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Open AccessFeature PaperArticle

Dual Doping of Silicon and Manganese in Hydroxyapatites: Physicochemical Properties and Preliminary Biological Studies

1
Department of Analytical Chemistry and Biomaterials, Analytical Group, Faculty of Pharmacy with Laboratory Medicine Division, Medical University of Warsaw, ul. Banacha 1, 02-097 Warsaw, Poland
2
Department of Environmental Health Sciences, Faculty of Pharmacy with Laboratory Medicine Division, Medical University of Warsaw, ul. Banacha 1, 02-097 Warsaw, Poland
*
Author to whom correspondence should be addressed.
Materials 2019, 12(16), 2566; https://doi.org/10.3390/ma12162566
Received: 4 July 2019 / Revised: 8 August 2019 / Accepted: 9 August 2019 / Published: 12 August 2019
(This article belongs to the Special Issue Novel Biomaterials for Orthopaedic/Musculoskeletal Tissue Engineering)
Silicated hydroxyapatite powders enriched with small amounts of manganese (Mn2+) cations were synthesized via two different methods: precipitation in aqueous solution and the solid-state method. The source of Mn2+ ions was manganese acetate, while silicon was incorporated using two different reagents: silicon acetate and sodium metasilicate. Powder X-ray diffraction (PXRD) analysis showed that the powders obtained via the precipitation method consisted of single-phase nanocrystalline hydroxyapatite. In contrast, samples obtained via the solid-state method were heterogenous and contaminated with other phases, (i.e., calcium oxide, calcium hydroxide, and silicocarnotite) arising during thermal treatment. The transmission electron microscope (TEM) images showed powders obtained via the precipitation method were nanosized and elongated, while solid-state synthesis produced spherical microcrystals. The phase identification was complemented by Fourier transform infrared spectroscopy (FTIR). An in-depth analysis via solid-state nuclear magnetic resonance (ssNMR) was carried out, using phosphorus 31P single-pulse Bloch decay (BD) (31P BD) and cross-polarization (CP) experiments from protons to silicon-29 nuclei (1H → 29Si CP). The elemental measurements carried out using wavelength-dispersive X-ray fluorescence (WD-XRF) showed that the efficiency of introducing manganese and silicon ions was between 45% and 95%, depending on the synthesis method and the reagents. Preliminary biological tests on the bacteria Allivibrio fisheri (Microtox®) and the protozoan Spirostomum ambiguum (Spirotox) showed no toxic effect in any of the samples. The obtained materials may find potential application in regenerative medicine, bone implantology, and orthopedics as bone substitutes or implant coatings. View Full-Text
Keywords: hydroxyapatite; manganese; silicon; biomaterials; infrared spectroscopy; nuclear magnetic resonance hydroxyapatite; manganese; silicon; biomaterials; infrared spectroscopy; nuclear magnetic resonance
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Szurkowska, K.; Drobniewska, A.; Kolmas, J. Dual Doping of Silicon and Manganese in Hydroxyapatites: Physicochemical Properties and Preliminary Biological Studies. Materials 2019, 12, 2566.

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