In vitro remineralization of acid-etched human enamel with Ca3SiO5

Bioactive and inductive silicate-based bioceramics play an important role in hard tissue prosthetics such as bone and teeth. In the present study, a model was established to study the acid-etched enamel remineralization with tricalcium silicate (Ca₃SiO₅, C₃S) paste in vitro. After soaking in simulated oral fluid (SOF), Ca-P precipitation layer was formed on the enamel surface, with the prolonged soaking time, apatite layer turned into density and uniformity and thickness increasingly from 250 to 350 nm for 1 day to 1.7-1.9 μm for 7 days. Structure of apatite crystals was similar to that of hydroxyapatite (HAp). At the same time, surface smoothness of the remineralized layer is favorable for the oral hygiene. These results suggested that C₃S treated the acid-etched enamel can induce apatite formation, indicating the biomimic mineralization ability, and C₃S could be used as an agent of inductive biomineralization for the enamel prosthesis and protection.     

Fluorine absorption in dental enamel assisted by UV irradiation

Summary A new method of dental fluorine prophylaxis based on the chemical reaction induced by UV irradiation in dental enamel has been presented. Fluorine ions from a gel topic can be retained to the dental apatite in the lamp-irradiated samples at about 70% and in the laser-irradiated samples at about 80% of the maximum deposited value. The¹⁹F(p,α)¹⁶O nuclear reaction was used to measure the fluorine concentrations in the first 3 μm of the enamel of healthy teeth before and after the gel topic applications with and without UV irradiation. This method of dental prefenction resolves the problem of the traditional fluorine prophylaxis which brings fluorine in the enamel without binding the apatite. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Functional mapping of carious enamel in human teeth with Raman microspectroscopy

We employed Raman microspectroscopy to measure the Raman spectra of phosphate in sound and carious tooth substance. The peak intensity at 960 cm⁻¹ of the phosphate (PO₄³⁻) symmetric stretching vibrational mode (υ₁) in sound enamel was stronger than that of sound dentin, which indicated that sound enamel contained more phosphate than sound dentin. Furthermore, the element analysis of phosphate in sound teeth substance, measured using a scanning electron microscope (SEM) equipped with an energy dispersive X‐ray spectroscope (EDX), gave similar results to those of the Raman measurement. In addition, the border between sound enamel and dentin was clearly demonstrated by mapping the image of the Raman spectrum of phosphate. The mapping image of phosphate in the carious enamel region revealed a heterogeneous low Raman spectrum intensity of phosphate in the area surrounding carious enamel; this finding indicates that phosphate had dissolved from the tooth substance in such areas. In contrast with the decrease in the Raman spectrum intensity of phosphate, the intensity of amide I increased mainly in the low‐phosphate area. Although it remains very difficult to clinically identify the accurate border between sound and carious tooth substance, this distinction may be enabled by using the Raman spectrum of carious tooth substance. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and IR reflection micro‐spectroscopic study of Er:YAG laser treated permanent and deciduous human teeth

Permanent and deciduous human teeth treated by a dental Er‐doped yttrium‐aluminium‐garnet pulse laser (λ = 2940 nm) as well as by classical drilling tools under conditions typical of the clinical practice were studied by ultraviolet Raman and Fourier transform infrared (FTIR) reflection microspectroscopy. Enamel was analyzed by both spectroscopic methods, whereas dentine was studied only by FTIR reflection because of the high level of photoluminescence continuum background even when a wavelength of 325 nm was used in inelastic light scattering experiments. The applied energy and pulse frequency of the dental laser varied between 200 and 500 mJ and between 10 and 30 Hz, respectively. The most important result is that after the laser treatment, the hydroxyapatite structure in both permanent and deciduous enamel is preserved: the apatite Ca‐P‐O framework remains intact, and the content of channel OH^‐ groups is not changed within experimental uncertainties. The calcium‐phosphate framework of dentine also exhibits negligible laser‐induced changes. The only alterations in enamel induced by laser as well as by mechanical drilling are reduction of the amount of CO₃^2‐ in apatite and changes in the protein conformation. The laser impact on the organic material and carbonate groups is strongest for laser power of 8 W; for powers of 4 or 5 W, the combination of higher pulse energy and lower pulse frequency has less impact than the combination of lower energy and higher frequency. No differences between deciduous and permanent teeth in their resistivity to laser irradiation with λ = 2940 nm were detected. Copyright © 2013 John Wiley & Sons, Ltd.     

