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.     

Phosphate and amide III mapping in sialoliths with Raman microspectroscopy

Sialoliths, a cause of the salivary gland infection, are reported to be composed of inorganic and organic substances. However, the precise mechanism of sialolith formation remains unclear. The purpose of this report is to elucidate this mechanism by analyzing the precise distribution of phosphate (an inorganic substance) and amide III (an organic substance) in sialoliths by using Raman microspectroscopy. Sialoliths from the submandibular gland duct were analyzed by this form of observation and by a scanning electron microscope (SEM) equipped with an energy‐dispersive X‐ray spectroscope (EDX). In Raman microspectroscopy we analyzed the spectral peak of the phosphate (PO₄³⁻) symmetric stretching vibrational mode (υ₁) at 960 cm⁻¹ and that of amide III at 1265 cm⁻¹ to demonstrate the mapping of an image of these elements showing a semiquantitative distribution of phosphate and amide III in the sialoliths. It was found that phosphate and amide III were concentrated at the center of the sialoliths, and the phosphate distribution in the sialoliths showed concentric laminations. These results indicated the possibility that the sialoliths originated from a nidus of organic materials and progressively grew by the deposition of layers of organic and inorganic materials. Copyright © 2008 John Wiley & Sons, Ltd.     

Applications of Raman Spectroscopy in Dentistry: Analysis of Tooth Structure

Abstract: Tooth enamel is the most mineralized tissue in the human body, and in this article the use of Raman spectroscopy for the analysis of tooth structure, a comparison with synthetic apatites, and use in dentistry are described. Spectral peaks that are related to dental hard and soft tissues are discussed, which provide crucial data in understanding the chemical structural properties of dentin and enamel. The Raman spectrum of dentin confirms the presence of crystalline phosphate-based minerals in dentin. Both dentin and enamel consist of two primary components: an inorganic or mineral phase that closely resembles hydroxyapatite and the Raman spectrum of dentin that confirms the presence of crystalline phosphate-based minerals in dentin. Hence, the mineral phase in dentin and enamel may be characterized essentially as nonstoichiometric substituted apatite. The presence of carbonate (A and B type) incorporated in the hydroxyapatite lattice is also confirmed by the presence of spectral bands. The organic phase, which is mainly composed of type I collagen, is confirmed by the spectral bands of amide I and amide II bands, tryptophan, and phenylalanine. Furthermore, these spectral bands associated with organic and inorganic parts of the enamel and dentin are useful in predicting early formation of carries formation.     

Study of the effects of unsupervised over‐the counter whitening products on dental enamel using μ‐Raman and μ‐EDXRF spectroscopies

The purpose of this in vitro study was to assess whether the mineralization degree and elemental content in tooth enamel are altered when bleaching the teeth with two different over‐the‐counter bleaching gels, exceeding the recommendations of the manufacturer. In order to perform this evaluation, 12 healthy teeth were used, six samples were treated with Teeth Whitening Home Kit, and the other six samples were treated with WHITE! (Bingo‐UK) bought in online shopping sites, for the period of 39 days. The pH of each product and the elemental content of each sample, before and after, were obtained by energy dispersive X‐ray spectrometry and phosphate (PO₄^3‐) profile was evaluated with Raman spectroscopy. Data was analyzed accordingly to a pre‐established plan with a mixed‐model ANOVA for repeated measures, significance was set at 5%. Both products were markedly acidic and below enamel critical level of 5.5. Moreover, seven days after treatment, demineralization was significant, wherein at the end of the study the degree of demineralization seems to be permanent. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Exposure of bremsstrahlung from beta-emitting therapeutic radionuclides

