Hydroxyapatite (Ca10(PO4)6(OH)2, abbreviated as HA) plays a crucial role in implantology, dentistry and bone surgery. Due to its considerable similarity to the inorganic fraction of the mineralized tissues (bones, enamel and dentin), it is used as component in many bone substitutes, coatings of metallic implants and dental materials. Biomaterial engineering often takes advantage of HA capacity for partial ion substitution because the incorporation of different ions in the HA structure leads to materials with improved biological or physicochemical properties. The objective of the work is to provide an overview of current knowledge about apatite materials substituted with silicon ions. Although the exact mechanism of action of silicon in the bone formation process has not been fully elucidated, research has shown beneficial effects of this element on bone matrix mineralization as well as on collagen type I synthesis and stabilization. The paper gives an account of the functions of silicon in bone tissue and outlines the present state of research on synthetic HA containing silicate ions (Si-HA). Finally, methods of HA production as well as potential and actual applications of HA materials modified with silicon ions are discussed

Osteoporosis is a worldwide chronic disease characterized by increasing bone fragility and fracture likelihood. In the treatment of bone defects, materials based on calcium phosphates (CaPs) are used due to their high resemblance to bone mineral, their non-toxicity, and their affinity to ionic modifications and increasing osteogenic properties. Moreover, CaPs, especially hydroxyapatite (HA), can be successfully used as a vehicle for local drug delivery. Therefore, the aim of this work was to fabricate hydroxyapatite-based composite beads for potential use as local carriers for raloxifene. HA powder, modified with magnesium and silicon ions (Mg,Si-HA) (both of which play beneficial roles in bone formation), was used to prepare composite beads. As an organic matrix, sodium alginate with chondroitin sulphate and/or keratin was applied. Cross-linking of beads containing raloxifene hydrochloride (RAL) was carried out with Mg ions in order to additionally increase the concentration of this element on the material surface. The morphology and porosity of three different types of beads obtained in this work were characterized by scanning electron microscopy (SEM) and mercury intrusion porosimetry, respectively. The Mg and Si released from the Mg,Si-HA powder and from the beads were measured by inductively coupled plasma optical emission spectrometry (ICP-OES). In vitro RAL release profiles were investigated for 12 weeks and studied using UV/Vis spectroscopy. The beads were also subjected to in vitro biological tests on osteoblast and osteosarcoma cell lines. All the obtained beads revealed a spherical shape with a rough, porous surface. The beads based on chondroitin sulphate and keratin (CS/KER-RAL) with the lowest porosity resulted in the highest resistance to crushing. Results revealed that these beads possessed the most sustained drug release and no burst release effect. Based on the results, it was possible to select the optimal bead composition, consisting of a mixture of chondroitin sulphate and keratin.

Powders of α-TCP containing various amounts of silicon were synthesized by two different methods: Wet chemical precipitation and solid-state synthesis. The obtained powders were then physico–chemically studied using different methods: Scanning and transmission electron microscopy (TEM and SEM), energy-dispersive X-ray spectroscopy (EDS), powder X-ray diffractometry (PXRD), infrared and Raman spectroscopies (FT-IR and R), and solid-state nuclear magnetic resonance (ssNMR). The study showed that the method of synthesis affects the morphology of the obtained particles, the homogeneity of crystalline phase and the efficiency of Si substitution. Solid-state synthesis leads to particles with a low tendency to agglomerate compared to the precipitation method. However, the powders obtained by the solid-state method are less homogeneous and contain a significant amount of other crystalline phase, silicocarnotite (up to 7.33%). Moreover, the microcrystals from this method are more disordered. This might be caused by more efficient substitution of silicate ions: The silicon content of the samples obtained by the solid-state method is almost equal to the nominal values.

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.

Hydroxyapatite materials, due to their high biocompatibility, play a crucial role in orthopaedics and bone surgery as alternatives to autologous bone grafts. It was also found that coatings of metallic implants with hydroxyapatite layer improve significantly their osseointegration. Due to its bioactivity, osteoconductivity and non-toxicity, hydroxyapatite is also widely used as a component of hybrid biomaterials. The implantation of “foreign” materials brings one major concern that is the risk of potential bone tissue infections or chronic osteomyelitis. In turn, the main problem concerning bacterial infection treatment is to obtain an adequate, bactericidal drug concentration maintained for a sufficient period of time in the bone tissue. Therefore, recent developments of materials engineering are focused on delivery antibiotics directly into the affected bone. To achieve this goal, hydroxyapatite-based materials are frequently studied as carriers for antibacterial drugs. For effective support of antibiotic therapy, the antibacterial activity of certain ions (including silver, zinc or copper) may be applied. In our work, we present recent developments on ceramic materials for bacterial bone infections: hydroxyapatite-based carriers for antibiotics and modifications of hydroxyapatite with antibacterial ions. In this review, state-of-the-art and current applications of such materials are presented and discussed. We want to also present our recent results.