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.     

Decomposition of the angular ESR spectra of fossil tooth enamel fragments

The ESR spectra of a fragment of fossil tooth enamel were measured by rotating it in 10° increments over 360° around its three major axes. We used an automated simulated annealing (SA) procedure for the mathematical decomposition of the spectra. The SA approach is particularly robust in finding global solutions rather than getting stuck in local minima. All angular measurements could be fitted with four Gaussian lines, all of which could be attributed to components of CO₂^? radicals. The results imply that the tooth enamel fragment contains at least two different types of oriented CO₂^? radicals, plus about 9% of non-oriented CO₂^? radicals. The oriented components were tentatively attributed to axial and orthorhombic CO₂^? radicals. Their explicit locations in the crystal domains of the tooth enamel remain unresolved.     

Evaluating the accuracy of ESR dose determination of pseudo-Early Pleistocene fossil tooth enamel samples using dose recovery tests

In ESR dating of Early Pleistocene fossil tooth enamel samples, the fitting function used for the evaluation of the D_E value is undoubtedly among the major sources of uncertainty. Dose recovery tests performed on fossil tooth enamel showing D_E values >1,000 Gy demonstrate: (i) that high precision ESR measurements (<0.5%) and high D_E reproducibility (<5%) may be achieved; (ii) the appropriateness of the Double Saturating Exponential (DSE) fitting function for ESR dose reconstruction. In contrast, the SSE function, which has been almost exclusively used so far, does simply not correctly describe the behavior of the radiation induced ESR signal of tooth enamel with the dose.Several fitting functions and data weighting options were tested and the combination of a DSE with data weighted by the inverse of the squared intensities is the procedure providing the most accurate D_E results. However, the SSE may nevertheless sometimes produce consistent results if D_max does not exceed 6*D_E. Further work is required in that direction in order to determine more precisely in which conditions the SSE could be used as a fair approximation of the DSE function for these samples.     

Effect of spectrum processing procedure on the linearity of EPR dose reconstruction in tooth enamel

Electron Paramagnetic Resonance (EPR) spectroscopy with tooth enamel is a widely used method of dosimetry. The accuracy of EPR tooth dosimetry depends on the spectrum processing procedure, the quality of which, in its turn, relies on instrumental noise and the signals from impurities. This is especially important in low-dose evaluation. The current paper suggests a method to estimate the accuracy of a specific spectrum processing procedure. The method is based on reconstruction of the radiation-induced signal (RIS) from a simulated spectrum with known RIS intensity. The Monte Carlo method was used for the simulations. The model of impurity and noise signals represents a composite residual spectrum (CRS) obtained by subtraction of the reconstructed RIS and the native background signal (BGS) from enamel spectra measured in HMGU (Neuherberg, Germany) and IMP (Yekaterinburg, Russia). The simulated spectra were deconvoluted using a standard procedure. The method provides an opportunity to compare the simulated “true” RIS with reconstructed values. Two modifications of the EPR method were considered: namely, with and without the use of the reference Mn²⁺ signals. It was observed that the spectrum processing procedure induces a nonlinear dose response of the reconstructed EPR amplitude when the height of the true RIS is comparable with the amplitudes of noise-like random splashes of CRS. The area of nonlinearity is below the limit of detection (DL). The use of reference Mn²⁺ signals can reduce the range of nonlinearity. However, the impact of the intensities of CRS random signals on nonlinearity is two times higher than the one observed when the reference signals were not used. The reproducibility of the software response is also dependent on both the amplitude of the CRS and the use of a reference signal, and it is also two times more sensitive to the amplitude of the CRS. In most EPR studies, all of the data are used, even those for which the dose value is lower than the DL. This study shows that low doses evaluated with the help of linear dose–response can be significantly overestimated. It is recommended that linear dose response calibration curves be constructed using only data above the DL. Data below the DL should be interpreted cautiously.     

Removal of inelastic scattering part from Ti2p XPS spectrum of TiO2 by deconvolution method using O1s as response function

Ti2p and O1s XPS spectra of a clean surface of single crystal TiO₂ fractured in situ were taken to study the removal of the inelastic scattering part from the Ti2p spectrum. The features of inelastic scattering peaks in EELS were more influenced by surface than O1s XPS. It indicates that O1s XPS is proper as the response function to deconvolute a Ti2p spectrum. FWHM of the non-energy loss peak of Ti2p_3/2 is smaller than that of O1s. When the raw O1s spectrum is used as the response function, the deconvoluted spectrum has negative intensity values in some regions and beat waves. The replacement of the non-energy loss peak of O1s with narrower Gaussian peak takes off the beat waves. Peak separation of the deconvoluted spectrum reveals that it has six peaks. Two of them are main peaks of Ti2p_3/2 and 2p_1/2. The others are classified into two kinds of satellite peaks, whose energy separation from the main peaks are 3 and 13 eV. Although the latter satellites have been discussed by many authors, the former satellites are first reported here.     