There has been an increased interest in beta therapeutic nuclear medicine, which emits relatively high-energy (>1 MeV) β-rays and the production in vivo of Bremsstrahlung sufficient for external imaging, the produced Bremsstrahlung radiation hazard warrants evaluation. The Bremsstrahlung dose from patient administered β-ray emitted radionuclide has been calculated by extending the national council on Radiation Protection and measurement model of a point source in air to account for biologic elimination of activity. We have estimated the probability of bremsstrahlung production, specific Bremsstrahlung constant (defined by Zanzonico et al.) and activity (A_release) in bone cortical, bone compact, different regions of tooth enamel (enamel dentin junction (EDJ), enamel middle surface, enamel inner surface), different regions of dentin (outer surface, middle surface, enamel dentin junction (EDJ)), soft tissue, lungs and skeleton for different therapeutic beta-emitting radionuclide. In the present calculations we have used modified atomic number (Z_mod) defined for bremsstrahlung process.Proper localization and quantification of incorporated beta emitters in bone and tooth are possible, because Bremsstrahlung production is greater in bone and tooth than soft tissue due to their high modified atomic number (Z_mod). Radionuclide therapy with pure β-ray emitters emitted in bone, tooth, soft tissue, lungs and skeleton does not require medical confinement of patients for radiation protection.     

Molecular structural analysis of noncarious cervical sclerotic dentin using Raman spectroscopy

Molecular structure of the sclerotic dentin in noncarious cervical lesions (NCCLs) including both the inorganic phase and organic phase was investigated using Raman spectroscopy. It was found that NCCL sclerotic dentin was hypermineralized with the mineral/matrix ratios 2–3 times higher than those of normal dentin, which was caused by both the increase of mineral content and decrease of organic matrix (collagen) content in the sclerotic dentin. For the inorganic phase, the phosphate band (PO₄³⁻, ν₁, symmetric stretching vibrational mode) in NCCL sclerotic dentin was shifted from 960 to 963 cm⁻¹, and the width of this band was decreased from 16.4 to 10.4 cm⁻¹, indicating that the degree of mineral crystallinity in NCCL sclerotic dentin was higher than that of normal dentin. In addition, the carbonate content in the mineral of NCCL sclerotic dentin was less than that of normal dentin. As compared to the inorganic phase, the changes within the organic phase were not dramatic. However, the changes in collagen cross‐link density along with other spectral changes were still detectable. There was a noteworthy reduction in the ratio of nonreducible to reducible cross‐links in the NCCL sclerotic dentin, indicating that cross‐link breaks occurred in the collagen matrix of the lesions. Copyright © 2009 John Wiley & Sons, Ltd.     

Background removal from polarized Raman spectra of tooth enamel using the wavelet transform

A wavelet transformation method is introduced to remove the large fluorescence background from polarized Raman spectra of stained tooth enamel. This method exploits the wavelet multiresolution decomposition where the experimental Raman spectrum is decomposed into signals with different frequency components, and where the lowest frequency background and highest frequency noise are removed. This method is optimized using a simulated collection of parallel‐polarized and cross‐polarized Raman spectra of the enamel and then applied to a set of experimental data. The results show that the wavelet transform technique can extract the pure spectra from background and noise, with the depolarization ratio used to discriminate between early dental caries and sound enamel preserved. Copyright © 2010 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.     

Investigation of adhesive–dentin interfaces using Raman microspectroscopy and small angle X‐ray scattering

Human dentin specimens were treated with two different etch‐and‐rinse adhesives, Single Bond 2 (SB2) and Prime & Bond NT (PBNT), and two composite resins, TPH and P60. Cross‐sectional samples, approximately 1 mm thick, were analyzed with Raman line mapping and imaging across the dentin–adhesive–composite interface. The integrated intensities of selected bands associated with adhesive, organic material, composite and hydroxyapatite of dentin were calculated to determine the distribution of adhesive infiltration into demineralized dentin. The results were compared with the enamel‐adhesive composite interface. The demineralized zone was smaller in the enamel‐adhesive interface than in the dentin–adhesive interface. The region of collagen‐adhesive crosslinking was wider in the PBNT adhesive than in the SB2 adhesive. However, a gap at the dentin–PBNT composite interface, which was not observed at the dentin–SB2 composite interface, might compromise the dentin–restoration bond. K‐means cluster analysis of the Raman images confirmed the findings. The ultrastructure of the dentin–resin interface was studied using scanning electron microscopy. Small‐angle X‐ray scattering was also applied to reveal and quantify fine‐scale structural features. SB2 adhesive was found to diffuse more into demineralized dentin along with greater nanosized aggregations in the hybrid layer. Copyright © 2011 John Wiley & Sons, Ltd.     

Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman and mid‐IR spectroscopic study of the magnesium carbonate minerals—brugnatellite and coalingite

Two hydrated hydroxy magnesium carbonate minerals brugnatellite and coalingite with a hydrotalcite‐like structure were studied by Raman spectroscopy. Intense bands are observed at 1094 cm⁻¹ for brugnatellite and at 1093 cm⁻¹ for coalingite attributed to the CO₃²⁻ν₁ symmetric stretching mode. Additional low intensity bands are observed at 1064 cm⁻¹. The existence of two symmetric stretching modes is accounted for in terms of different anion structural arrangements. Very low intensity bands at 1377 and 1451 cm⁻¹ are observed for brugnatellite, and the Raman spectrum of coalingite displays two bands at 1420 and 1465 cm⁻¹ attributed to the (CO₃)²⁻ν₃ antisymmetric stretching modes. Very low intensity bands at 792 cm⁻¹ for brugnatellite and 797 cm⁻¹ for coalingite are assigned to the CO₃²⁻ out‐of‐plane bend (ν₂). X‐ray diffraction studies by other researchers have shown that these minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality and explains why the Raman spectra of these minerals have not been previously or sufficiently described. A comparison is made with the Raman spectra of other hydrated magnesium carbonate minerals. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of uranium tetrafluoride (UF4) with Raman spectroscopy

The Raman spectrum of uranium tetrafluoride (UF₄) is unambiguously characterized with multiple Raman excitation laser sources for the first time. Across different laser excitation wavelengths, UF₄ demonstrates 16 distinct Raman bands within the 50–400 cm⁻¹ region. The observed Raman bands are representative of various F–F vibrational modes. UF₄ also shows intense fluorescent bands in the 325–750 nm spectral region. Comparison of the UF₄ spectrum with the ZrF₄ spectrum, its crystalline analog, demonstrates a similar Raman band structure consistent with group theory predictions for expected Raman bands. Additionally, a demonstration of combined scanning electron microscopy and in situ Raman spectroscopy microanalytical measurements of UF₄ particulates shows that despite the inherent weak intensity of Raman bands, identification and characterization are possible for micron‐sized particulates with modern instrumentation. The published well‐characterized UF₄ spectrum is extremely relevant to nuclear materials and nuclear safeguard applications. Published 2016. This article is a U.S. Government work and is in the public domain in the USA. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd.     

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.     

Transition of synthetic chromium oxide gel to crystalline chromium oxide: a hot‐stage Raman spectroscopic study

Chromium oxide gel material was synthesised and appeared to be amorphous in X‐ray diffraction study. The changes in the structure of the synthetic chromium oxide gel were investigated using hot‐stage Raman spectroscopy based upon the results of thermogravimetric analysis. The thermally decomposed product of the synthetic chromium oxide gel in nitrogen atmosphere was confirmed to be crystalline Cr₂O₃ as determined by the hot‐stage Raman spectra. Two bands were observed at 849 and 735 cm⁻¹ in the Raman spectrum at 25 °C, which were attributed to the symmetric stretching modes of O Cr^III OH and O Cr^III O. With temperature increase, the intensity of the band at 849 cm⁻¹ decreased, while that of the band at 735 cm⁻¹ increased. These changes in intensity are attributed to the loss of OH groups and formation of O Cr^III O units in the structure. A strongly hydrogen‐bonded water H O H bending band was found at 1704 cm⁻¹ in the Raman spectrum of the chromium oxide gel; however, this band shifted to around 1590 cm⁻¹ due to destruction of the hydrogen bonds upon thermal treatment. Six new Raman bands were observed at 578, 540, 513, 390, 342 and 303 cm⁻¹ attributed to the thermal decomposed product Cr₂O₃. The use of the hot‐stage Raman spectroscopy enabled low‐temperature phase changes brought about through dehydration and dehydroxylation to be studied. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopy of the sampleite group of minerals