Local study of fissure caries by Fourier transform infrared microscopy and X‐ray diffraction using synchrotron radiation

Investigations of intact dental enamel as well as carious‐affected human dental enamel were performed using infrared spectromicroscopy and X‐ray diffraction applying synchrotron radiation. Caries of enamel was shown to be characterized by an increase in the number of deformation and valence vibrations for N—C—O, N—H and C=O bonds, a decrease of the crystallinity index, and by the absence of the preferable orientation of hydroxyapatite crystals within the affected enamel. This indicates the presence of destructive processes in the organic matrix of hard tooth tissues.     

Photoluminescence Properties of Nanoporous Nanocrystalline Carbonate-Substituted Hydroxyapatite

Luminescence characteristics of an analogue of the mineral component of dental enamel—nanocrystalline B-type carbonate-substituted calcium hydroxyapatite (CHAP)—with defects (nanopores ～2?5 nm in size) on the surface of nanocrystals are studied. It is shown that laser-induced luminescence of CHAP samples synthesized by us occurs in the region of ～515 nm (～2.4 eV) and is related to the existence of CO₃ groups substituting PO₄ groups in the CHAP lattice. It is determined that the luminescence intensity of the CHAP samples depends on the amount of structurally bound CO₃ groups and decreases with decreasing concentration of these intracenter defects in the apatite structure. The results obtained in this work are of potential importance for developing the fundamentals of precision and early detection of caries in human hard dental tissue.     

EPR-dosimetry with carious teeth

The effect of caries in EPR dosimetry of tooth enamel (in the dose range of 0–1 Gy) was investigated. The enamel of each tooth was divided into carious, non-carious and intermediate portions. The EPR signals of enamel at g = 2.0018 (dosimetric) and g = 2.0045 (native) were examined. The intensity of the dosimetric signal was the same for all three portions, while that of the native signal was higher for carious portions than for non-carious and intermediate portions. Reconstruction of the laboratory applied doses was done using all portions. Reasonable correlation between nominal and reconstructed doses was found in most cases. The effect of alkali treatment on the native and dosimetric signals of enamel was also tested. Reduction of the native signal intensity, particularly in the carious portions, was found to be the only significant effect. This resulted in a slight improvement in the accuracy of the reconstructed doses.     

FT‐Raman investigation of human dental enamel surfaces

FT‐Raman spectra of human enamel surfaces from sound, affected (with 1 cavity) and highly affected (with at least 3 cavities) tooth samples were analyzed by principal component analysis (PCA). Major differences between the unaffected and affected tooth samples seem to arise from the structural changes along the c‐axis of hydroxyapatite, the chief crystalline component of human dental enamel. Based on Fisher index calculations, the most discriminative value was obtained for the intensity of the only Raman active ν₂PO₄³⁻ (E₁) symmetric deformation mode at 428 cm⁻¹. Moreover, these changes can be observed through the whole tooth enamel surface, establishing a predisposition to caries correlated to chemical and structural composition of tooth enamel. No spectral changes regarding the CO₃²⁻ substitution were detected by both nondestructive FT‐Raman and FTIR (Fourier transform infrared) spectroscopy of the powdered teeth samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Lasers effects on enamel for caries prevention

The aim of this study was to ascertain whether laser irradiation is able to reduce caries incidence. For this purpose, the effects of laser on enamel and on fluoride uptake were discussed. Current literature regarding the preventive effect of laser irradiation on dental hard tissue has been reviewed. An evaluation of the results of the available in vitro and in vivo studies on the efficacy of anticaries and induced changes on enamel by laser irradiation were also performed. Articles were selected using the Medline, Web of Science, Embase, and Cochrane databases, and the results of these studies were described. The most common lasers employed for caries prevention on enamel are Nd:YAG; CO₂; Er:YAG; Er,Cr:YSGG; and argon. The percentage of inhibition of dental caries varied from 30 to 97.2%, and the association with fluoride has demonstrated the best results on inhibition of caries development. Laser irradiation under specific conditions can change the crystallographic properties of apatite crystals, increasing the acid resistance of lased enamel. The combined treatment of laser irradiation with fluoride propitiates an expressive fluoride uptake, reducing the progression of carieslike lesions, and this treatment is more effective than laser or fluoride alone. Available data suggest that lasers combined with fluoride is a promising treatment in caries prevention.     

