Simulated body fluid (SBF) and artificial saliva (AS) are used in biomedical and dental research to mimic the physiological conditions of the human body. In this study, the biomimetic precipitation of double-doped amorphous calcium phosphate in SBF and AS are compared by thermodynamic modelling of chemical equilibrium in the SBF/AS-CaCl₂-MgCl₂-ZnCl₂-K₂HPO₄-H₂O and SBF/AS-CaCl₂-MgCl₂-ZnCl₂-K₂HPO₄-Glycine/Valine-H₂O systems. The saturation indices (SIs) of possible precipitate solid phases at pH 6.5, close to pH of AS, pH 7.5, close to pH of SBF, and pH 8.5, chosen by us based on our previous experimental data, were calculated. The results show possible precipitation of the same salts with almost equal SIs in the two biomimetic environments at the studied pHs. A decrease in the saturation indices of magnesium and zinc phosphates in the presence of glycine is a prerequisite for reducing their concentrations in the precipitates. Experimental studies confirmed the thermodynamic predictions. Only X-ray amorphous calcium phosphate with incorporated Mg (5.86–8.85 mol%) and Zn (0.71–2.84 mol%) was obtained in the experimental studies, irrespective of biomimetic media and synthesis route. Solid-state nuclear magnetic resonance (NMR) analysis showed that the synthesis route affects the degree of structural disorder of the precipitates. The lowest concentration of dopant ions was obtained in the presence of glycine. Further, the behaviour of the selected amorphous phase in artificial saliva was studied. The dynamic of Ca²⁺, Mg²⁺, and Zn²⁺ ions between the solid and liquid phases was monitored. Both direct excitation ³¹P NMR spectra and ¹H-³¹P CP-MAS spectra proved the increase in the nanocrystalline hydroxyapatite phase upon increasing the incubation time in AS, which is more pronounced in samples with lower additives. The effect of the initial concentration of doped ions on the solid phase transformation was assessed by solid-state NMR.

The preparation of specially doped calcium phosphates (CaPs) is receiving a great deal of attention from researchers due to CaPs’ enhanced capabilities for application in medicine. Complexation and precipitation in a complicated electrolyte system including simulated body fluids that are enriched with Mg²⁺ and Zn²⁺ ions and modified with glycine, alanine and valine were first evaluated using a thermodynamic equilibrium model. The influence of the type and concentration of amino acid on the incorporation degree of Mg and Zn into the solid phases was predicted. Experimental studies, designed on the basis of thermodynamic calculations, confirmed the predictions. Amorphous calcium phosphates double-doped with Mg and Zn were biomimetically precipitated and transformed into Mg, Zn-β—tricalcium phosphates (TCP) upon calcination. The Rietveld refinement confirmed that Mg²⁺ and Zn²⁺ substituted Ca²⁺ only at the octahedral sites of β-TCP, and in some cases, fully displacing the Ca²⁺ from them. The resulting Mg, Zn-β–TCP can serve as a reservoir for Mg and Zn ions when included in the formulation of a biomaterial for bone remodeling. The research conducted reveals the effect of combining mathematical models with experimental studies to pre-evaluate the influence of various additives in the design of materials with predetermined properties.

Bacterial infection is one of the most common and harmful medical issues following the implantation of materials and devices in the body leading to antibiotic resistance of diverse bacterial strains. In this work, a novel approach is presented combining adopted laser-based patterning method in addition to doping (Mg and Zn) metal ions to prepare calcium phosphate ceramic substrate, applicable in medicine, with enhanced surface antimicrobial characteristics. The preparation of tablets containing Mg (8.44 mol%) and Zn (2.63 mol%) β-tricalcium phosphate involved biomimetic precipitation of amorphous calcium phosphate in media of simulated body fluid enriched with Mg²⁺ and Zn²⁺ ions as well as the presence of valine as an organic additive, followed by step-wise calcination up to 1000 °C. The results from laser processing showed formation of deeper patterns with increased surface roughness (from 4.9 µm to 9.4 µm) as laser power and velocity increase, keeping constant the hatch sizes of 50 µm. The textured surfaces consist of peaks and valleys arrangement that change the morphology of Escherichia coli cells and decrease of cell viability. Our study reveals the possibilities of the application of ultra-short laser radiation as a potential alternative therapy for controlling the antimicrobial effect of the ceramic surface.

Hybrid materials based on calcium phosphates and synthetic polymers can potentially be used for caries protection due to their similarity to hard tissues in terms of composition, structure and a number of properties. This study is focused on the biomimetic synthesis of hybrid materials consisting of hydroxiapatite and the zwitterionic polymers polysulfobetaine (PSB) and polycarboxybetaine (PCB) using controlled media conditions with a constant pH of 8.0–8.2 and Ca/P = 1.67. The results show that pH control is a dominant factor in the crystal phase formation, so nano-crystalline hydroxyapatite with a Ca/P ratio of 1.63–1.71 was observed as the mineral phase in all the materials prepared. The final polymer content measured for the synthesized hybrid materials was 48–52%. The polymer type affects the final microstructure, and the mineral particle size is thinner and smaller in the synthesis performed using PCB than using PSB. The final intermolecular interaction of the nano-crystallized hydroxyapatite was demonstrated to be stronger with PCB than with PSB as shown by our IR and Raman spectroscopy analyses. The higher remineralization potential of the PCB-containing synthesized material was demonstrated by in vitro testing using artificial saliva.