Raman and infrared spectroscopy enabled insights into the molecular structure of the sampleite group of minerals. These minerals are based upon the incorporation of either phosphate or arsenate with chloride anion into the structure, and as a consequence the spectra reflect the bands attributable to these anions, namely, phosphate or arsenate with chloride. The sampleite vibrational spectrum reflects the spectrum of the phosphate anion and consists of ν₁ at 964 cm⁻¹, ν₂ at 451 cm⁻¹, ν₃ at 1016 and 1088 cm⁻¹ and ν₄ at 643, 604, 591 and 557 cm⁻¹. The lavendulan spectrum consists of ν₁ at 854 cm⁻¹, ν₂ at 345 cm⁻¹, ν₃ at 878 cm⁻¹ and ν₄ at 545 cm⁻¹. The Raman spectrum of lemanskiite is different from that of lavendulan consistent with a different structure. Low wavenumber bands at 227 and 210 cm⁻¹ may be assigned to CuCl transverse/longitudinal (TO/LO) optic vibrations. Raman spectroscopy identified the substitution of arsenate by phosphate in zdenekite and lavendulan. Copyright © 2007 John Wiley & Sons, Ltd.     

Density functional theory study and vibrational analysis of FT‐IR and FT‐Raman spectra of N‐hydroxyphthalimide

The Fourier transform infrared (FT‐IR) spectrum of N‐hydroxyphthalimide has been recorded in the range of 4000–400 cm⁻¹, and the Fourier transform Raman (FT‐Raman) spectrum of N‐hydroxyphthalimide has been recorded in the range of 4000–50 cm⁻¹. With the hope of providing more and effective information on the fundamental vibrations, the Density Functional Theory (DFT)‐Becke3‐Lee‐Yang‐Parr (B3LYP) level with 6‐31G* basis set has been employed in quantum chemical analysis, and normal coordinate analysis has been performed on N‐hydroxyphthalimide by assuming C_s symmetry. The computational wavenumbers are in good agreement with the observed results. The theoretical spectra obtained along with intensity data agree well with the observed spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Nanocarbon hybrids of graphene‐based materials and ultradispersed diamond: investigating structure and hierarchical defects evolution with electron‐beam irradiation

We report the influence of electron‐beam (E‐beam) irradiation on the structural and physical properties modification of monolayer graphene (Gr), reduced graphene oxide (rGO) and graphene oxide (GO) with ultradispersed diamond (UDD) forming novel hybrid composite ensembles. The films were subjected to a constant energy of 200 keV (40 nA over 100 nm region or electron flux of 3.9 × 10¹⁹ cm⁻²s⁻¹) from a transmission electron microscope gun for 0 (pristine) to 20 min with an interval of 2.5 min continuously – such conditions resemble increased temperature and/or pressure regime, enabling a degree of structural fluidity. To assess the modifications induced by E‐beam, the films were analyzed prior to and post‐irradiation. We focus on the characterization of hierarchical defects evolution using in situ transmission electron microscopy combined with selected area electron diffraction, Raman spectroscopy (RS) and Raman mapping techniques. The experiments showed that the E‐beam irradiation generates microscopic defects (most likely, interstitials and vacancies) in a hierarchical manner much below the amorphization threshold and hybrids stabilized with UDD becomes radiation resilient, elucidated through the intensity, bandwidth, and position variation in prominent RS signatures and mapping, revealing the defects density distribution. The graphene sheet edges start bending, shrinking, and generating gaps (holes) at ~10–12.5 min owing to E‐beam surface sputtering and primary knock‐on damage mechanisms that suffer catastrophic destruction at ~20 min. The microscopic point defects are stabilized by UDD for hybrids in the order of GO > rGO ≥ Gr besides geometric influence, i.e. the int erplay of curvature‐induced (planar vs curved) energy dispersion/absorption effects. Furthermore, an attempt was made to identify the nature of defects (charged vs residual) through inter‐defect distance (i.e. L_D). The trends of L_D for graphene‐based hybrids with E‐beam irradiation implies charged defects described in terms of dangling bonds in contrast to passivated residual or neutral defects. More importantly, they provided a contrasting comparison among variants of graphene and their hybrids with UDD. Copyright © 2015 John Wiley & Sons, Ltd.     

