whitlockite and Dental-Caries

It is well known that caries invasion leads to the differentiation of dentin into zones with altered composition, collagen integrity and mineral identity. However, understanding of these changes from the fundamental perspective of molecular structure has been lacking so far. In light of this, the present work aims to utilize Fourier transform infrared spectroscopy (FTIR) to directly extract molecular information regarding collagen's and hydroxyapatite's structural changes as dentin transitions from the transparent zone (TZ) into the normal zone (NZ). Unembedded ultrathin dentin films were sectioned from carious teeth, and an FTIR imaging system was used to obtain spatially resolved FTIR spectra. According to the mineral-to-matrix ratio image generated from large-area low-spectral-resolution scan, the TZ, the NZ and the intermediate subtransparent zone (STZ) were identified. High-spectral-resolution spectra were taken from each zone and subsequently examined with regard to mineral content, carbonate distribution, collagen denaturation and carbonate substitution patterns. The integrity of collagen's triple helical structure was also evaluated based on spectra collected from demineralized dentin films of selected teeth. The results support the argument that STZ is the real sclerotic layer, and they corroborate the established knowledge that collagen in TZ is hardly altered and therefore should be reserved for reparative purposes. Moreover, the close resemblance between the STZ and the NZ in terms of carbonate content, and that between the STZ and the TZ in terms of being A-type carbonate-rich, suggest that the mineral that initially occludes dentin tubules is hydroxyapatite newly generated from odontoblastic activities, which is then transformed into whitlockite in the demineralization/remineralization process as caries progresses.

Topics: Amides; Calcium Phosphates; Carbonates; Collagen; Dental Caries; Dentin; Dentin, Secondary; Durapatite; Humans; Minerals; Odontoblasts; Phosphates; Sclerosis; Spectroscopy, Fourier Transform Infrared

This study correlated ultrastructural observations on the presence of beta-tricalcium phosphate (beta-TCP) in arrested dentin caries with physico-chemical observations on the in vitro formation of Mg-substituted beta-TCP. The ultrastructural studies were made using high-resolution transmission electron microscopy (TEM) with the capability of microdiffraction and microanalysis on sites less than 10 nm in diameter. Mg-substituted beta-TCP was obtained, by a precipitation method, from solutions with Mg/Ca molar ratios of 5/95 and higher. Such correlations led to the postulation of a possible chronological sequence of physico-chemical events occurring at the crystal level during the progress and arrest of caries in human dentin. It is suggested that the initial mechanism for the observed occurrence of large crystals of Mg-substituted beta-TCP and of apatite in the tubule lumen is due to the dissolution of the dentin mineral (a CO3- and Mg-rich calcium OH-apatite) and reprecipitation of Mg-substituted beta-TCP, followed by that of CO3- and Mg-poor apatite.

Topics: Calcium Phosphates; Chemical Phenomena; Chemistry, Physical; Crystallography; Dental Caries; Dentin; Electron Probe Microanalysis; Humans; Microscopy, Electron; Phosphates; X-Ray Diffraction