Abstract
In the present work, nanostructured hydroxyapatite (nano-Hap) was synthesized by following a hydrothermal process using calcium hydroxide and ammonium phosphate. The nano-Hap was unpurified with different amounts of dysprosium oxide (Dy2O3), from 0.5 to 2.0 wt%. Its physicochemical properties were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR). TEM confirmed the formation of rod structures (L/D aspect ratio > 1) with average sizes ranging from ~ 15 to 19 nm in diameter, and ~ 26 to 32 nm in length. The presence of the monoclinic and hexagonal crystalline phases of Hap was confirmed by XRD. The thermoluminescence (TL) studies showed a linear relationship between the Dy2O3 concentration and TL intensity induced by gamma radiation in a dose range from 10 to 200 Gy. The nano-Hap unpurified with 2.0 wt% of Dy2O3 showed the highest TL response. Additionally, in the perspective of exploring the therapeutic potential of Dy2O3-unpurified Hap, the viability of human prostatic epithelial cells was evaluated. The safety of pure Hap was confirmed by performing resazurin/resorufin fluorescence-based assays. A significant toxicity was observed as a function of the impurity content and nanopowders concentration. In summary, the nano-Hap TL results make it a good candidate for ionizing radiation sensoring and, the in vitro test encourages the development of a biomimetic Dy-Hap drug-free nanotherapeutic platform.
Similar content being viewed by others
References
M. Sadat-Shojai, M.T. Khorasani, E. Dinpanah-Khoshdargi, A. Jamshidi, Synthesis methods for nanosized hydroxyapatite with diverse structures. Acta Biomater. 9, 7591–7621 (2013). https://doi.org/10.1016/j.actbio.2013.04.012
H. Daneshvar, M. Shafaei, F. Manouchehri, S. Kakaei, F. Ziaie, Influence of morphology and chemical processes on thermoluminescence response of irradiated nanostructured hydroxyapatite. J. Lumin. 219, 116906 (2020). https://doi.org/10.1016/j.jlumin.2019.116906
D. Aquilano, M. Bruno, M. Rubbo, L. Pastero, F.R. Massaro, Twin laws and energy in monoclinic hydroxyapatite, Ca5(PO4)3(OH). Cryst. Growth Des. 15, 411–418 (2015). https://doi.org/10.1021/cg501490e
G. Ma, X.Y. Liu, Hydroxyapatite: hexagonal or monoclinic? Cryst. Growth Des. 9, 2991–2994 (2009). https://doi.org/10.1021/cg900156w
V. Rodríguez Lugo, V.M. Castaño, E. Rubio-Rosas, Biomimetic growth of hydroxylapatite on SiO 2-PMMA hybrid coatings. Mater. Lett. 184, 265–268 (2016). https://doi.org/10.1016/j.matlet.2016.08.068
V. Rodríguez-Lugo, C. Angeles, A. DelaIsla, V.M. Castano, Effect of bio-calcium oxide on the morphology of hydroxyapatite. Int. J. Basic Appl. Sci. 4, 395 (2015). https://doi.org/10.14419/ijbas.v4i4.5240
A. Szcześ, L. Hołysz, E. Chibowski, Synthesis of hydroxyapatite for biomedical applications. Adv. Colloid Interf. Sci. 249, 321–330 (2017). https://doi.org/10.1016/j.cis.2017.04.007
R.E. Riman, W.L. Suchanek, K. Byrappa, C.W. Chen, P. Shuk, C.S. Oakes, Solution synthesis of hydroxyapatite designer particulates. Solid State Ionics 151, 393–402 (2002). https://doi.org/10.1016/S0167-2738(02)00545-3
V.M. Rusu, C.H. Ng, M. Wilke, B. Tiersch, P. Fratzl, M.G. Peter, Size-controlled hydroxyapatite nanoparticles as self-organized organic-inorganic composite materials. Biomaterials 26, 5414–5426 (2005). https://doi.org/10.1016/j.biomaterials.2005.01.051
