In our paper, we discuss the results of a comprehensive structural-spectroscopic and microscopic analysis of non-stoichiometric nanocrystalline hydroxyapatite (CHAp) with low carbonate anion content and biomimetic hybrid nanomaterials produced on its basis. It was shown that hydroxyapatite nanocrystals synthesized by chemical precipitation and biogenic calcium source mimic the properties of biogenic apatite and also have a morphological organization of “core–shell” type. The “core” of the CHAp nanocrystal is characterized by an overabundance of calcium Ca/P~1.9. Thus “a shell” with thickness of ~3–5 nm is formed from intermediate apatite-like phases where the most probable are octocalcium phosphate, dicalcium phosphate dihydrate and tricalcium phosphate. The multimode model of the Raman profile of samples CHAp and biomimetic composites for spectral region 900–1100 cm⁻¹ proposed in our work has allowed to allocate precise contribution of B-type carbonate substitution, taking into account the presence on a surface of “core” HAp nanocrystal of various third-party intermediate apatite-like phases. The calibration function constructed on the basis of the described model makes it possible to reliably determine small concentrations of carbonate in the structure of hydroxyapatite with the application of Raman express method of diagnostics. The results of our work can inspire researchers to study the processes of induced biomineralization in mineralized tissues of the human body, using non-destructive methods of control with simultaneous analysis of chemical bonding, as well as determining the role of impurity atoms in the functions exhibited by biotissue.

In this exploratory study, we searched for associations between the two most common diseases of the oral cavity—dental caries and periodontal diseases—taking into account additional factors, such as personalized clinical pictures (the individual risk factors of the patient), based on the method of a multivariate data analysis of the molecular changes in the composition of human gingival crevicular fluid (GCF). For this purpose, a set of synchrotron Fourier-transform infrared spectroscopy (FTIR) spectra of gingival crevicular fluid samples from patients with different demographics, levels of dental caries development and periodontal diseases, and the presence/absence of concomitant chronic diseases were obtained and analyzed. Using a set of techniques (v-, F-, Chi-square tests; a principal component analysis (PCA); and the hierarchical clustering of principal components (HCPCs)) implemented in the R package FactoMineR allowed us to assess the relationship between the principal components (PCs) and characteristics of the respondents. By identifying the features (vibrational modes in the FTIR spectra) that contribute most to the differentiation of the spectral dataset, and by taking into account the interrelationships between the patients’ characteristics, we were able to match specific biological markers (specific molecular groups) to the two factors of interest—two types of oral pathologies. The results obtained show that the observed changes in the quantitative and qualitative composition of the modes in the infrared (IR) spectra of the GCF samples from patients with different dental caries developments and periodontal diseases present confirm the difficulty of identifying patient-specific spectral information. At the same time, different periodontal pathologies are more closely associated with other characteristics of the patients than the level of their caries development. The multivariate analysis performed on the spectral dataset indicates the need to take into account not only the co-occurrence of oral diseases, but also some other factors. The lack of this consideration (typical in lots of studies in this area) may lead to misinterpretations and consequently to a loss of data when searching for biological markers of certain oral diseases.

The creation of buffer (hybrid) layers that provide improved adhesion to two heterogeneous materials is a promising and high-priority research area in the field of dental materials science. In our work, using FTIR and Raman microspectroscopy at the submicron level in a system of dental composites/intact dental enamel, we assessed the molecular features of formation and chemically visualized the hybrid interface formed on the basis of a nature-like adhesive, polydopamine (PDA). It is shown that a homogeneous bioinspired PDA–hybrid interface with an increased content of O-Ca-O bonds can be created using traditional methods of dental tissue pretreatment (diamond micro drilling, acid etching), as well as the subsequent alkalinization procedure and the developed synthesis technology. The development of the proposed technology for accelerated deposition of PDA–hybrid layers, as well as the creation of self-assembled biomimetic nanocomposites with antibacterial properties, may in the future find clinical application for minimally invasive dental restoration procedures.

