In this work, for the first time, the influence of the coordination environment as well as Ca and P atomic states on biomimetic composites integrated with dental tissue was investigated. Bioinspired dental composites were synthesised based on nanocrystalline calcium carbonate-substituted hydroxyapatite Ca4ICa6IIPO46−xCO3x+yOH2−y (nano-cHAp) obtained from a biogenic source and a set of polar amino acids that modelled the organic matrix. Biomimetic composites, as well as natural dental tissue samples, were investigated using Raman spectromicroscopy and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. Molecular structure and energy structure studies revealed several important features related to the different calcium atomic environments. It was shown that biomimetic composites created in order to reproduce the physicochemical properties of dental tissue provide good imitation of molecular and electron energetic properties, including the carbonate anion CO32− and the atomic Ca/P ratio in nanocrystals. The features of the molecular structure of biomimetic composites are inherited from the nano-cHAp (to a greater extent) and the amino acid cocktail used for their creation, and are caused by the ratio between the mineral and organic components, which is similar to the composition of natural enamel and dentine. In this case, violation of the nano-cHAp stoichiometry, which is the mineral basis of the natural and bioinspired composites, as well as the inclusion of different molecular groups in the nano-cHAp lattice, do not affect the coordination environment of phosphorus atoms. The differences observed in the molecular and electron energetic structures of the natural enamel and dentine and the imitation of their properties by biomimetic materials are caused by rearrangement in the local environment of the calcium atoms in the HAp crystal lattice. The surface of the nano-cHAp crystals in the natural enamel and dentine involved in the formation of bonds with the organic matrix is characterised by the coordination environment of the calcium atom, corresponding to its location in the CaI position—that is, bound through common oxygen atoms with PO4 tetrahedrons. At the same time, on the surface of nano-cHAp crystals in bioinspired dental materials, the calcium atom is characteristically located in the CaII position, bound to the hydroxyl OH group. The features detected in the atomic and molecular coordination environment in nano-cHAp play a fundamental role in recreating a biomimetic dental composite of the natural organomineral interaction in mineralised tissue and will help to find an optimal way to integrate the dental biocomposite with natural tissue.
In this short communication, we provide information on the use of the hierarchical cluster analysis of synchrotron ATR-FTIR 2D chemical imaging spectral data as a useful and powerful approach to the microspectroscopic diagnostics of molecular composition in the hybrid sound dentin/dental composite interfaces and materials, including ones developed with the use of biomimetic strategies. The described diagnostic approach can be successfully transferred to the analysis and visualisation of 2D spectral data, collected using laboratory Raman and FTIR microspectroscopy techniques.
The aim of the investigation was to study the integration between native human dental tissue and new-generation biomimetic materials replicating the mineral-organic complex of dentin and enamel using IR microspectroscopy for multidimensional visualization and analysis. Materials and Methods. The conditions for stable integration at the interface between biomimetic material and natural hard tissue were identified using a biocomposite buffer system of nanocrystalline carbonate-substituted calcium hydroxyapatite corresponding in its total characteristics to human dentin-enamel apatite and a number of amino acids present in the organic matrix of dentin and enamel: L-histidine, L-lysine hydrochloride, L-arginine hydrochloride, and hyaluronic acid. The finished samples were studied using IR microspectroscopy on IRM channel equipment (The Australian Synchrotron, Melbourne, Australia). Results. The characteristic features of the biomimetic buffer layer at the interface between the enamel and dental material were revealed and visualized based on IR mapping of absorption intensity for particular functional molecular groups with the use of synchrotron radiation, location of the functional groups involved in the processes of biomimetic composite integration was identified.
The study of molecular composition of the biomimetic composites on the basis of nanocrystalline carbonate-substituted (C-HAP) and polar amino acids of L-lysine hydrochloride and L-arginine hydrochloride was performed in the work. Results of the study show that the change in acidity of the medium (pH≥11.2, ≥7.55 и ≤5) occurs under transformation of the conformational environment of L-lysine hydrochloride molecules with the formation of L-lysine structure as while increase of pH level as in the presence of C-HAP nanocrystals. At the same time composites basing on L-arginine keep their amorphous structure in the presence of synthesized C-HAP in the different media. The detected differences in the molecular environment of hydrochloride forms of amino acids during the interaction with nanocrystalline C-HAP prove to be significant for the development of technology of the integration between biocomposites and hard dental tissues.
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