Effects of annealing in nitrogen atmosphere and HCl-etching on the photoluminescence spectra of spray-deposited CdS:In thin films

The aim of this work is to find the effect of processing on the photoluminescence (PL) of spray-deposited CdS:In thin films. So the PL spectra of the as-deposited, annealed and HCl-etched CdS:In thin films prepared by the spray pyrolysis (SP) technique were recorded at T = 23 K. The yellow and red bands were observed in the spectrum of the as-deposited film beside bands with weaker intensity in the infrared region. The PL signal was weakened by annealing in nitrogen atmosphere at T = 400 °C and HCl-etching. A deconvolution peak fit was established to find the effects of these treatments on the different bands. The spectrum of the as-deposited film was deconvoluted to 12 peaks, which were reduced to 6 peaks after both treatments. It was found that both treatments have approximately the same effects on the PL spectra; that is they removed most of the peaks and shoulders in the red and infrared regions and attenuated most of the peaks in the yellow region. Some peaks were blue-shifted after annealing which was explained by the growth of nanocrystallites due to the thermal stress that results from the different expansion coefficients of the film and the substrate. These changes were accompanied by a phase change from the mixed (cubic and hexagonal) phase to the hexagonal phase as shown in the X-ray diffractograms.     

Fractional volume integration in two-dimensional NMR spectra: CAKE, a Monte Carlo approach

Quantitative information from multi-dimensional NMR experiments can be obtained by peak volume integration. The standard procedure (selection of a region around the chosen peak and addition of all values) is often biased by poor peak definition because of peak overlap. Here we describe a simple method, called CAKE, for volume integration of (partially) overlapping peaks. Assuming the axial symmetry of two-dimensional NMR peaks, as it occurs in NOESY and TOCSY when Lorentz-Gauss transformation of the signals is carried out, CAKE estimates the peak volume by multiplying a volume fraction by a factor R. It represents a proportionality ratio between the total and the fractional volume, which is identified as a slice in an exposed region of the overlapping peaks. The volume fraction is obtained via Monte Carlo Hit-or-Miss technique, which proved to be the most efficient because of the small region and the limited number of points within the selected area. Tests on simulated and experimental peaks, with different degrees of overlap and signal-to-noise ratios, show that CAKE results in improved volume estimates. A main advantage of CAKE is that the volume fraction can be flexibly chosen so as to minimize the effect of overlap, frequently observed in two-dimensional spectra.     

Alpha and beta dose gradients in tooth enamel

New results describing gradients in effective alpha and beta doses within a layer of tooth enamel in planar geometry are presented. The alpha (track) dose to an enamel layer is calculated using an algorithm similar to that of Aitken (Aitken, M.J., 1987. Alpha dose to a thin layer. Ancient TL 5, 1–3.). The code for ROSY version 1.4 (Brennan, B.J., Rink, W.J., Rule, E.M., Schwarcz, H.P., Prestwich, W.V., 1999. The ROSY ESR dating software. Ancient TL, in press.) incorporates this algorithm. The approach allows for variation of the alpha track dose near the edges of the enamel, and we describe the gradient of the alpha track dose within 40 μm of each edge of the enamel for natural sources. In ESR or luminescence dating of naturally thin layers, for which stripping of the surface layer containing the alpha dose gradients may not be feasible, age estimates may change by as much as 5–10% when the detailed alpha dose calculation is included. Modern Monte Carlo-based results for the variation of beta dose for depths up to 2 mm are compared with ROSY results. For external irradiation by different sources, the attenuation of the ROSY dose estimate with depth is usually less rapid than that of the Monte Carlo-based estimate. The ROSY estimate of average beta dose to a layer in this case is between 5 and 18% higher than the Monte Carlo estimate.     

Experimental determinations of beta attenuation in planar dose geometry and application to ESR dating of tooth enamel

Two experiments were performed to determine the distribution of beta dose in a target medium as a function of distance from a planar source (2π geometry). In Experiment 1 planar absorbers were used to simulate depth in the target medium, and the attenuated dose that penetrated the intervening absorbers was detected using thermoluminescence from CaSO₄:Tm. In experiment 2 pellets of powdered tooth enamel were situated in a cavity in solid tooth enamel. Dose response of the electron spin resonance (ESR) signals in the pellets allowed direct detection of dose distribution within the target medium. The dose distributions were found to agree more closely with Monte Carlo calculations and with one-group transport theory (Prestwich et al., 1997 and Brennan et al., 1997) than with approximations used widely in ESR dating applications (Grün, 1986). Although the latter were supported by experiments by Aitken et al. (1985), the results of experiment 1 provided data to suggest that departure from 2π geometry was unacceptably large in the Aitken et al. (1985) configuration. The beta doses obtained by one-group theory in typical target volumes of enamel were 17 to 40% lower than those obtained using the Grün approximation. It was concluded that one-group transport theory provides the best available routine tool for calculations of beta dose attenuation in near-planar target materials (e.g. tooth enamel and shell) irradiated by natural sources, although Monte Carlo methods are better and could eventually be introduced into the ROSY ESR dating program (Brennan et al., 1997). It was also concluded that a revision of previously published ESR ages using one-group transport for beta dosimetry will be needed. For cases where the U concentrations in enamel are generally low (less than a few ppm), previously published ESR ages on tooth enamel are systematically too young by 5–30%.     