This work unveils the idea that the cariogenic status of the oral cavity (the presence of active caries lesions) can be predicted via a lineshape analysis of the infrared spectral signatures of the secondary structure of proteins in dental biofilms. These spectral signatures that work as natural markers also show strong sensitivity to the application in patients of a so-called modulator—a medicinal agent (a pelleted mineral complex with calcium glycerophosphate). For the first time, according to our knowledge, in terms of deconvolution of the complete spectral profile of the amide I and amide II bands, significant intra- and intergroup differences were determined in the secondary structure of proteins in the dental biofilm of patients with a healthy oral cavity and with a carious pathology. This allowed to conduct a mathematical assessment of the spectral shifts in proteins’ secondary structure in connection with the cariogenic situation in the oral cavity and with an external modulation. It was shown that only for the component parallel β-strands in the amide profile of the biofilm, a statistically significant (p < 0.05) change in its percentage weight (composition) was registered in a cariogenic situation (presence of active caries lesions). Note that no significant differences were detected in a normal situation (control) and in the presence of a carious pathology before and after the application of the modulator. The change in the frequency and percentage weight of parallel β-strands in the spectra of dental biofilms proved to be the result of the presence of cariogenic mutans streptococci in the film as well as of the products of their metabolism—glucan polymers. We foresee that the results presented here can inherently provide the basis for the infrared spectral diagnosis of changes (shifts) in the oral microbiome driven by the development of the carious process in the oral cavity as well as for the choice of optimal therapeutic treatments of caries based on microbiome-directed prevention measures.

In our work, the effect of a dental Er:YAG pulsed laser and a diamond cylindrical drill with a turbine handpiece on dentin tissue was studied using spectral imaging. The combination of spectral imaging of FTIR microspectroscopy data and subsequent multivariate analysis (hierarchical cluster analysis (HCA) and principal component analysis (PCA)) was shown to unambiguously detect visually indistinguishable structural changes occurring in the hard dental tissue (dentin) depending on the method used for their pre-processing, and to classify and differentiate the identified features at the submicron level with high spatial resolution. The detectable spectral transformations indicate that the preparation of dental tissue with a dental laser leads to significant changes in the organic components of dentin, which may affect adhesion. The use of a diamond cylindrical drill with a turbine handpiece is characterized by a larger area (depth) of the altered hard tissue than in the case of a dental laser for dental cavity preparation. The observed redistribution of the phase composition of the inorganic component in the tissue is associated with the emergence of additional phases of weak calcium phosphates, and changes in the organic component with transformations in the secondary structure of proteins. Active use of the proposed integrated approach in the future will clarify the areas of its applicability to the analysis of biological tissues and pathologies in them, which will help in the clinical setting to choose the optimal personalized approach for patients.

The growth of nanoscale columnar Al_xGa_1-xN/AlN heterostructures on the surface of silicon substrates using plasma-activated nitrogen molecular-beam epitaxy was investigated in this work. Silicon substrates include atomic-smooth cSi substrate, Si substrate with a transition layer of porous silicon porSi/cSi and a hybrid substrate involving a silicon carbide layer grown with matched substitution of the atoms on the surface of porous silicon SiC/porSi/cSi. A complex analysis performed using a set of structural and spectroscopic techniques demonstrated that the epitaxial growth of the nuclear AlN layer on all types of the substrates in a N-enriched environment resulted in the formation of Al_xGa_1-xN/AlN heterostructures with a Ga-polar surface, which was realized only on the SiC/porSi/cSi substrate. The layer of Al_xGa_1-xN on cSi and porSi/cSi substrates was in the state of disordered alloy with an excess of gallium atom content. It was shown that a great difference in the lattice parameters of a substrate–film pair resulted not only in the appearance of a number of various defects but also in a considerable effect on the chemical process of the formation of the alloys, in our case, the Al_xGa_1-xN alloy. It was shown that nanoscale columns of Al_xGa_1-xN formed on SiC/porSi/cSi substrate were inclined relative to the c-axis, which was connected with the features of the formation of a SiC layer by the matched substitution of the atoms on the porous Si substrate, resulting in the formation of the inclined (111) SiC facets at the boundary of the (111) Si surface and pores in Si. Optical studies of the grown samples demonstrated that the optical band-to-band transition for the AlxGa1-xN alloy with E_g = 3.99 eVB was observed only for the heterostructure grown on the SiC/porSi/cSi substrate. A qualitative model is proposed to explain the difference in the formation of Al_xGa_1-xN layers on the substrates of cSi, porSi/cSi and SiC/porSi/cSi. The results obtained in our work demonstrate the availability of using SiC/porSi/cSi substrates for the integration of silicon technology and that used for the synthesis of nanoscale columnar Al_xGa_1-xN heterostructures using plasma-activated molecular-beam epitaxy with a nitrogen source.