Tegafur and lamivudine complexes with MoS2: Structures, interaction energies, and vibrational spectra
DOI (Low Temperature Physics):
https://doi.org/10.1063/10.0043344Ключові слова:
molybdenum disulfide, tegafur, lamivudine, conformers, stacked complexes, covalently bonded complexes, quantum mechanical calculations, DFT, IR spectra, Raman spectra, Wiberg bond indicesАнотація
Досліджено структури, енергії взаємодії та коливальні спектри комплексів двох молекул лікарських засобів (ламівудину та тегафуру) з MoS2, а також з MoS2, що містить поверхневі точкові дефекти. Оцінено потенціал MoS2 як платформи для доставки лікарських засобів, таких як тегафур та ламівудин. Вичерпний пошук конформерів тегафуру та ламівудину проведено за допомогою методу MP2/aug-cc-pVDZ. Знайдено чотири конформери тегафуру та шістнадцять конформерів ламівудину. Розрахунки комплексів MoS2 з найбільш стабільними конформерами молекул, що досліджуються, проведено за допомогою методу DFT/M06-2X. Продемонстровано можливість утворення стекінг-комплексів, а також комплексів з утворенням координаційних зв’язків. Комплекси з незбуреною поверхнею MoS2 стабілізуються лише стекінг-взаємодією та мають відносно низькі за абсолютними значеннями енергії взаємодії. Врахування водного середовища значно послаблює стекінг-взаємодію приблизно до –2 ккал/моль. Для комплексів, стабілізованих координаційними зв’язками, енергії взаємодії знаходяться в діапазоні від –90 до –40 ккал/моль. Цього достатньо для зв’язування молекул тегафуру та ламівудину, навіть з урахуванням ослаблення взаємодії у воді приблизно до –20 ккал/моль. Аналіз коливальних спектрів комплексів те гафуру та ламівудину з MoS2 дозволив визначити їхні спектральні маркери.
Посилання
1. S. Ghosh and J.-Y. Lai, “An insight into the dual role of MoS2-based nanocarriers in anticancer drug delivery and therapy,” Acta Biomater. 179, 36 (2024). https://doi.org/10.1016/j.actbio.2024.03.019
2. T. Liu, C. Wang, X. Gu, H. Gong, L. Cheng, X. Shi, L. Feng, B. Sun, and Z. Liu, “Drug delivery with PEGylated MoS2 nano-sheets for combined photothermal and chemotherapy of cancer,” Adv. Mater. 26, 3433 (2014). https://doi.org/10.1002/adma.201305256
3. K. Zhang, Y. Zhuang, W. Zhang, Y. Guo, and X. Liu, “Functionalized MoS2-nanoparticles for transdermal drug delivery of atenolol,” Drug Deliv. 27, 909 (2020). https://doi.org/10.1080/10717544.2020.1778815
4. Y. Liu and J. Liu, “Hybrid nanomaterials of WS2 or MoS2 nanosheets with liposomes, biointerfaces and multiplexed drug delivery,” Nanoscale 9, 13187 (2017). https://doi.org/10.1039/C7NR04199C
5. J. Liu, K. Lu, F. Gao, L. Zhao, H. Li, and Y. Jiang, “Multifunctional MoS2 composite nanomaterials for drug delivery and synergistic photothermal therapy in cancer treatment,” Ceram. Int. 48, 22378 (2022). https://doi.org/10.1016/j.ceramint.2022.04.244
6. X. Yu, C. Xu, J. Sun, H. Xu, H. Huang, Z. Gan, A. George, S. Ouyang, and F. Liu, “Recent developments in two-dimensional molybdenum disulfide-based multimodal cancer theranostics,” J. Nanobiotechn. 22, 515 (2024). https://doi.org/10.1186/s12951-024-02785-x
7. F. Wang, F.-Y. Lv, K.-L. Liu, Z.-H. Li, S. Niu, Y.-Y. Zhang, H.-L. Cong, Y.-Q. Shen, and B. Yu, “Synthesis of MoS2 nanosheets drug delivery system and its drug release behaviors,” Ferroelectrics 578, 31 (2021). https://doi.org/10.1080/00150193.2021.1902761
8. M. Liu, H. Zhu, Y. Wang, C. Sevencan, and B. L. Li, “Functionalized MoS2-based nanomaterials for cancer phototherapy and other biomedical applications,” ACS Mater. Lett. 3, 462 (2021). https://doi.org/10.1021/acsmaterialslett.1c00073
9. Z. Yu, T. Huang, S. Ullah, Y. Wang, and G. Luo, “Controllable synthesis of porous 1T-MoS2 with large surface area via continuous hydrothermal system,” Ind. Eng. Chem. Res. 63, 15113 (2024). https://doi.org/10.1021/acs.iecr.4c01796
