Citation: Chun-Hua BAI, Huan-Jian HOU, Xiao-Ning YANG, Guang-Hui LI. Fluorescence and Biomineralization Ability of Erbium-Doped Hydroxyapatite[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(11): 2154-2164. doi: 10.11862/CJIC.2022.224 shu

Fluorescence and Biomineralization Ability of Erbium-Doped Hydroxyapatite

1.
College of Mining and Coal, Inner Mongolia University of Science and Technology, Baotou, Inner Mongolia 014010, China
2.
Sinosteel Maanshan General Institute of Mining Research Co., Ltd., Ma′anshan, Anhui 243000, China

Corresponding author: Guang-Hui LI, ligh@imust.edu.cn
Received Date: 21 March 2022
Revised Date: 5 September 2022

Figures(11)

Erbium - doped hydroxyapatite (Er - HAP) particles were prepared by the co - precipitation method. The crystal structure, surface chemical composition, and fluorescent properties of Er-HAP particles were characterized by the methods of X- ray diffraction combined with Materials Studio, scanning electron microscopy-energy dispersive spectroscopy, X - ray photoelectron spectroscopy, and fluorescence spectroscopy. The results showed that Er³⁺ can competitively substitute for a Ca2+ site in the crystal lattice. Under the excitation of a 340 nm light source, Er-HAP particles emitted significant fluorescence at around 419 nm (purple), 458 nm (blue), 501 nm (green), and 535 nm (green), respectively. The four corresponding luminescence bands are attributed to ⁴F_3/2 → ⁴I_15/2, ⁴F_5/2 → ⁴I_15/2, ⁴F_7/2 →4I_15/2, and 4S_3/2 → 4I_15/2 transition states, respectively. Further, we evaluated the biomineralization ability by analyzing the formation of an interfacial layer after Er-HAP particles were immersed in simulated body fluid. When the dopant content (molar fraction) of Er³⁺ was 1%, it was observed that Er-HAP particles could form the mineralized layer with plate-like structures, and Er³⁺ incorporation affected the biomineralization ability, whereas the biomineralization rate and osteogenic performance significantly decreased with the increasing of the dopant content of Er³⁺. Therefore, the stronger biomineralization ability of Er-HAP particles might be exhibited while the Er dopant content was about 1%.
- Er³⁺ doped hydroxyapatite,
- biomineralization,
- photoluminescence
1. [1]
  Wang X G, Yu Y M, Ji L L, Geng Z, Wang J, Liu C S. Calcium Phosphate-Based Materials Regulate Osteoclast-Mediated Osseointegration[J]. Bioact. Mater., 2021,6(12):4517-4530. doi: 10.1016/j.bioactmat.2021.05.003
2. [2]
  Alshemary A Z, Akram M, Goh Y F, Kadir M R A, Abdolahi A, Hussain R. Structural Characterization, Optical Properties and In Vitro Bioactivity of Mesoporous Erbium-Doped Hydroxyapatite[J]. J. Alloy. Compd., 2015,645:478-486. doi: 10.1016/j.jallcom.2015.05.064
3. [3]
  Cheng K, Zhang S, Weng W J. The F Content in Sol-Gel Derived FHA Coatings: An XPS Study[J]. Surf. Coat. Technol., 2004,198(1):237-241.
4. [4]
  Neacsu I A, Stoica A E, Vasile B S, Andronescu E. Luminescent Hydroxyapatite Doped with Rare Earth Elements for Biomedical Applications[J]. Nanomaterials, 2019,9(2)239. doi: 10.3390/nano9020239
5. [5]
  Li Y, Ooi C P, Cheang P H N, Khor K A. Synthesis and Characterization of Neodymium and Gadolinium -Substituted Hydroxyapatite as Biomaterials[J]. Int. J. Appl. Ceram. Technol., 2019,6(4):501-512.
