Luminescent Hydroxyapatite Doped with Rare Earth Elements for Biomedical Applications
Abstract
:1. Introduction
2. Hydroxyapatite Doped with Photoluminescent Elements
2.1. Hydroxyapatite Doped with Terbium
2.2. Hydroxyapatite Doped with Erbium
2.3. Hydroxyapatite Doped with Europium
2.4. Hydroxyapatite Doped with Lanthanum
2.5. Hydroxyapatite Doped with Dysprosium
3. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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Cation (M) | Sample Form | Doping Range {M/(M + Ca)}100 (at %) | Bio-Functionality/Effect of the Dopant |
---|---|---|---|
Tb | Powder | 2–17 | In vitro cytocompatibility with MC3T3-E1 (doses of 25–100 µg mL−1 Tb-HA-NPs) and A549 (doses of 20–320 µg mL−1 Tb-HA-NPs) cell lines. |
Er | Powder | 2–10 | Induces the formation of biomimetic apatite in-growths in simulated body fluid (SBF). |
Eu | Powder | 0.1–20 | Induces the in vitro formation of bone-like apatite in SBF; In vitro cytocompatibility with MG-63 (cell proliferation up to 4 days), HeLa, human embryonic kidney HEK 293, L929 (viability >80% for Eu-HA doses of 25–500 µg mL−1); Low cytotoxicity for human gingival fibroblast (HGF-1) cells after 24 h (500–2000 µg mL−1); Cytotoxicity for transformed human umbilical vein endothelial cells (T-HUVEC) after treatment with 0.3–30 µg mL−1 of 5 at % doped HA; Ability to kill cervical HeLa cells after 24 h when combined with 5 fluorouracil (5FU); Negligible toxicity by hen’s egg test on the chick area vasculosa (HET-CAV); Antibacterial effect against E. faecalis * (ATCC 29212), S. aureus * (0364), and P. aeruginosa * (1397); No antibacterial activity against E. coli * even at high doping; Antifungal effect against C. albicans * (ATCC 10231) with a doping content of 20 at %. |
La | Powder Coating | 2–30 | In vitro cytocompatibility with MC3T3-E1 and L929 cell lines; No cytotoxicity for adenocarcinoma (MCF-7) and human embryonic kidney HEK cells at a doping level of 2 at %; Antibacterial effect against S. aureus (e.g., ATCC 25175), E. coli, P. aeruginosa, and Bacillus; Improvement of mechanical properties: bonding strength and Vickers hardness. |
Dy | Powder | 0.5–10 | In vitro cytocompatibility with L929 cell line; Negligible toxicity by hen’s egg test on the chick area vasculosa (HET-CAV); Increase of oxidative stress lipoperoxides and nitric oxide indicators in the kidney, lungs, and liver of rats; lower activity of anti-oxidant glutathione peroxidase enzyme. |
Samples | (b) 300 °C | (c) 400 °C | (d) 500 °C | (e) 600 °C | (f) 700 °C |
---|---|---|---|---|---|
X | 0.2893 | 0.2910 | 0.2981 | 0.2985 | 0.3000 |
Y | 0.3682 | 0.3976 | 0.4161 | 0.4234 | 0.3743 |
Doping Element | Synthesis Method | Improvements of Photoluminescent Properties | Biomedical Application | References |
---|---|---|---|---|
Terbium | microemulsion-mediated solvothermal process | the particles could be excited by a visible light beam at 400 nm | fluorescent bio-probe | Wang et al., 2010 [60] |
chemical deposition | excitation light is 378 nm when the wavelength of the monitoring light is 545 nm | fluorescent probe | Qiao et al., 2015 [62] | |
Erbium | microwave-assisted precipitation method | red and green emission in the spectra | sensing material | Alshemary et al., 2015 [9] |
Microwave-assisted wet precipitation | photoluminescence spectra—green and red emissions | bone healing process | Alshemary et al., 2015 [9] | |
co-precipitation | near-infrared emission peaks ~1540 nm | biomedicine | Pham et al., 2016 [24] | |
Europium | microwave-assisted synthesis | red luminescence; negligible toxicity for Vero cells | potential tools for biomedical applications | Escudero, 2013 [47] |
wet chemical precipitation in water without the addition of any surfactant | luminescence at peaks at 536, 590, 615, 650, and 695 nm under 397 nm excitation | fluorescent probe for in vivo imaging | Chen et al., 2014 [38] | |
simple one-step method using cationic surfactant as a template | red luminescence of Eu3+ (5D0–7F1,2) under UV irradiation | drug delivery disease therapy | Yang et al., 2008 [63] | |
precipitation | strong green and red fluorescence by irradiation of blue and green light | biocompatible fluorescent labeling material in biological studies | Han et al., 2010 [64] | |
synthetized at low temperatures (37 °C) | red luminescence is photostable; luminescence could be obtained under visible irradiation | bio-probe | Doat et al., 2003 [66] | |
Europium and Terbium | microemulsion process under hydrothermal treatment | typical emission lines of Eu3+ and Tb3+ | carriers for drug release and targeting | Yang et al., 2008 [65] |
Lanthanum | wet chemical synthesis method | in vitro bioactivity and biocompatibility | bioimaging phosphor/luminescent labeling materials for bioimaging | Ghosh et al., 2016 [69] |
modified sol–gel method at a low temperature of 100 °C | fluorescence detected under TRITC (Tetramethylrhodamine) and FITC (Fluorescein isothiocyanate) filters using epifluorescence microscopy | fluorescent probes for cellular internalization and biolabeling | Jadalannagari et al., 2014 [71] | |
sol–gel route | decrease in the dissolution of the samples as the dopant concentration increases | implant in biomedical field | Ahymah, 2011 [72] | |
Dysprosium and Europium | co-doping | increased photoluminescent properties; strong transverse relaxation effects | contrast agent for MRI in implantology or functional coatings | Tesch et al., 2017 [67] |
Dysprosium | co-precipitation | fluorescent character—stimulated at 344 or 360 nm | bimodal probes with low toxicity | Sánchez et al., 2015 [6] |
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Neacsu, I.A.; Stoica, A.E.; Vasile, B.S.; Andronescu, E. Luminescent Hydroxyapatite Doped with Rare Earth Elements for Biomedical Applications. Nanomaterials 2019, 9, 239. https://doi.org/10.3390/nano9020239
Neacsu IA, Stoica AE, Vasile BS, Andronescu E. Luminescent Hydroxyapatite Doped with Rare Earth Elements for Biomedical Applications. Nanomaterials. 2019; 9(2):239. https://doi.org/10.3390/nano9020239
Chicago/Turabian StyleNeacsu, Ionela Andreea, Alexandra Elena Stoica, Bogdan Stefan Vasile, and Ecaterina Andronescu. 2019. "Luminescent Hydroxyapatite Doped with Rare Earth Elements for Biomedical Applications" Nanomaterials 9, no. 2: 239. https://doi.org/10.3390/nano9020239