A Fourier transform infrared spectroscopy analysis of carious dentin from transparent zone to normal zone

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.