6. [6]
  Heng C N, Zhou X, Zheng X Y, Liu M Y, Wen Y Q, Huang H Y, Fan D D, Hui J F, Zhang X Y, Wei Y. Surface Grafting of Rare-Earth Ions Doped Hydroxyapatite Nanorods (HAp: Ln(Eu/Tb)) with Hydrophilic Copolymers Based on Ligand Exchange Reaction: Biological Imaging and Cancer Treatment[J]. Mater. Sci. Eng. C-Mater. Biol. Appl., 2018,91:556-563. doi: 10.1016/j.msec.2018.05.079
7. [7]
  LIU L, DAI J Q, ZHI Q, WANG H L. Research Progress of Rare Earth Damage to Human Health[J]. China Occupational Medicine, 2019,46(5):625-627.
8. [8]
  ZHANG J C, LI X X, XU S J, WANG K, YU S F, LIN Q. Effects of Rare Earth Ions on the Proliferation, Differentiation and Functional Expression of Osteoblasts Cultured In Vitro[J]. Progress in Natural Science, 2004,14(4):46-51.
9. [9]
  Zaichick S, Zaichick V, Karandashev V, Nosenko S. Accumulation of Rare Earth Elements in Human Bone within the Lifespan[J]. Metallomics, 2011,3(2):186-194. doi: 10.1039/C0MT00069H
10. [10]
  TAO T T, WANG J X, DONG X Y, YU W S, LI Q L. Preparation and Cytotoxicity of HA: RE (RE=Eu³⁺, Tb³⁺) Nanorods[J]. J. Inorg. Mater., 2013,28(5):557-560.
11. [11]
  MA M, LU W P, CAO X F, MAO K Y, GUO Y C. Luminescent and Cytotoxic Characteristics of an Ellipsoidal and Microsized Europium (Eu)-Doped Hydroxyapatite[J]. J. Inorg. Mater., 2016,31(8):890-896.
12. [12]
  Elmadani E, Jha A, Perali T, Jappy C, Walsh D, Leburn C, Brown T, Sibbett W, Duggal M, Toumba J. Characterization of Rare-Earth Oxide Photoactivated Calcium Phosphate Minerals for Resurfacing Teeth[J]. J. Am. Ceram. Soc., 2012,95(9):2716-2724. doi: 10.1111/j.1551-2916.2012.05324.x
13. [13]
  Idris N M, Gnanasammandhan M K, Zhang J, Ho P C, Mahendran R, Zhang Y. In Vivo Photodynamic Therapy Using Upconversion Nanoparticles as Remote Controlled Nanotransducers[J]. Nat. Med., 2012,18(10):1580-1585. doi: 10.1038/nm.2933
14. [14]
  Yang Y, Sun Y, Cao T Y, Peng J J, Liu Y, Wu Y Q, Feng W, Zhang Y J, Li F Y. Hydrothermal Synthesis of NaLuF₄: 153Sm, Yb, Tm Nanoparticles and Their Application in Dual-Modality Upconversion Luminescence and SPECT Bioimaging[J]. Biomaterials, 2013,34(3):774-783. doi: 10.1016/j.biomaterials.2012.10.022
15. [15]
  Xing H Y, Bu W B, Zhang S J, Zheng X P, Li M, Chen F, He Q J, Zhou L P, Peng W J, Hua W Q, Shi J L. Multifunctional Nanoprobes for Upconversion Fluorescence, MR and CT Trimodal Imaging[J]. Biomaterials, 2012,33(4):1079-1089. doi: 10.1016/j.biomaterials.2011.10.039
16. [16]
  Gu Y W, Khor K A, Cheang P. Bone -like Apatite Layer Formation on Hydroxyapatite Prepared by Spark Plasma Sintering (SPS)[J]. Biomaterials, 2004,25(18):4127-4134. doi: 10.1016/j.biomaterials.2003.11.030
17. [17]
  Mandal S, Dey A, Pal U. Low Temperature Wet-Chemical Synthesis of Spherical Hydroxyapatite Nanoparticles and Their In Situ Cytotoxicity Study[J]. Adv. Nano Res., 2016,4(4):295-307. doi: 10.12989/anr.2016.4.4.295
18. [18]
  Mondal S, Nguyen V T, Park S, Choi J, Tran L H, Yi M, Shin J H, Lee C Y, Oh J. Bioactive, Luminescent Erbium-Doped Hydroxyapatite Nanocrystals for Biomedical Applications[J]. Ceram. Int., 2020,46(10):16020-16031. doi: 10.1016/j.ceramint.2020.03.152
19. [19]
  HONG J, LU Y M, GONG C H, BEN Y G. Preparation and Characterization of Hydroxyapatite/Chitosan Composite Microspheres[J]. Journal of Guangdong Pharmaceutical University, 2021,37(5):1-5.