10. C. A. Sălăgean, L. C. Cotet, M. Baia, C. I. Fort, G. L. Turdean, L. Barbu-Tudoran, M. D. Lazar, and L. Baia, “Influence of precursors on physical characteristics of MoS2 and their correlation with potential electrochemical applications,” Materials 18, 2111 (2025). https://doi.org/10.3390/ma18092111
11. C. Calais, N. Matsubayashi, C. Geantet, Y. Yoshimura, H. Shimada, A. Nishijima, M. Lacroix, and M. Breysse, “Crystallite size determination of highly dispersed unsupported MoS2 catalysts,” J. Catalysis 174, 130 (1998). https://doi.org/10.1006/jcat.1998.1934
12. K. H. Hu, G. H. Xian, F. X. Yu, and X. Z. Pan, “The effect of morphology and size on the photocatalytic properties of MoS2,” React. Kinet. Mech. Catal. 100, 153 (2010).https://doi.org/10.1007/s11144-010-0173-3
13. M. Wang, G. Li, H. Xu, Y. Qian, and J. Yang, “Enhanced lithium storage performances of hierarchical hollow MoS2 nanoparticles assembled from nanosheets,” ACS Appl. Mat. Interfaces 5, 1003 (2013). https://doi.org/10.1021/am3026954
14. M. Salimi, M. A. Shokrgozar, D. H. Hamid, and M. Vossoughi, “Photothermal properties of two-dimensional molybdenum disulfide (MoS2) with nanoflower and nanosheet morphology,” Mater. Res. Bull. 152, 111837 (2022). https://doi.org/10.1016/j.materresbull.2022.111837
15. A. Sharma, D. Bhalothia, R. Vankayala, and A. Bagaria, “Morphology-driven photothermal performance of polymer-functionalized MoS2 nanoplatforms for targeted therapeutic applications,” Sci. Rep. 15, 26028 (2025). https://doi.org/10.1038/s41598-025-09648-x
16. A. Abareshi, M. M. Shahidi, and N. Salehi, “Comparison of structural, optical, and thermal properties in MoS2-based nanocomposites into cancer therapy,” J. Mater. Sci. Mater. Med. 36, 33 (2025). https://doi.org/10.1007/s10856-025-06883-6
17. T. Liu, C. Wang, W. Cui, H. Gong, C. Liang, X. Shi, Z. Li, B. Suna, and Z. Liu, “Combined photothermal and photodynamic therapy delivered by PEGylated MoS2 nanosheets,” Nanoscale 6, 11219 (2014). https://doi.org/10.1039/C4NR03753G
18. H. Lin, D.-K. Ji, M. A. Lucherelli, G. Reina, S. Ippolito, P. Samorì, and A. Bianco, “Comparative effects of graphene and molybdenum disulfide on human macrophage toxicity,” Small 16, 2002194 (2020). https://doi.org/10.1002/smll.202002194
19. E. Tan, B. L. Li, K. Ariga, C.-T. Lim, S. Garaj, and D. T. Leong, “Toxicity of two-dimensional layered materials and their heterostructures,” Bioconjugate Chem. 30, 2287 (2019). https://doi.org/10.1021/acs.bioconjchem.9b00502
20. M. Sadeghi, M. Jahanshahi, M. Ghorbanzadeh, and G. Najafpour, “Adsorption of DNA/RNA nucleobases onto single-layer MoS2 and Li-doped MoS2, A dispersion-corrected DFT study,” Appl. Surf. Sci. 434, 176 (2018). https://doi.org/10.1016/j.apsusc.2017.10.162
21. S. G. Stepanian, V. A. Karachevtsev, and L. Adamowicz, “Structure of the stacked and covalently bonded MoS2-nucleobase complexes, A first-principles study,” Chem. Phys. Lett. 844, 141270 (2024). https://doi.org/10.1016/j.cplett.2024.141270
22. H. Vovusha and B. Sanyal, “Adsorption of nucleobases on 2D transition-metal dichalcogenides and graphene sheet, a first-principles density functional theory study,” RSC Adv. 5, 67427 (2015). https://doi.org/10.1039/C5RA14664J
23. M. Sharma, A. Kumar, and P. K. Ahluwalia, “Optical fingerprints and electron transport properties of DNA bases adsorbed on monolayer MoS2,” RSC Adv. 6, 60223 (2016). https://doi.org/10.1039/C6RA10008B
24. T. Piddubnyi, S. Stepanian, V. Karachevtsev, and L. Adamowicz, “IR and Raman markers of the interactions between MoS2 and pyrimidine bases,” Low Temp. Phys. 50, 196 (2024) [Fiz. Nyzk. Temp. 50, 210 (2024)]. https://doi.org/10.1063/10.0024968
25. Y. M. El-Sayed and W. Sadée, “Metabolic activation of R,S-1-(tetrahydro-2-furanyl)-5-fluorouracil) (ftorafur) to 5-fluorouracil by soluble enzymes,” Cancer Res. 43, 4039 (1983), see https://aacrjournals.org/cancerres/article/43/9/4039/487850/Metabolic-Activation-of-R-S-1-Tetrahydro-2-furanyl.