H. Zhang, B.W. Darvell, Morphology and structural characteristics of hydroxyapatite whiskers: Effect of the initial Ca concentration, Ca/P ratio and pH. Acta Biomater. 7, 2960–2968 (2011). https://doi.org/10.1016/j.actbio.2011.03.020
V. Rodríguez-Lugo, E. Salinas-Rodríguez, R.A. Vázquez, K. Alemán, A.L. Rivera, Hydroxyapatite synthesis from a starfish and β-tricalcium phosphate using a hydrothermal method. RSC Adv. 7, 7631–7639 (2017). https://doi.org/10.1039/c6ra26907a
V. Jokanović, D. Izvonar, M.D. Dramićanin, B. Jokanović, V. Živojinović, D. Marković, B. Dačić, Hydrothermal synthesis and nanostructure of carbonated calcium hydroxyapatite. J. Mater. Sci. Mater. Med. 17, 539–546 (2006). https://doi.org/10.1007/s10856-006-8937-z
X. Zhang, K.S. Vecchio, Hydrothermal synthesis of hydroxyapatite rods. J. Cryst. Growth. 308, 133–140 (2007). https://doi.org/10.1016/j.jcrysgro.2007.07.059
Y. Zhu, L. Xu, C. Liu, C. Zhang, N. Wu, Nucleation and growth of hydroxyapatite nanocrystals by hydrothermal method. AIP Adv. 8, 085221 (2018). https://doi.org/10.1063/1.5034441
L. An, W. Li, Y. Xu, D. Zeng, Y. Cheng, G. Wang, Controlled additive-free hydrothermal synthesis and characterization of uniform hydroxyapatite nanobelts. Ceram. Int. 42, 3104–3112 (2016). https://doi.org/10.1016/j.ceramint.2015.10.099
S. Zhong, J. Chen, Q. Li, Z. Wang, X. Shi, K. Lin, Q. Zhang, Assembly synthesis of spherical hydroxyapatite with hierarchical structure. Mater. Lett. 194, 1–4 (2017). https://doi.org/10.1016/j.matlet.2017.01.146
V. Rodríguez-Lugo, T.V.K. Karthik, D. Mendoza-Anaya, E. Rubio-Rosas, L.S. Villaseñor Cerón, M.I. Reyes-Valderrama, E. Salinas-Rodríguez, Wet chemical synthesis of nanocrystalline hydroxyapatite flakes: effect of pH and sintering temperature on structural and morphological properties. R. Soc. Open Sci. 5, 180962 (2018). https://doi.org/10.1098/rsos.180962
S. Lopez Ortiz, A.D. Mendoza, C. Sanchez, M.E. Fernandez Garcia, R.E. Salinas, M.I. Reyes Valderrama, V. Rodriguez Lugo, The pH effect on the growth of hexagonal and monoclinic hydroxyapatite synthesized by the hydrothermal method. Nanomaterial 2020, 1–10 (2020)
D. Sánchez-Campos, D. Mendoza-Anaya, M.I. Reyes-Valderrama, S. Esteban-Gómez, V. Rodríguez-Lugo, Cationic surfactant at high pH in microwave HAp synthesis. Mater. Lett. 265, 3–6 (2020). https://doi.org/10.1016/j.matlet.2020.127416
J. Liu, X. Ye, H. Wang, M. Zhu, B. Wang, H. Yan, The influence of pH and temperature on the morphology of hydroxyapatite synthesized by hydrothermal method. Ceram. Int. 29, 629–633 (2003). https://doi.org/10.1016/S0272-8842(02)00210-9
Y. Qi, J. Shen, Q. Jiang, B. Jin, J. Chen, X. Zhang, The morphology control of hydroxyapatite microsphere at high pH values by hydrothermal method. Adv. Powder Technol. 26, 1041–1046 (2015). https://doi.org/10.1016/j.apt.2015.04.008
A. Rabiei, T. Blalock, B. Thomas, J. Cuomo, Y. Yang, J. Ong, Microstructure, mechanical properties, and biological response to functionally graded HA coatings. Mater. Sci. Eng. C. 27, 529–533 (2007). https://doi.org/10.1016/j.msec.2006.05.036