20. [20]
  Yang H W, Xia K D, Wang T L, Niu J C, Song Y M, Xiong Z Q, Zheng K, Wei S Q, Lu W. Growth, In Vitro Biodegradation and Cytocompatibility Properties of Nano-Hydroxyapatite Coatings on Biodegradable Magnesium Alloys[J]. J. Alloy. Compd., 2016,672:366-373. doi: 10.1016/j.jallcom.2016.02.156
21. [21]
  Yigit O, Ozdemir N, Dikici B, Kaseem M. Surface Properties of Graphene Functionalized TiO₂/nHA Hybrid Coatings Made on Ti₆Al₇Nb Alloys via Plasma Electrolytic Oxidation (PEO)[J]. Molecules, 2021,26(13)3903. doi: 10.3390/molecules26133903
22. [22]
  Ebrahimi M, Botelho M G, Dorozhkin S V. Biphasic Calcium Phosphates Bioceramics (HA/TCP): Concept, Physicochemical Properties and the Impact of Standardization of Study Protocols in Biomaterials Research[J]. Mater. Sci. Eng. C-Mater. Biol. Appl., 2017,71:1293-1312. doi: 10.1016/j.msec.2016.11.039
23. [23]
  Dikici B, Niinomi M, Topuz M, Koc S G, Nakai M. Synthesis of Biphasic Calcium Phosphate (BCP) Coatings on β-Type Titanium Alloys Reinforced with Rutile-TiO₂ Compounds: Adhesion Resistance and In-Vitro Corrosion[J]. J. Sol-Gel Sci. Technol., 2018,87:713-724. doi: 10.1007/s10971-018-4755-2
24. [24]
  LIAO J G, ZANG L, ZOU Y, WANG Y L, LI Y B. Study on Surface Properties of Nano -Hydroxyapatite Modified by Stearic Acid[J]. Chinese J. Inorg. Chem., 2009,25(7):1267-1273. doi: 10.3321/j.issn:1001-4861.2009.07.023
25. [25]
  Amedlous A, Amadine O, Essamlali Y, Maati H, Semlal N, Zahouily M. Copper Loaded Hydroxyapatite Nanoparticles as Eco-Friendly Fenton-like Catalyst to Effectively Remove Organic Dyes[J]. J. Environ. Chem. Eng., 2021,9(4)115501.
26. [26]
  Murugesan M, Krishnamurthy V, Hebalkar N, Devanesan M, Nagamony P, Palaniappan M, Krishnaswamy S, Yuan A H. Nano-Hydroxyapatite (Hap) and Hydroxyapatite/Platinum (HAp/Pt) Core Shell Nanorods: Development, Structural Study, and Their Catalytic Activity[J]. Can. J. Chem. Eng., 2020,99(1):268-280.
