Abstract
Large-scale single crystals of Ca9Mg(PO4)6(PO3OH), Ca9Zn(PO4)6(PO3OH), and Ca9Co(PO4)6(PO3OH) were synthesized using hydrothermal technique, and turned out to be similar to natural bone whitlockite. The hexagonal single crystals about 1 mm with high-quality were obtained with this method for the first time. The crystals were of sufficiently good quality for the precision X-ray structural investigation. The compounds crystallize in usual for this structural type trigonal space group R3c. Presence of hydrogen atom in the structure was confirmed by means of infra-red (IR) spectroscopy, differential scanning calorimetry (DSC) and differential thermogravimetry (DTG) methods. Based on the analysis of the local bond valence sum (BVS), a conclusion on the localization of H atoms was made. The formation of O–H groups and hydrogen bonds H⋯O in vicinity of PO4 tetrahedra was shown and similar to bone whitlockite. This research provides new data on possibility of using hydrothermal technique for obtaining doped bone whitlockites. Hydrogen-containing doped whitlockites can combine bioactive properties and improve biocompatibility due to similarity to natural bond. New structural data are useful for finding the ways to better biocompatibility of whitlockite-based materials.
Funding source: Russian Science Foundation
Award Identifier / Grant number: 23-33-00270
Funding source: Scholarship of the President of Russia Federation
Award Identifier / Grant number: СП-859.2021.1
Funding source: Development Program of the Interdisciplinary Scientific and Educational School of Lomonosov Moscow State University’s
Funding source: Chemistry Department of Moscow State University
Award Identifier / Grant number: АААА-А21-121011590086-0
Funding source: Russian Federation
Award Identifier / Grant number: 122011300125-2
Acknowledgment
A.S.V. is grateful to the Institute of Geology and Geochemistry of Ural Branch of RAS for the possibility of taking measurements on FT-IR spectrometer. IR spectroscopy measurements were performed in Common Use Center of the Ural Branch of RAS “Geoanalyst”. The single crystals X-ray diffraction study was performed within the State Assignment of FSRC “Crystallography and Photonics” RAS in part of X-ray diffraction studies. The single crystals X-ray diffraction study was performed using the equipment of the Shared Research Center FSRC.
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Author contributions: The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.
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Research funding: The study was supported by Russian Science Foundation (Project No. 23-23-00270). D.V.D. is grateful to the Scholarship of the President of Russia Federation (СП-859.2021.1). The study was supported by the Development Program of the Interdisciplinary Scientific and Educational School of Lomonosov Moscow State University’s “The future of the planet and global environmental change” and the state assignment of the Chemistry Department of Moscow State University (Agreement No. АААА-А21-121011590086-0). The X-ray study was carried out in accordance with the state of the Russian Federation, state registration number 122011300125-2.
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Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
Abbreviations
- WH
-
whitlockite
- HAp
-
hydroxyapatite
- DSC
-
differential scanning calorimetry
- DTG
-
differential thermogravimetry
- BVS
-
Bond-valence sum calculations
- PXRD
-
powder X-ray diffraction
- IR
-
infra-red
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Supplementary Material
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