In situ synthesis of silicon-substituted biphasic calcium phosphate and their performance in vitro

In situ preparation of silicon (Si) substituted biphasic calcium phosphate (BCP) of hydroxyapatite (HAp)/ β-tricalcium phosphate (β-TCP) were carried out through aqueous co-precipitation method. The concentrations of added silicon were varied with the phosphor in order to obtain constant Ca/(P+Si) ratios of 1.602. X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy were used to characterize the structure of synthesized silicon substituted BCP powders. The characterization revealed that the formation of biphasic mixtures of different HAp/ β-TCP ratios was dependent on the content of silicon. After immersing in Hanks' balanced salt solution (HBSS) for 1 week, 3 wt% silicon substituted BCP powders were degraded and precipitation started to be formed with small granules consisting of number of flake-like crystal onto the surface of synthesized powders. In the case of 1 wt% silicon substituted BCP powders, the degradation behavior was detected after immersion in HBSS for 3 weeks. On the other hand, silicon unsubtituted BCP powders were not degraded even after that duration. On the basis of these results, silicon substituted BCP is able to develop a new apatite phase on the surface in contact with physiological fluids faster than BCP does. This enhanced reactivity resulted in reduction for the stability of the β-TCP structure due to SiO₄ tetrahedral distortion and disorder at the hydroxyl site when silicon incorporates into BCP.     

电感耦合等离子体-原子发射光谱法测定龋齿中微量元素

牙齿样品经HNO3-HClO4体系消解,采用电感耦合等离子体-原子发射光谱法(ICP-AES)测定龋齿和健康齿的牙釉质与牙本质中Zn、Fe、Cu、Sr、Mg、Cr、Al和Pb等微量元素。方法相对标准偏差在1.1%—2.7%之间,标准回收率在90.0%—106.7%之间。实验测得龋齿牙釉质与牙本质中Zn、Fe、Cu和Sr含量均明显低于健康齿,而Mg、Cr、Al和Pb含量则均高于健康齿,说明牙齿中的微量元素是指示龋病的一种因子。本实验为口腔医学研究提出了一个简单、准确和可行的研究方法,也为医院口腔科预防和治疗龋齿,提供参考数据。     

Ageing of calcium silicate cements for endodontic use in simulated body fluids: a micro‐Raman study

To evaluate bioactivity properties, a calcium silicate experimental cement (wTC) and a phosphate‐doped wTC cement (wTC‐TCP) were aged for different times (1–180 days) at 37 °C in two simulated body fluids, i.e. Dulbecco's phosphate buffered saline (DPBS) and Hank's balanced salt solution (HBSS). The cements were analyzed by micro‐Raman spectroscopy to investigate the presence of calcium phosphate deposits and the composition changes as a function of the storage time (hydration of anhydrite/gypsum and formation of ettringite; hydration of belite/alite and formation of hydrated silicates). After 1 day of ageing in DPBS, the two cements already showed a different behavior: only the surface of wTC‐TCP cement showed the band at 965 cm⁻¹, suggesting the formation of a detectably thick calcium phosphate deposit. The trend of the I₉₆₅/I₉₉₀ Raman intensity ratio indicated the formation of a meanly thicker apatite deposit on the wTC‐TCP cement until 90 days. After 60 days of ageing in DPBS, the thickness of the apatite deposit on wTC and wTC‐TCP was about 200 and 500 µm, respectively, whereas at 180 days, the two cements did not appear significantly different (thickness of about 900 µm). The bioactivity of both cements in HBSS was less pronounced than in DPBS, according to the lower phosphate concentration of HBSS; at the same time, higher amounts of calcite were found on the surface of both cements. The wTC‐TCP cement showed a higher bioactivity in this medium also; after 180 days, the thickness of the apatite deposit on wTC and wTC‐TCP was < 50 µm and about 100 µm, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Multi-frequency EPR study of radiation-induced radicals in tooth enamel