26. M. Shahabi and H. Raissi, “Investigation of the solvent effect, molecular structure, electronic properties and adsorption mechanism of tegafur anticancer drug on graphene nanosheet surface as drug delivery system by molecular dynamics simulation and density functional approach,” J Incl. Phenom. Macrocycl. Chem. 88, 159 (2017). https://doi.org/10.1007/s10847-017-0713-9
27. B. Makiabadi, M. Zakarianezhad, and S. S. Hosseini, “Investigation and comparison of pristine/doped BN, AlN, and CN nanotubes as drug delivery systems for tegafur drug, a theoretical study,” Struct. Chem. 32, 1019 (2021). https://doi.org/10.1007/s11224-020-01680-z
28. M. Shahabi and H. Raissi, “Payload delivery of anticancer drug tegafur with the assistance of graphene oxide nanosheet during biomembrane penetration, molecular dynamics simulation survey,” Appl. Surf. Sci. 517, 146186 (2020). https://doi.org/10.1016/j.apsusc.2020.146186
29. Y. Zhao and D. G. Truhlar, “The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements, Two new functionals and systematic testing of four M06-class functionals and 12 other functionals,” Theor. Chem. Acc. 120, 215 (2008). https://doi.org/10.1007/s00214-007-0310-x
30. A. Glamazda, E. Usenko, A. Svidzerska, V. Valeev, I. Voloshin, A. Laguta, S. Petrushenko, S. Stepanian, L. Adamowicz, and V. Karachevtsev, “Binding of native DNA to MoS2 nanoflakes, The role of defects and edge atoms of MoS2 nanostructures in their biofunctionalization,” Low Temp. Phys. 51, 1283 (2025) [Fiz. Nyzk. Temp. 51, 1418 (2025)]. https://doi.org/10.1063/10.0039430
31. P. J. Hay and W. R. Wadt, “Ab initio effective core potentials for molecular calculations. potentials for the transition metal atoms Sc to Hg,” J. Chem. Phys. 82, 270 (1985). https://doi.org/10.1063/1.448799
32. P. J. Hay and W. R. Wadt, “Ab initio effective core potentials for molecular calculations. potentials for main group elements Na to Bi,” J. Chem. Phys. 82, 284 (1985). https://doi.org/10.1063/1.448800
33. P. J. Hay and W. R. Wadt, “Ab initio effective core potentials for molecular calculations. potentials for K to Au including the outermost core orbitals,” J. Chem. Phys. 82, 299 (1985). https://doi.org/10.1063/1.448975
34. C. E. Check, T. O. Faust, J. M. Bailey, B. J. Wright, T. M. Gilbert, and L. S. Sunderlin, “Addition of polarization and diffuse functions to the LANL2DZ basis set for p-block elements,” J. Phys. Chem. A 105, 8111 (2001). https://doi.org/10.1021/jp011945l
35. S. F. Boys and F. Bernardi, “Calculation of small molecular interactions by differences of separate total energies—some procedures with reduced errors,” Mol. Phys. 19, 553 (1970). https://doi.org/10.1080/00268977000101561
36. G. Scalmani and M. J. Frisch, “Continuous surface charge polarizable continuum models of solvation. I. general formalism,” J. Chem. Phys. 132, 114110 (2010). https://doi.org/10.1063/1.3359469
37. K. M. Merz, Jr. and P. A. Kollman, “Atomic charges derived from semiempirical methods,” J. Comp. Chem. 11, 431 (1990). https://doi.org/10.1002/jcc.540110404
38. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian 16, Revision B.01 (Gaussian, Inc., Wallingford CT, 2016).
