Phase Separation of L-Menthol an Aqueous Dispersion of Biologically Active Nanoparticles of Chitosan L- and D-Aspartate

Xenia M. Shipenok orcid (Login required)
Saratov National Research State University named after N.G. Chernyshevsky, Russian Federation

Aliya M. Mazhikenova orcid
Saratov National Research State University named after N.G. Chernyshevsky, Russian Federation

Evgeny G. Glukhovskoy orcid
Saratov National Research State University named after N.G. Chernyshevsky, Russian Federation

Anna B. Shipovskaya orcid
Saratov National Research State University named after N.G. Chernyshevsky, Russian Federation


Paper #9184 received 23 Oct 2024; revised manuscript received 21 Nov 2024; accepted for publication 25 Nov 2024; published online 14 Dec 2024.

DOI: 10.18287/JBPE24.10.040316

Abstract

Phase separation in an ethanol solution of L-menthol in an aqueous dispersion of biologically active nanoparticles of chitosan L- and D-aspartate was studied. The process was found to proceed through the mechanism of selective extraction crystallization and to combine two types of phase separation (liquid-liquid and liquid-crystal). Liquid phase separation involves spontaneous dispersion of the ethanol macrophase to form a water microemulsion with hydrophobic content and subsequent coalescence of the dispersed phase. Crystalline phase separation involves L-menthol crystallization into optically anisotropic fibrillar particles. The size of microdroplets and fibrils and their packing density in the condensed phase are significantly affected by the concentration of the components and surface tension of the aqueous macrophase and the enantiomeric form of chitosan aspartate. It has been suggested that the system under study is promising for the development of new approaches to studying the fundamental principles of phase separation during intracellular communication and regulation

Keywords

chitosan; L- and D-aspartic acid; chitosan L- and D-aspartate; nanoparticles; L-menthol; phase separation; extraction crystallization; intracellular regulation; subcellular organization

Full Text:

PDF

References


1. H. Zhong, J. Deng “Organic polymer-constructed chiral particles: preparation and chiral applications,” Polymer Reviews 62(4), 826–859 (2022).

2. L. Song, M. Pan, R. Zhao, J. Deng, and Y. Wu, “Recent advances, challenges and perspectives in enantioselective release,” Journal of Controlled Release 324, 156–171 (2020).

3. H. Yu, X. Yong, J. Liang, J. Deng, and Y. Wu, “Materials established for enantioselective release of chiral compounds,” Industrial and Engineering Chemistry Research 55(21), 6037–6048 (2016).

4. S. V. Nesterov, N. S. Ilyinsky, and V. N. Uversky, “Liquid-liquid phase separation as a common organizing principle of intracellular space and biomembranes providing dynamic adaptive responses,” Biochimica et Biophysica Acta - Molecular Cell Research 1868(11), 119102 (2021).

5. D. M. Mitrea, R. W. Kriwacki, “Phase separation in biology; functional organization of a higher order,” Cell Communication and Signaling 14(1), 1 (2016).

6. M. Feric, N. Vaidya, T. S. Harmon, D. M. Mitrea, L. Zhu, T. M. Richardson, R. W. Kriwacki, R. V. Pappu, and C. P. Brangwynne, “Coexisting liquid phases underlie nucleolar subcompartments,” Cell 165(7), 1686–1697 (2016).

7. P. Robbins, A. Morelli, “Regulation of immune responses by extracellular vesicles,” Nature Reviews Immunology 14, 195–208 (2014).

8. A. C. Dixson, T. R. Dawson, and D. Di Vizio, “Context-specific regulation of extracellular vesicle biogenesis and cargo selection,” Nature Reviews Molecular Cell Biology 24, 454–476 (2023).

9. L. P. Bergeron-Sandoval, N. Safaee, and S. W. Michnick, “Mechanisms and consequences of macromolecular phase separation,” Cell 165(5), 1067–1079 (2016).

10. L. Zhu, C. P. Brangwynne, “Nuclear bodies: the emerging biophysics of nucleoplasmic phases,” Current Opinion in Cell Biology 34, 23–30 (2015).