Human tooth enamel powders, unheated as well as heated prior to X -irradiation at room temperature, have been investigated by means of Q - and W -band Electron Paramagnetic Resonance (EPR). Upon irradiation of enamel, carbonate-derived radicals are generated. The simplest acquired EPR spectra in this study consist mainly of a group of three different \hbox{CO}_3^{3-} signals, with a very weak \hbox{CO}_2^{-} contribution. The characterisation of the paramagnetic species in enamel is quite important for the reliability of EPR applications ( e.g. , EPR retrospective dosimetry). The spectra from the heated samples reveal a striking resemblance with spectra from certain irradiated synthetic apatite powders. The spin Hamiltonian parameters obtained from the computer simulations of the Q - and W -band spectra are compared with those reported in the literature.     

NMR T1–T2 correlation analysis of molecular absorption inside a hardened cement paste containing silanised silica fume

ABSTRACT

The influence of silanised silica fume addition on the pore size distribution and wettability of white cement paste was investigated using T₁–T₂ correlation nuclear magnetic resonance (NMR) relaxometry. Surface silanisation of silica fume particles was achieved by the hydrolysis reaction of APTES (3-Aminopropyltriethoxysilane) and condensation of the silanol functional groups on the surface. The methods used for characterisation of the silanised silica fume particles were scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). By adding silanised silica fume to the cement paste, the accessibility of water molecules to the porous system becomes restricted, leading to a lower permeability in comparison with the unmodified cement paste. Differential scanning calorimetry (DSC) measurements on the cement pastes saturated with Octamethylcyclotetrasiloxane confirm also that the size of inter-C–S–H and capillary pores is not influenced by the addition of silica fume in a detectable manner.     

Structural and Spectroscopic Investigation of Biomimetic Composites—Promising Agents for the Remineralization of Native Dental Tissue

Biomimetic materials (biocomposites) with an organic-mineral composition related to natural dental tissues (enamel and dentin) are obtained for the first time and their structural and optical characteristics are studied. It is demonstrated by a complex of structural and spectroscopic methods that in the formation of biocomposites, the introduced organic component, bearing a number of amino acids, does not affect the structure of the inorganic component (carbonate-substituted calcium hydroxyapatite) of the sample. The carbonate-substituted calcium hydroxyapatite synthesized using a biogenic source of calcium, which forms the basis of the biocomposite, has a luminescence spectrum similar to that of apatite tooth enamel. The spectrum of the intact dentin of a human tooth has a broader luminescence band than that for the enamel spectrum. It is determined that both organic and inorganic components contribute to the dentin luminescence band. The features found in the luminescence spectra of intact tissues and in simulating biocomposites can be used to develop a procedure for effective early diagnosis of the demineralization of hard dental tissues and general dental examination.     

Broad‐beam PIXE and µ‐PIXE analysis of normal and in vitro demineralized dental enamel

Dental enamel has been widely studied by particle‐induced x‐ray emission (PIXE), but less attention was paid to its demineralization, which leads to caries formation. Using broad‐beam PIXE and µ‐PIXE, we investigated normal enamel and the in vitro formation of pre‐carious lesion in lactic acid solution, aiming also to evaluate intercusp differences within the same tooth. Broad‐beam PIXE was performed using 3.0 MeV protons, and µ‐PIXE maps of Ca, Fe and Zn were collected with 3.1 MeV protons at ～4 µm resolution. In normal enamel a differentiated Ca‐rich surface layer was observed, where Fe and Zn reached their highest levels. In deeper layers, Fe and Zn evidenced quasiperiodic patterns of maxima, possibly due to coupled diffusion‐reaction catalytic processes involved in the enamel growth. Both Fe and Zn appeared to be located in a few distinct types of pools. Near the surface, demineralization induced an increase of Fe, Cu, Zn, Sr and Pb with respect to Ca, attributed to partial hydroxyapatite dissolution and/or to chelate extraction and concentration of trace metals. Ca maps revealed limited changes in the surface layer and a massive loss in the inner enamel; here, Fe was almost depleted and Zn partially removed. The maps of Ca, Fe and Zn demonstrated major intercusp variations in both normal and altered enamel. Thus, broad‐beam PIXE and µ‐PIXE, which do not require (semi)thin sectioning of the tooth as the conventional methods, provide compositional and structural insight of normal dental enamel, of its intercusp variability and of the alterations produced by in vitro demineralization, largely not accessible to the current techniques, and highly relevant for understanding the incipient caries formation. Copyright © 2008 John Wiley & Sons, Ltd.     

