Synthesis of nanohydroxyapatite modified with lanthanum and cerium ions: composition and properties
O.A. Golovanova
Dostoevsky Omsk State University
DOI: 10.26456/pcascnn/2024.16.837
Original article
Abstract: Lanthanide-doped hydroxyapatite nanoparticles can be used as luminescent labels and become an alternative to organic fluorophores, as they are more stable and have a longer service life. Such materials allow tissue studies in surgery, the bone engineering and tissue regeneration. Lanthanides are known to have a high affinity for hydroxyapatite. This is due to the fact that lanthanides have ionic radii close to that of the calcium ion which is associated with their biological activity. Rare earth elements inhibit the formation of osteoclast-like cells and the process of the bone resorption. At the same time, lanthanides have a biological effect on the body, as a result bacterial growth is suppressed and, at the same time, the structure of the outer cell membrane, responsible for cell permeability, changes. Substituted hydroxyapatites were synthesized with varying content of the lanthanum (III) and cerium (III) ions. The formation of substituted hydroxyapatite was proven by X-ray diffraction and infrared spectroscopy. The parameters of the crystal lattices of the synthesized phases were shown to change, indicating the replacement of calcium ions by rare earth element ions in the hydroxyapatite structure. The presence of rare earth element ions in solid phases was proven by inductively coupled plasma atomic emission spectroscopy. The study of the resorption of thesynthesized samples revealed that cation-substituted hydroxyapatites are less soluble than unmodified hydroxyapatite. Thus, lanthanum (III) and cerium (III) ions can inhibit and suppress the action of osteoclasts and thereby prevent the destruction of the bone tissue maintaining its integrity. Accordingly, the material based on hydroxyapatite dosed with rare earth element ions can have a positive effect when used in bone engineering.
Keywords: synthesis, hydroxyapatite, modification, bioactivity, structure, rare earth elements
- Olga A. Golovanova – Dr. Sc., Professor, Head of the Department of Inorganic Chemistry, Dostoevsky Omsk State University
Reference:
Golovanova, O.A. Synthesis of nanohydroxyapatite modified with lanthanum and cerium ions: composition and properties / O.A. Golovanova // Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials. — 2024. — I. 16. — P. 837-847. DOI: 10.26456/pcascnn/2024.16.837. (In Russian).
Full article (in Russian): download PDF file
References:
1. Barinov S.M., Komlev S.V. Biokeramika na osnove fosfatov kal'tsiya [Bioceramics based on calcium phosphates]. Moscow, Nauka Publ., 2005, 204 р. (In Russian).
2. Dorozhkin S.V. Calcium orthophosphates (CaPO4): occurrence and properties. Review paper, Progress in Biomaterials, 2016, vol. 5, pp. 9-70. DOI: 10.1007/s40204-015-0045-z.
3. Mucalo M. Hydroxyapatite (HAp) for biomedical applications. Woodhead Publishing Series in Biomaterials. Amsterdam, Elsevier/Woodhead Publishing, 2015, XIX+381 p.
4. Yelten-Yilmaza A., Yilmaza S. Wet chemical precipitation synthesis of hydroxyapatite (HA) powders, Ceramics International, 2018, vol. 44, issue 8, pp. 9703-9710. DOI: 10.1016/j.ceramint.2018.02.201.
5. Rodríguez-Lugo V., Karthik T.V.K., Mendoza-Anaya D. et al. Wet chemical synthesis of nanocrystalline hydroxyapatite flakes: effect of pH and sintering temperature on structural and morphological properties, Royal Society Open Science, 2018, vol. 5, issue 8, art. no. 180962, 14 p. DOI: 10.1098/rsos.180962.
6. Cox S., Walton R.I., Mallick R.I. Comparison of techniques for the synthesis of hydroxyapatite, Bioinspired, Biomimetic and Nanobiomaterials, 2014, vol. 4, issue 1, pp. 37-47. DOI: 10.1680/bbn.14.00010.
7. Cawthray J. F., Creagh L. A., Haynes C. A., Orvig C. Ion exchange in hydroxyapatite with lanthanides. Inorganic Chemistry, 2015, vol. 54, issue 4, pp. 1440-1445. DOI: 10.1021/ic502425e.
8. Guoqing M. Three common preparation methods of hydroxyapatite, IOP Conference Series: Materials Science and Engineering, 2018, vol. 688, issue 3, art. no. 033057, 12 p. DOI: 10.1088/1757-899X/688/3/033057.
9. Tang S., Fei X. Refractory calcium phosphate-derived phosphorus fertilizer based on hydroxyapatite nanoparticles for nutrient delivery, ACS Applied Nano Materials, 2021, vol. 4, no.2, pp. 1364-1376. DOI: 10.1021/acsanm.0c02921.
10. Lamkhao S., Phaya M., Jansakun C. et al. Synthesis of hydroxyapatite with antibacterial properties using a microwave-assisted combustion method, Scientific Reports, 2019, vol. 9, no. 1, art. no. 4015, 9 p. DOI: 10.1038/s41598-019-40488-8.
11. Nasiri N., Clarke C. Nanostructured gas sensors for medical and health applications: low to high dimensional materials, Biosensors, 2019, vol. 9, issue 1, art. no. 43, 22 p. DOI: 10.3390/bios9010043.
12. George S., Mehta D., Saharan V. K. Application of hydroxyapatite and its modified forms as adsorbents for water defluoridation: an insight into process synthesis, Reviews in Chemical Engineering, 2020, vol. 36, issue 3, pp. 369-400. DOI: 10.1515/revce-2017-0101.
13. Thales R., Júlio M., Sczancoskia C. et al. Structural properties and self-activated photoluminescence emissions in hydroxyapatite with distinct particle shapes, Ceramics International, 2018, vol. 44, issue 1, pp. 236-245. DOI: 10.1016/j.ceramint.2017.09.164.
14. Kazin P. E., Pogosova M. A., Trusov L. A. et al. Crystal structure details of La- and Bi-substituted hydroxyapatites: evidence for LaO + and BiO + with a very short metal–oxygen bond. Journal of Solid-State Chemistry, 2016, vol. 237, pp. 349-357. DOI: 10.1016/j.jssc.2016.03.004.
15. Kaur K., Singh K.J., Anand V. et al. Lanthanide (= Ce, Pr, Nd and Tb) ions substitution at calcium sites of hydroxyl apatite nanoparticles as fluorescent bio probes: experimental and density functional theory study, Ceramics International, 2017, vol. 43, issue 13, pp. 10097-10108. DOI: 10.1016/j.ceramint.2017.05.029.
16. Gopi D., Sathishkumar S., Karthika A. et al. Development of Ce3+/Eu3+ dual-substituted hydroxyapatite coating on surgical grade stainless steel for improved antimicrobial and bioactive properties, Industrial & Engineering Chemistry Research, 2014, vol. 53, issue 52, pp. 20145-20153. DOI: 10.1021/ie504387k.
17. Golovanova O.A. Synthesis of of нydroxylapatite substituted with ions (La3+ and Y3+):сomposition, structure, and properties, Journal of Inorganic Chemistry, 2023, vol. 68, issue 3, pp. 334-341. DOI: 10.1134/S0036023622700139.