INVESTIGATION OF THERANOSTIC PROPERTIES OF SILICATE-SUBSTITUTED HYDROXYAPATITE CO-DOPED WITH Eu3+ Gd3+ AND Li+ IONS

Natalia Charczuk1, Sara Targońska1, Rafal J. Wiglusz1

1 Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wroclaw, 50-422 Poland

[email protected], [email protected]

Searching for multifunctional biocompatible materials is of fundamental importance for theragnostic and bioimaging development. Although, hydroxyapatite's (HAp) usefulness in bone repair and tissue medicine is well known, still its potential as a drug delivery agent has been hardly investigated. Mesoporous HAp materials not only have high specific surface areas but also have OH- groups that react with appropriate drug functional groups [1]. Because of that HAp-based materials are suitable carriers for loading and releasing drug molecules. What is more, doping the material with rare earth ions (RE3+) results in highly promising materials applied in disease diagnosis and therapy [2].

Herein, novel silicate-substituted hydroxyapatites (Si-HAp), co-doped with rare earth ions (e.g. Eu3+ and Gd3+ ions ) and alkaline metal ions (e.g. Li+ ion)were obtained via short hydrothermal synthesis. Co-doping with both Eu3+ and Gd3+ ions results in obtaining materials showing simultaneously photoluminescent and magnetic properties. Likewise, the addition of Li+ ion and silicate group (SiO4)4- increases nerve and bone regeneration processes [3,4].

To characterize the physicochemical properties of obtained nSi-HAps, the XRPD (X-ray Powder Diffraction), SEM-EDS (Scanning Electron Microscopy-Energy-Dispersive Spectrometry), TEM (Transmission Electron Microscopy), FT-IR (Fourier Transform Infrared) spectroscopy and ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometry) techniques were used. In further steps photoluminescence (PL) spectra of obtained materials were studied to determine the optimal dopants concentration for novel drug carriers. The effect of alkaline metal ions on the spectroscopic properties of Eu3+ and Gd3+ ions was thoroughly studied. In the final step, screening in vitro assays were used for the determination of biomaterials cytocompatibility.

In the results new nSi-HAp/Li+/Eu3+,Gd3+ compounds with the hexagonal structure of hydroxyapatite (P63/m group) were synthesized and analyzed. Overall, the presented materials show promising physicochemical properties for potential theranostics applications and are expected to be evaluated in future investigations as potential drug carriers.

Figure 1
Fig. 1. Outline of our research on new HAp-based drug nanocarriers.

[1] V. Paterlini, M. Bettinelli, et al.,. Characterization and Luminescence of Eu3+- and Gd3+-Doped Hydroxyapatite Ca10(PO4)6(OH)2. Crystals, 10, 806 (2020).

[2] S. Targonska, R.J. Wiglusz, Investigation of Physicochemical Properties of the Structurally Modified Nanosized Silicate-Substituted Hydroxyapatite Co-Doped with Eu3+ and Sr2+ Ions, Nanomaterials 11, 27 (2021).

[3] ZY. Qiu, IS. Noh, SM. Zhang, Silicate-doped hydroxyapatite and its promotive effect on bone mineralization. Front. Mater. Sci. 7, 40 (2013).

[4] K. Marycz, P. Sobierajska, A. Smieszek, M. Maredziak, K. Wiglusz, RJ. Wiglusz, Li+ activated nanohydroxyapatite doped with Eu3+ ions enhances proliferative activity and viability of human stem progenitor cells of adipose tissue and olfactory ensheathing cells. Further perspective of nHAP:Li+, Eu3+ application in theranostics, Materials Science and Engineering: C, 78, 151 (2017).