M.J. Robles-Águila, J.A. Reyes-Avendaño, M.E. Mendoza, Structural analysis of metal-doped (Mn, Fe Co, Ni, Cu, Zn) calcium hydroxyapatite synthetized by a sol-gel microwave-assisted method. Ceram. Int. 43, 12705–12709 (2017). https://doi.org/10.1016/j.ceramint.2017.06.154
F. Ziaie, N. Farhadi Moein, M. Shafaei, Thermoluminescent characteristics of nano-structure hydroxyapatite:Dy. Kerntechnik 79, 500–503 (2014). https://doi.org/10.3139/124.110445
P. Seth, S. Aggarwal, S. Rao, Thermoluminescence study of rare earth ion (Dy3+) doped LiF: Mg crystals grown by EFG technique. J. Rare Earths. 30, 641–646 (2012). https://doi.org/10.1016/S1002-0721(12)60105-7
A. Tesch, C. Wenisch, K.H. Herrmann, J.R. Reichenbach, P. Warncke, D. Fischer, F.A. Müller, Luminomagnetic Eu3 +- and Dy3 +-doped hydroxyapatite for multimodal imaging. Mater. Sci. Eng. C. 81, 422–431 (2017). https://doi.org/10.1016/j.msec.2017.08.032
T. Tite, A.C. Popa, L.M. Balescu, I.M. Bogdan, I. Pasuk, J.M.F. Ferreira, G.E. Stan, Cationic substitutions in hydroxyapatite: current status of the derived biofunctional effects and their in vitro interrogation methods. Materials (Basel). 11, 1–62 (2018). https://doi.org/10.3390/ma11112081
I.A. Neacsu, A.E. Stoica, B.S. Vasile, E. Andronescu, Luminescent hydroxyapatite doped with rare earth elements for biomedical applications. Nanomaterials 9, 239 (2019). https://doi.org/10.3390/nano9020239
K. Madhukumar, H.K. Varma, M. Komath, T.S. Elias, V. Padmanabhan, C.M.K. Nair, Photoluminescence and thermoluminescence properties of tricalcium phosphate phosphors doped with dysprosium and europium. Bull. Mater. Sci. 30, 527–534 (2007). https://doi.org/10.1007/s12034-007-0082-x
S.L. Ortiz, V. Rodríguez-Lugo, L.S. Villaseñor-Cerón, M.I. Reyes-Valderrama, D.E. Salado-Leza, D. Mendoza-Anaya, The Potential of the Hydroxyapatite as a thermoluminescent sensor of ionizing radiation. ICBI 8, 85 (2020). https://doi.org/10.29057/icbi.v8iEspecial.6310
J. Azorin Nieto, Present status and future trends in the development of thermoluminescent materials. Appl. Radiat. Isot. 117, 135–142 (2016). https://doi.org/10.1016/j.apradiso.2015.11.111
L.S. Villaseñor Cerón, V. Rodríguez Lugo, J.A. Arenas Alatorre, M.E. Fernández-Garcia, M.I. Reyes-Valderrama, P. González-Martínez, D. Mendoza Anaya, Characterization of hap nanostructures doped with AgNp and the gamma radiation effects. Results Phys. 15, 102702 (2019). https://doi.org/10.1016/j.rinp.2019.102702
D. Mendoza-Anaya, E. Flores-Díaz, G. Mondragón-Galicia, M.E. Fernández-García, E. Salinas-Rodríguez, T.V.K. Karthik, V. Rodríguez-Lugo, The role of Eu on the thermoluminescence induced by gamma radiation in nano hydroxyapatite. J. Mater. Sci. Mater. Electron. 29, 15579–15586 (2018). https://doi.org/10.1007/s10854-018-9147-4
H. Daneshvar, M. Shafaei, F. Manouchehri, S. Kakaei, F. Ziaie, The role of La, Eu, Gd, and Dy lanthanides on thermoluminescence characteristics of nano-hydroxyapatite induced by gamma radiation. SN Appl. Sci. 1, 1146 (2019). https://doi.org/10.1007/s42452-019-1162-4
A.K. Sánchez Lafarga, F.P. Pacheco Moisés, A. Gurinov, G.G. Ortiz, G.G. Carbajal Arízaga, Dual responsive dysprosium-doped hydroxyapatite particles and toxicity reduction after functionalization with folic and glucuronic acids. Mater. Sci. Eng. C. 48, 541–547 (2015). https://doi.org/10.1016/j.msec.2014.12.033