Development of a two‐dimensional imaging system of X‐ray absorption fine structure

A two‐dimensional imaging system of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I₀ measurement, a sample stage, and a two‐dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X‐ray intensity. The X‐ray energy shift in the vertical direction, which originates from the vertical divergence of the X‐ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ～0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn₂O₄ cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li⁺‐defect sites in the spinel crystal structure. The two‐dimensional‐imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes.     

Raman microspectroscopic mapping or thermal system used to investigate milling‐induced solid‐state conversion of famotidine polymorphs

Confocal Raman microspectroscopy was used to nondestructively determine the polymorphic conversion of famotidine in the course of the milling process. A mapping system was applied to assess the blending uniformity of each polymorphic component in the milled mixture. Raman microspectroscopy combined with a thermal analyzer was also used to investigate the synergistic co‐effects of milling and heating on the polymorphic conversion of famotidine polymorphs. Famotidine has two polymorphs, forms A and B, the raw material of famotidine used was proved to be of form B. The Raman peak intensity ratio of the 2920 cm⁻¹ band for form A and 2897 cm⁻¹ band for form B was used to act as an indicator to evaluate the polymorphic conversion of famotidine form B to form A after different milling courses. The results indicate that the peak intensity at 2897 cm⁻¹ gradually decreased with the milling time, whereas the peak intensity at 2920 cm⁻¹ slowly enlarged, suggesting the polymorphic conversion of famotidine from form B to form A. The longer milling process might strongly induce and promote this polymorphic conversion of famotidine. Both polymorphic forms of famotidine were found to be well uniformly distributed within the milled samples due to their smaller varieties by using the Raman microscopic mapping system. The temperature effect could synergistically accelerate the polymorphic conversion of famotidine from form B to form A in the milled sample. The thermal‐dependent critical temperature for sharply enhancing the content of famotidine form A in each milled sample was also identified. Copyright © 2007 John Wiley & Sons, Ltd.     

Observation of resonance electronic and non‐resonance‐enhanced vibrational natural Raman optical activity

Natural resonance electronic Raman optical activity (ROA) is observed for the first time. Coincidently, the first example of vibrational ROA enhanced by low‐lying electronic transition is reported. These new phenomena were measured using the rare‐earth complex Eu(tfc)₃ (+)‐tris[3‐trifluoroacetyl‐D ‐camphorato]europium(III), where electronic resonance occurs between the 532‐nm laser excitation and the ⁷F₁ → ⁵D₁ transition of the Eu³⁺ metal center. Electronic Raman spectra involve the Raman transitions terminating on the low‐lying electronic states of Eu(tfc)₃. The observed vibrational ROA spectra are enhanced relative to typical ROA spectra by the proximity of vibrational states of Eu(tfc)₃ to its low‐lying electronic states with significant magnetic‐dipole character, whereas the parent vibrational Raman spectra do not appear to be resonance‐enhanced since the 532‐nm vibrational Raman spectrum has similar relative intensities to the corresponding Raman spectrum measured with 1064‐nm laser excitation. Copyright © 2010 John Wiley & Sons, Ltd.