Low-fluence CO2 laser irradiation decreases enamel solubility

This study investigated whether subablative-pulsed CO₂ laser (10.6 μm) irradiation, using fluences lower than 1 J/cm², was capable of reducing enamel acid solubility. Fifty-one samples of bovine dental enamel were divided into three groups: control group, which was not irradiated (CG); group laser A (LA) irradiated with 0.3 J/cm²; and group laser B (LB) irradiated with 0.7 J/cm². After irradiation, the samples were subjected to demineralization in an acetate buffer solution and were then analyzed by SEM. A finite-element model was used to calculate the temperature increase. The calcium and phosphorous content in the demineralization solution were measured with an ICP-OES. ANOVA and the t-test pairwise comparison (p < 0.016) revealed that LB showed significantly lower mean Ca and P content values in the demineralization solution than other groups. A reduction in the enamel solubility can be obtained with pulsed CO₂ laser irradiation (0.7 J/cm², 135 mJ/pulse, 74 Hz, 100 μs) without any surface photomodification and a less than 2°C temperature increase at a 3-mm depth from the surface.     

Characterization of enamel caries lesions in rat molars using synchrotron X‐ray microtomography

Dental caries is a ubiquitous infectious disease with a nearly 100% lifetime prevalence. Rodent caries models are widely used to investigate the etiology, progression and potential prevention or treatment of the disease. To explore the suitability of these models for deeper investigations of intact surface zones during enamel caries, the structures of early‐stage carious lesions in rats were characterized and compared with previous reports on white spot enamel lesions in humans. Synchrotron X‐ray microcomputed tomography non‐destructively mapped demineralization in carious rat molar specimens across a range of caries severity, identifying 52 lesions across the 30 teeth imaged. Of these lesions, 13 were shown to have intact surface zones. Depth profiles of fractional mineral density were qualitatively similar to lesions in human teeth. However, the thickness of the surface zone in the rat model ranges from 10 to 58 µm, and is therefore significantly thinner than in human enamel. These results indicate that a fraction of lesions in rat caries possess an intact surface zone and are qualitatively similar to human lesions at the micrometer scale. This suggests that rat caries models may be a suitable analog through which to investigate the structure of surface zone enamel and its role during dental caries.     

Comparative EPR study CO2− radicals in modern and fossil tooth enamel

Comparative EPR investigation of CO₂⁻ radicals in modern (γ-irradiated) and fossil samples of tooth enamel was performed. The samples studied were the enamel powders and plates, the latter demonstrating an orientation dependence of EPR spectra in an external magnetic field. It was found that the ratio between the axial and orthorhombic CO₂⁻ centers amounts appears to be different for modern and fossil enamels. This ratio can be estimated by modeling of EPR spectra lineshape of powders or, in the case of plates, from the orientation dependence of EPR spectra in an external magnetic field. It was assumed that the difference between modern and fossil enamels is caused by the transformation, in the course of time, of orthorhombic CO₂⁻ centers into axial ones. The equations that describe this process were deduced. Their solutions show that the ratio between the amounts of the axial and orthorhombic centers does not depend on the dose rate. This finding can be used for the development of the method to determine the fossil enamel age avoiding the determination of the annual dose.     

Raman spectroscopy with an integrated arrayed-waveguide grating

An integrated arrayed-waveguide grating fabricated in silicon-oxynitride technology is applied to Raman spectroscopy. After its validation by reproducing the well-known spectrum of cyclohexane, polarized Raman spectra are measured of extracted human teeth containing localized initial carious lesions. Excellent agreement is obtained between the spectra of healthy and carious tooth enamel measured with our integrated device and spectra recorded using a conventional Raman spectrometer. Our results represent a step toward the realization of compact, hand-held, integrated spectrometers, e.g. for the detection of dental caries at an early stage.