M.R. Chapman, A.G. Miller, T.G. Stoebe, Thermoluminescence in hydroxyapatite. Med. Phys. 6, 494–499 (1979). https://doi.org/10.1118/1.594611
V. Rodríguez-Lugo, D.E. Salado-Leza, S.L. Ortiz, D. Mendoza-Anaya, L.S. Villaseñor-Cerón, M.I. Reyes-Valderrama, Overview of nanostructured hydroxyapatite as an alternative to treat cancer. ICBI. 8, 115 (2020). https://doi.org/10.29057/icbi.v8iEspecial.6466
J. Reyes-Gasga, E.L. Martínez-Piñeiro, É.F. Brès, Crystallographic structure of human tooth enamel by electron microscopy and x-ray diffraction: hexagonal or monoclinic? J. Microsc. 248, 102–109 (2012). https://doi.org/10.1111/j.1365-2818.2012.03653.x
D. Sánchez-campos, M.I.R. Valderrama, S. López-ortíz, D. Salado-leza, M.E. Fernández-garcía, D. Mendoza-anaya, E. Salinas-rodríguez, V. Rodríguez-lugo, Modulated monoclinic hydroxyapatite: the effect of ph in the microwave assisted method. Minerals 11, 1–13 (2021). https://doi.org/10.3390/min11030314
M. Chandrasekhar, D.V. Sunitha, N. Dhananjaya, H. Nagabhushana, S.C. Sharma, B.M. Nagabhushana, C. Shivakumara, R.P.S. Chakradhar, Thermoluminescence response in gamma and UV irradiated Dy2O3 nanophosphor. J. Lumin. 132, 1798–1806 (2012)
D. Salado-Leza, E. Mendoza-Mendoza, J.A. Castillo-Ramírez, C. Escudero-Lourdes, L.A. García-Cerda, A simple approach to room-temperature synthesis of cubic Al-doped HfO2 nanoparticles and their toxicity evaluation in normal prostate cells. Mater. Lett. 274, 128048 (2020). https://doi.org/10.1016/j.matlet.2020.128048
T. Pousa Ribeiro, F. Monteiro, M. Laranjeira, Duality of iron (III) doped nano hydroxyapatite in triple negative breast cancer monitoring and as a drug-free therapeutic agent. Ceram. Int. 46, 16590 (2020). https://doi.org/10.1016/j.ceramint.2020.03.231
X. Cui, T. Liang, C. Liu, Y. Yuan, J. Qian, Correlation of particle properties with cytotoxicity and cellular uptake of hydroxyapatite nanoparticles in human gastric cancer cells. Mater. Sci. Eng. C. 67, 453–460 (2016). https://doi.org/10.1016/j.msec.2016.05.034
Acknowledgements
Our gratitude to Ph.D. Bernardo Yañez Soto for providing the facilities to evaluate the Hap/cell interaction by fluorescence microscopy at the National Laboratory for Out of Equilibrium Matter Engineering (LANIMFE). In vitro evaluation was partially supported by UASLP (Project/C19-FAI-05-87.87). We would like to thank Ph.D. Mildred Quintana Ruíz and Eng. Celina González Gallegos for their support to measure fluorescence in solution. We also thank CONACYT for supporting the generation of infrastructure through the INFR-2015-251767 project and for the scholarship awarded to Susana López Ortiz belonging to the Doctorate program 0432 in Materials Sciences from the Autonomous University of the State of Hidalgo.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Ortiz, S.L., Lugo, V.R., Salado-Leza, D. et al. Dy2O3-unpurified hydroxyapatite: a promising thermoluminescent sensor and biomimetic nanotherapeutic. Appl. Phys. A 127, 893 (2021). https://doi.org/10.1007/s00339-021-05010-w
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00339-021-05010-w