27. [27]
  Anirudhan T S, Shainy F, Sekhar V C, Athira V S. Highly Efficient Photocatalytic Degradation of Chlorpyrifos in Aqueous Solutions by Nano Hydroxyapatite Modified CFGO/ZnO Nanorod Composite[J]. J. Photochem. Photobiol. A, 2021,418113333. doi: 10.1016/j.jphotochem.2021.113333
28. [28]
  Soliman H, Pu S M, Zhang W T, Makhlouf A S, Wan G J. Deposition of Anti-corrosion Hybrid Film of Hexamethylene Diaminetetrakis (Methylene Phosphonic Acid)/Hydroxyapatite on Biodegradable Mg: Influence of Deposition Procedures[J]. Surf. Coat. Technol., 2020,402126242. doi: 10.1016/j.surfcoat.2020.126242
29. [29]
  HUANG Z H, WAN Y Z, ZHU X B, ZHANG Q C, YANG Z W, LUO H L. Effect of Modified Agent on Properties of Nanoscale Hydroxyapatite/Polylactic Acid Composites[J]. Acta Materiae Compositae Sinica, 2021,38(3):749-760.
30. [30]
  Mahraz Z A S, Sahar M R, Ghoshal S K, Dousti M R. Concentration Dependent Luminescence Quenching of Er³⁺-Doped Zinc Boro -Tellurite Glass[J]. J. Lumin., 2013,144(6):139-145.
31. [31]
  Li L, Tang X H, Jiang Z Q, Zhou X J, Jiang S, Luo X B, Xiang G T, Zhou K N. NaBaLa ₂ (PO ₄)₃: A Novel Host Lattice for Sm³⁺-Doped Phosphor Materials Emitting Reddish-Orange Light[J]. J. Alloy. Compd., 2017,701:515-523. doi: 10.1016/j.jallcom.2017.01.171
32. [32]
  Guo Q F, Wang Q D, Jiang L W, Liao L B, Liu H K, Mei L F. A Novel Apatite, Lu₅(SiO₄) ₃N: (Ce, Tb), Phosphor Material: Synthesis, Structure and Applications for NUV -LEDs[J]. Phys. Chem. Chem. Phy., 2016,18(23):15545-15554. doi: 10.1039/C6CP01512C
33. [33]
  Deliormanli A M, Rahman B, Oguzlar S, Ertekin K. Structural and Luminescent Properties of Er³⁺ and Tb³⁺ -Doped Sol-Gel-Based Bioactive Glass Powders and Electrospun Nanofibers[J]. J. Mater. Sci., 2021,56(26):14487-14504. doi: 10.1007/s10853-021-06203-7
34. [34]
  Ahmad N, Khan S. Effect of (Mn-Co) Co-doping on the Structural, Morphological, Optical, Photoluminescence and Electrical Properties of SnO₂[J]. J. Alloy. Compd., 2017,720(5):502-509.
35. [35]
  ZHU Q X, SONG J P, LIAN A M, LUO M H. Effect of Carbonate Substitution on the Mineralization of Apatite Blocks and Coatings[J]. Bulletin of the Chinese Ceramic Society, 2019,38(12):3959-3963.
36. [36]
  Hirayama B, Anada T, Shiwaku Y, Miyatake N, Tsuchiya K, Nakamura M, Takahashi T, Suzuki O. Immune Cell Response and Subsequent Bone Formation Induced by Implantation of Octacalcium Phosphate in a Rat Tibia Defect[J]. RSC Adv., 2016,6:S7475-S7484.
37. [37]
  Simon P, Gruner D, Worch H, Pompe W, Lichte H, El Khassawna T, Heiss C, Wenisch S, Kniep R. First Evidence of Octacalcium Phosphate@Osteocalcin Nanocomplex as Skeletal Bone Component Directing Collagen Triple-Helix Nanofibril Mineralization[J]. Sci. Rep., 2018,8(1)13696.
38. [38]
  Okuyama K, Shiwaku Y, Hamai R, Mizoguchi T, Tsuchiya K, Takahashi T, Suzuki O. Differentiation of Committed Osteoblast Progenitors by Octacalcium Phosphate Compared to Calcium-Deficient Hydroxyapatite in Lepr-cre/Tomato Mouse Tibia[J]. Acta Biomater., 2022,142:332-344.
39. [39]
  SHEN J F, CHANG C K, MAO D L, WU J S. Preparation and Characterization of Hydroxyapatite Coating Materials[J]. J. Inorg. Mater., 2001,16(5):993-998.
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