11. A. Molliex, J. Temirov, J. Lee, M. Coughlin, A. P. Kanagaraj, H. J. Kim, T. Mittag, and J. P. Taylor, “Phase separation by low complexity domains promotes stress granule assembly and drives pathological fibrillization,” Cell 163(1), 123–133 (2015).

12. Y. Lin, D. S. W. Protter, M. K. Rosen, and R. Parker, “Formation and maturation of phase-separated liquid droplets by RNA-binding proteins,” Molecular Cell 60(2), 208–219 (2015).

13. A. B. Shipovskaya, N. O. Gegel, and X. M. Shipenok, “Features of L-menthol crystallization in optically active medium based on L- and D-asparaginate chitosan features of L-menthol crystallization in optically active medium based on L- and D-asparaginate chitosan,” Journal of Biomedical Photonics 9(1), 010305 (2023).

14. N. J. Ayon, “Features, roles and chiral analyses of proteinogenic amino acids,” AIMS Molecular Science 7(3), 229−268 (2020).

15. L. Tu, Y. K. Lin, “The origin of life and the crystallization of aspartic acid in water,” Crystal Growth and Design 10(4), 1652−1660 (2010).

16. A. V. Chervyakov, N. V. Gulyaeva, and M. N. Zakharova, “D-Amino acids in normal ageing and pathogenesis of neurodegenerative diseases,” Neurochemical Journal 5(2), 100−114 (2011).

17. A. G. Shtukenberg, Y. O. Punin, A. Gujral, and B. Kahr, “Growth actuated bending and twisting of single crystals,” Angewandte Chemie International Edition 53(3), 672−699 (2014).

18. E. Betz-Güttner, M. Righi, S. Micera, and A. Fraleoni-Morgera, “Directional growth of cm-long PLGA nanofibers by a simple and fast wet-processing method,” Materials 15(2), 687 (2022).

19. S. Kim, S. C. Peterson, “Optimal conditions for the encapsulation of menthol into zein nanoparticles,” LWT 144, 111213 (2021).

20. T. Kovács, R. Szűcs, G. Holló, Z. Zuba, J. Molnár, H. K. Christenson, and I. Lagzi, “Self-assembly of chiral menthol molecules from a liquid film into ring-banded spherulites,” Crystal Growth and Design 19(7), 4063−4069 (2019).

21. T. N. Lugovitskaya, A. B. Shipovskaya, S. L. Shmakov, and X. M. Shipenok, “Formation, structure, properties of chitosan aspartate and metastable state of its solutions for obtaining nanoparticles,” Carbohydrate Polymers 277, 118773 (2022).

22. A. Shipovskaya, X. Shipenok, T. Lugovitskaya, and T. Babicheva, “Self-assembling nano- and microparticles of chitosan L-and D-aspartate: preparation, structure, and biological activity,” Materials Proceedings 14(1), 31 (2023).

23. A. B. Shipovskaya, T. N. Lugovitskaya, and I. V. Zudina, “Biocidal activity of chitosan aspartate nanoparticles,” Microbiology 92(1), 75–82 (2023).

24. E. V. Shadrina, O. N. Malinkina, T. G. Khonina, A. B. Shipovskaya, V. I. Fomina, E. Yu. Larchenko, N. A. Popova, I. G. Zyryanova, and L. P. Larionov, “Formation and pharmacological activity of silicon—chitosan-containing glycerohydrogels obtained by biomimetic mineralization,” Russian Chemical Bulletin 64, 1633–1639 (2015).

25. G. Kaptay, “On the temperature dependence of surface tension: Historical perspective on the Eötvös equation of capillarity, celebrating his 175th anniversary,” Advances in Colloid and Interface Science 332, 103275 (2024).

26. A. M. Emelianenko, and L. B. Boinovich, “Role of disperger particles in physical-chemical movement of nanofluids,” Colloid Journal 85(6), 727–737 (2023).

27. T. N. Lugovitskaya, and A.B. Shipovskaya “Physicochemical properties of aqueous solutions of L-aspartic acid containing chitosan,” Russian Journal of General Chemistry 87(4), 782–787 (2017).




Bookmark and Share


© 2014-2025 Authors
Public Media Certificate (RUS). 12+