Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body Fluid
Bone supports animal bodies, is the place where blood is produced, and is essential for the immune system, among other important functions. The dominant inorganic component in bone is hydroxyapatite (Hap), the structure and dynamics of which still pose many unsolved puzzles. An updated understanding...
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MDPI AG
2022-01-01
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| Online Access: | https://www.mdpi.com/2073-4352/12/2/139 |
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| author | Dinbandhu Thakur Sheng-Chi Yeh Ren-Hao Cheng Song-Seng Loke Hung-Hsiang Wei Po-Yu Cheng Yi-Chun Lai Hsuan-Ying Chen Yu-Ren Huang Shang-Wu Ding |
| author_facet | Dinbandhu Thakur Sheng-Chi Yeh Ren-Hao Cheng Song-Seng Loke Hung-Hsiang Wei Po-Yu Cheng Yi-Chun Lai Hsuan-Ying Chen Yu-Ren Huang Shang-Wu Ding |
| author_sort | Dinbandhu Thakur |
| collection | DOAJ |
| description | Bone supports animal bodies, is the place where blood is produced, and is essential for the immune system, among other important functions. The dominant inorganic component in bone is hydroxyapatite (Hap), the structure and dynamics of which still pose many unsolved puzzles. An updated understanding of HAp is of great significance to osteology, dentistry, and the development of artificial bone and other biomaterials. In this work, HAp nanoparticles were synthesized with the wet chemical precipitation method and their structure and morphologies were controlled by varying pH and adding fluoride ions by two different routes: (1) fluoride ions were added during synthesis, and (2) fluoride ions were introduced after the samples were synthesized by soaking the samples in solutions with fluoride ions. XRD and HRTEM were employed to confirm the composition and structure, while various multinuclear (<sup>1</sup>H, <sup>19</sup>F, <sup>31</sup>P) solid-state nuclear magnetic resonance (NMR) methods including 1D single pulse, cross-polarization under magic-angle spinning (CPMAS), and 2D heteronuclear correlation (HETCOR) were used to characterize the structure, morphology, and dynamics, validating the general core-shell morphology in these F-HAp samples. It was found that all hydroxide ions were substituted when the fluoride ion concentration was above 0.005 M. An NMR peak corresponding to water structure emerged and the bulk water peak was shifted upfield, indicating that fluoride substitution modifies both the crystalline core and the amorphous shell of F-HAp nanoparticles. With the second route of fluoride substitution, increases in soaking time or fluoride ion concentration could increase fluoride substitution in HAp, but could not achieve complete substitution. Finally, with <sup>1</sup>H-<sup>31</sup>P CPMAS and HETCOR, it was established that there are two types of phosphorous, one in the crystalline core (PO<sub>4</sub><sup>3−</sup>) and the other in the amorphous shell (HPO<sub>4</sub><sup>2−</sup>). These results are valuable for clarifying the fluoride substitution mechanism in HAp in biomaterials or in organisms, and provide insights for developing next generation replacement materials for bone, tooth, or coating films, drug delivery systems, etc. |
| first_indexed | 2024-03-09T22:15:27Z |
| format | Article |
| id | doaj.art-8b4900e4688746f1a3f9499edce6ed99 |
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| language | English |
| last_indexed | 2024-03-09T22:15:27Z |
| publishDate | 2022-01-01 |
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| series | Crystals |
| spelling | doaj.art-8b4900e4688746f1a3f9499edce6ed992023-11-23T19:23:32ZengMDPI AGCrystals2073-43522022-01-0112213910.3390/cryst12020139Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body FluidDinbandhu Thakur0Sheng-Chi Yeh1Ren-Hao Cheng2Song-Seng Loke3Hung-Hsiang Wei4Po-Yu Cheng5Yi-Chun Lai6Hsuan-Ying Chen7Yu-Ren Huang8Shang-Wu Ding9Department of Chemistry and Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, TaiwanDepartment of Chemistry and Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, TaiwanDepartment of Chemistry and Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, TaiwanDepartment of Family Medicine, Kaohsiung Chang Gung Memorial Hospital and Chang