The aim of this work is to develop a biomimetic interface between the natural tooth tissue and the restorative composite and to study it on the basis of synchrotron micro-FTIR mapping and multidimensional processing of the spectral data array. Using hierarchical cluster analysis of 3D FTIR data revealed marked improvements in the formation of the dentine/adhesive/dental hybrid interface using a biomimetic approach. The use of a biomimetic strategy (application of an amino acid–modified primer, alkaline calcium and a nano-c-HAp–modified adhesive) allowed the formation of a matrix that can be structurally integrated with natural dentine and dental composite. The biomimetic hybrid layer was characterised by homogeneous chemical composition and a higher degree of conversion of the adhesive during polymerisation, which should provide optimal integration of the dental composite with the dentine.

The detected features in the IR spectra of mixed saliva as well as the calculated changes in the ratios between organic and inorganic components can be used as biomarkers of cariogenesis in the oral cavity, as a diagnostic criterion in the analysis of the oral fluid samples.

This study is aimed at investigating the features of mineralization of the enamel apatite at initial stages of fluorosis development. Samples of teeth with intact and fluorotic enamel in an early stage of the disease development (Thylstrup–Fejerskov Index = 1–3) were studied by Raman scattering and FTIR using Infrared Microspectroscopy beamline at Australian Synchrotron equipment. Based on the data obtained by optical microspectroscopy and calculation of the coefficient R [A-type/B-type], which represents the ratio of carbonation fraction of CO32−, replacing phosphate or hydroxyl radicals in the enamel apatite lattice, the features of mineralization of enamel apatite in the initial stages of development of the pathology caused by an increased content of fluorine in the oral cavity were established. Statistical analysis of the data showed significant differences in the mean values of R [A-type/B-type] ratio between the control and experimental groups for surface layers (p < 0.01). The data obtained are potentially significant as benchmarks in the development of a new approach to preventive diagnostics of the development of initial and clinically unregistered stages of human teeth fluorosis, as well as personalized control of the use of fluoride-containing caries-preventive agents.

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 report, we demonstrated the formation of a biomimetic mineralizing layer obtained on the surface of dental enamel (biotemplate) using bioinspired nanocrystalline carbonate-substituted calcium hydroxyapatite (ncHAp), whose physical and chemical properties are closest to the natural apatite dental matrix, together with a complex of polyfunctional organic and polar amino acids. Using a set of structural, spectroscopy, and advanced microscopy techniques, we confirmed the formation of a nanosized ncHAp-based mineralized layer, as well as studying its chemical, substructural, and morphological features by means of various methods for the pretreatment of dental enamel. The pretreatment of a biotemplate in an alkaline solution of Ca(OH)2 and an amino acid booster, together with the executed subsequent mineralization with ncHAp, led to the formation of a mineralized layer with homogeneous micromorphology and the preferential orientation of the ncHAp nanocrystals. It was shown that the homogeneous crystallization of hydroxyapatite on the biotemplate surface and binding of individual nanocrystals and agglomerates into a single complex by an amino acid booster resulted in an increase (~15%) in the nanohardness value in the enamel rods area, compared to that of healthy natural enamel. Obtaining a similar hierarchy and cleavage characteristics as natural enamel in the mineralized layer, taking into account the micromorphological features of dental tissue, is an urgent problem for future research.