautdinova I. T., Smirnov V. V., Antonova E. M., Grechukhina O. N. The use of IR spectroscopy and density functional theory for estimating the relative concentration of triglycerides of oleic and linoleic acids in a mixture of olive and sunflower seed oils. Opt. Spectrosc., 2019, vol. 127, iss. 6, pp. 955–961. https://doi.org/10.1134/S0030400X1912004X
  13. Berezin K. V., Dvoretskii K. N., Chernavina M. L., Novoselova A. V., Nechaev V. V., Antonova E. M., Shagautdinova I. T., Likhter A. M. The Use of Raman spectroscopy and methods of quantum chemistry for assessing the relative concentration of triglycerides of oleic and linoleic acids in a mixture of olive oil and sunflower seed oil. Opt. Spectrosc., 2018, vol. 125, iss. 3, pp. 311–316. https://doi.org/10.1134/S0030400X18090059
  14. Berezin K. V., Antonova E. M., Shagautdinova I. T., Chernavina M. L., Dvoretskiy K. N., Grechukhina O. N., Vasilyeva L. M., Rybakov A. V., Likhter A. M. FTIR spectrum of grape seed oil and quantum models of fatty acids triglycerides. Proc. SPIE, 2018, vol. 10716, art. 1071625. https://doi.org/10.1117/12.2316488
  15. Van der Spoel D., Lindahl E., Hess B., Groenhof G., Mark E. A., Berendsen H .J. C. GROMACS: Fast, flexible, and free. J. Comput. Chem., 2005, vol. 26, iss. 16, pp. 1701–1718. https://doi.org/10.1002/jcc.20291
  16. Duan Y., Wu C., Chowdhury S., Lee M. C., Xiong G., Zhang W., Yang R., Cieplak P., Luo R., Lee T., Caldwell J., Wang J., Kollman P. A point-charge force field for molecular mechanics simulations of proteins based on condensed-phase quantum mechanical calculations. J. Comp. Chem., 2003, vol. 24, iss. 16, pp. 1999–2012. https://doi.org/10.1002/jcc.10349
  17. Berendsen H. J. C., Postma J. P. M., van Gunsteren W. F., DiNola A., Haak J. R., Molecular dynamics with coupling to an external bath. J. Chem. Phys., 1984, vol. 81, iss. 8, pp. 3884–3690. https://doi.org/10.1063/1.448118
  18. Humphrey W., Dalke A., Schulten K. VMD: Visual molecular dynamics. J. Mol. Graph., 1996, vol. 14, iss. 1, pp. 33–38. https://doi.org/10.1016/0263-7855(96)00018-5
  19. Loof H. D., Nilsson L., Rigler R., Molecular dynamics simulation of galanin in aqueous and nonaqueous solution. J. Am. Chem. Soc., 1992, vol. 114, iss. 11, pp. 4028–4035. https://doi.org/10.1021/ja00037a002
  20. Frisch M. J., Trucks G., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M. [et al.]. Gaussian 09, Revision A.02. Gaussian, Inc., Wallingford CT, 2009.
  21. Kollipost F., Wugt Larsen R., Domanskaya A. V., Nörenberg M., Suhm M. A., Communication: The highest frequency hydrogen bond vibration and an experimental value for the dissociation energy of formic acid dimer. J. Chem. Phys., 2012, vol. 136, iss. 15, art. 151101. https://doi.org/10.1063/1.4704827
  22. Rocher-Casterline B. E., Ch’ng L. C., Mollner A. K., Reisler H. Communication: Determination of the bond dissociation energy (D0) of the water dimer, (H2O)2, by velocity map imaging. J. Chem. Phys., 2011, vol. 134, iss. 21, art. 211101. https://doi.org/10.1063/1.3598339
  23. Nakayama T., Fukuda H., Kamikawa T., Sakamoto Y. Sugita A., Kawasaki M., Amano T., Sato H., Sakaki S., Morino I., Inoue G. Effective interaction energy of water dimer at room temperature: An experimental and theoretical study. J. Chem. Phys., 2007, vol. 127, iss. 13, art. 134302. https://doi.org/10.1063/1.2773726
  24. Ruscic B. Active thermochemical tables: Water and Water Dimer. J. Phys. Chem. A, 2013, vol. 117, iss. 46, pp. 11940–11953. https://doi.org/10.1021/jp403197t
  25. Becke A. Density‐functional thermochemistry. III. The role of exact exchange. J. Chem. Phys., 1993, vol. 98, iss. 7, pp. 5648–5652. https://doi.org/10.1063/1.464913
  26. Lee C., Yang W., Parr R. G., Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B, 1988, vol. 37, iss. 2, pp. 785–789. https://doi.org/10.1103/PhysRevB.37.785
  27. Chai J.-D., Head-Gordon M. Systematic optimization of long-range corrected hybrid density functionals. J. Chem. Phys, 2008, vol. 128, iss. 8, art. 084106. https://doi.org/10.1063/1.2834918
  28. Simon S., Duran M., Dannenberg J. How does basis set superposition error change the potential surfaces for hydrogen‐bonded dimers? J. Chem. Phys., 1996, vol. 105, iss. 24, pp. 11024–11031. https://doi.org/10.1063/1.472902
  29. Fayfel A. B., Berezin K. V. Program for calculating thermodynamic characteristics of intermolecular complexes based on quantum-mechanical calculations. Tuchin V. V., ed. Problemy opticheskoj fiziki: Materialy 7 Mezhdunarodnoj molodezhnoj nauchnoj shkoly po optike, lazernoj fizike i biofizike. Vol. 2 [Problems of Optical Physics: Proceedings of the 7th International youth scientific school on optics, laser physics and biophysics. Vol. 2]. Saratov, The State Scientific Center “College” Publ., 2004, pp. 100–101 (in Russian).
  30. Iogansen A. V. Infrared spectroscopy and spectral determination of hydrogen bond energy. In: Sokolov N. D., ed. Vodorodnaya svyaz’ [Hydrogen bond]. Moscow, Nauka, 1981, pp. 112–155 (in Russian).
Received: 
30.06.2025
Accepted: 
10.09.2025
Published: 
28.11.2025
  • 92 reads