Gung University Colloge of Medicine, 123, Dapi Road, Niaosong District, Kaohsiung 833, TaiwanDepartment of Chemistry and Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, TaiwanDepartment of Chemistry and Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, TaiwanDepartment of Chemistry and Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, TaiwanDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, 100, Shih-Chuan 1st Road, Kaohsiung 80708, TaiwanDepartment of Applied Science, R.O.C. Naval Academy, No. 669, Junxiao Road, Zuoying District, Kaoshiung 813, TaiwanDepartment of Chemistry and Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, TaiwanBone supports animal bodies, is the place where blood is produced, and is essential for the immune system, among other important functions. The dominant inorganic component in bone is hydroxyapatite (Hap), the structure and dynamics of which still pose many unsolved puzzles. An updated understanding of HAp is of great significance to osteology, dentistry, and the development of artificial bone and other biomaterials. In this work, HAp nanoparticles were synthesized with the wet chemical precipitation method and their structure and morphologies were controlled by varying pH and adding fluoride ions by two different routes: (1) fluoride ions were added during synthesis, and (2) fluoride ions were introduced after the samples were synthesized by soaking the samples in solutions with fluoride ions. XRD and HRTEM were employed to confirm the composition and structure, while various multinuclear (<sup>1</sup>H, <sup>19</sup>F, <sup>31</sup>P) solid-state nuclear magnetic resonance (NMR) methods including 1D single pulse, cross-polarization under magic-angle spinning (CPMAS), and 2D heteronuclear correlation (HETCOR) were used to characterize the structure, morphology, and dynamics, validating the general core-shell morphology in these F-HAp samples. It was found that all hydroxide ions were substituted when the fluoride ion concentration was above 0.005 M. An NMR peak corresponding to water structure emerged and the bulk water peak was shifted upfield, indicating that fluoride substitution modifies both the crystalline core and the amorphous shell of F-HAp nanoparticles. With the second route of fluoride substitution, increases in soaking time or fluoride ion concentration could increase fluoride substitution in HAp, but could not achieve complete substitution. Finally, with <sup>1</sup>H-<sup>31</sup>P CPMAS and HETCOR, it was established that there are two types of phosphorous, one in the crystalline core (PO<sub>4</sub><sup>3−</sup>) and the other in the amorphous shell (HPO<sub>4</sub><sup>2−</sup>). These results are valuable for clarifying the fluoride substitution mechanism in HAp in biomaterials or in organisms, and provide insights for developing next generation replacement materials for bone, tooth, or coating films, drug delivery systems, etc.https://www.mdpi.com/2073-4352/12/2/139hydroxyapatitefluorine substitutionbonesimulated body fluidschemical precipitation methodsolid-state NMR |
| spellingShingle | Dinbandhu Thakur Sheng-Chi Yeh Ren-Hao Cheng Song-Seng Loke Hung-Hsiang Wei Po-Yu Cheng Yi-Chun Lai Hsuan-Ying Chen Yu-Ren Huang Shang-Wu Ding Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body Fluid Crystals hydroxyapatite fluorine substitution bone simulated body fluids chemical precipitation method solid-state NMR |
| title | Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body Fluid |
| title_full | Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body Fluid |
| title_fullStr | Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body Fluid |
| title_full_unstemmed | Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body Fluid |
| title_short | Varying Synthesis Conditions and Comprehensive Characterization of Fluorine-Doped Hydroxyapatite Nanocrystals in a Simulated Body Fluid |
| title_sort | varying synthesis conditions and comprehensive characterization of fluorine doped hydroxyapatite nanocrystals in a simulated body fluid |
| topic | hydroxyapatite fluorine substitution bone simulated body fluids chemical precipitation method solid-state NMR |
| url | https://www.mdpi.com/2073-4352/12/2/139 |
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