PLE spectra analysis of the sub-structure in the absorption spectra of CdSeS quantum dots

The semiconductor CdSeS quantum dots (QDs) embedded in glass are analysed by means of absorption spectra, photoluminescence (PL) spectra and photoluminescence excitation (PLE) spectra. The peaks of absorption spectra shift to lower energies with the size of QD increasing, which obviously shows a quantum-size effect. Using the PLE spectra, the physical origin of the lowest absorption peak is analysed. In PLE spectra, the lowest absorption peak can be deconvoluted into two peaks that stem from the transitions of 1S_3/2--1S_e and 2S_3/2--1S_e respectively. The measured energy difference between the two peaks is found to decrease with the size of QD increasing, which agrees well with the theoretical calculation for the two transitions. The luminescence peak of defect states is also analysed by PLE spectra. Two transitions are present in the PLE, which indicates that the transitions of 1S_3/2--1S_e and 2S_3/2--1S_e are responsible for the defect states luminescence.     

Feasibility of radiation sterilization and dosimetric features of ampicillin: an electron spin resonance study

In the present work, it was aimed to identify radical species produced by gamma irradiation (3–34?kGy) of solid ampicillin, to determine its spectroscopic, dosimetric, stability and kinetic behavior, and to investigate feasibility of the radiation sterilization feature of ampicillin by using electron spin resonance (ESR) spectroscopy. ESR experiments were performed at low and high temperatures (130–400?K) to examine the characteristic properties of the radical intermediates that are produced in ampicillin by gamma radiation treatment. Unirradiated ampicillin presented no ESR signal but irradiated samples exhibited ESR spectra with four resonance peaks spread over a magnetic field range of 8?mT. The spectral parameters of the central resonance line of the spectrum are g?=?2.0044 and ΔH_pp?=?0.08?mT. An exponential growth function of the applied dose was found to describe best the experimental dose–response data and it was found that ampicillin did not exhibit the feature of a good dosimetric material as its ESR intensity was relatively weak even for the samples irradiated at high level of doses. G_mean value of gamma-irradiated ampicillin was found to be 4.6?±?0.9?×?10^?9?mol/J, which is very small compared to irradiated alanine solid sample. However, the discrimination of irradiated ampicillin from unirradiated one was possible even ～3 months after storage at normal conditions. The simulation calculations indicated that gamma irradiation created two different radical species in solid ampicillin. Decay activation energy of the radical species which is mostly responsible from central intense resonance line is calculated to be 55.6?±?3.2?kJ/mol by using the signal intensity decay data derived from annealing studies. It was concluded that ampicillin could be sterilized by gamma radiation and ESR spectroscopy can be used as a potential technique to monitor its radiosterilization process.     

Luminescence studies of rare earth doped yttrium gadolinium mixed oxide phosphor

This paper reports the photoluminescence and thermoluminescence properties of gamma ray induced rare earth doped yttrium gadolinium mixed oxide phosphor. The europium (Eu³⁺) was used as rare earth dopant. The phosphor was prepared by chemical co-precipitation method according to the formula (Y_2−x−yGd_x) O₃: Eu_y³⁺ (x=0.5; y=0.05). The photoluminescence emission spectrum of the prepared phosphor shows intense peaks in the red region at 615 nm for ⁵D₀→⁷F₂ transitions and the photoluminescence excitation spectra show a broad band located around 220–270 nm for the emission wavelength fixed at 615 nm. The thermoluminescence studies were carried out after irradiating the phosphor by gamma rays in the dose range from 100 Gy to 1 KGy. In the thermoluminescence glow curves, one single peak was observed at about 300 °C of which the intensity increases linearly in the studied dose range of gamma rays. The glow peak was deconvoluted by GlowFit program and the kinetic parameters associated with the deconvoluted peaks were calculated. The kinetic parameters were also calculated by various glow curve shape and heating rate methods.     

Radiation sensitivity and dosimetric features of sultamicillin tosylate: an electron spin resonance study

Particular interest now centers on the preparation of sterile unit-dose preparations. When preparations are purified from microorganisms using classic sterilization techniques, serious degradations may occur, especially in temperature sensitive drugs and drug active components. Sultamicillin is the tosylate salt of the double ester of sulbactam plus ampicillin. Sultamicillin (SULT) tosylate has previously been shown to be clinically and bacteriologically effective in a variety of infections. The use of high-energy radiation, such as gamma rays, for the sterilization of pharmaceuticals offers considerable interest because of the clear advantages this process has compared with other methods of sterilization. However, radiosensitivity of irradiated pharmaceuticals is important in this respect. Thus, radiosensitivity of SULT and its potential use as a dosimetric material were investigated by electron spin resonance (ESR) spectroscopy in the present work. Samples of SULT powder were irradiated at doses of 3, 6, 10 and 15 kGy and ESR spectra were recorded at room and at different temperatures. Variations of different spectroscopic parameters with irradiation dose, temperature and storage time were evaluated using data derived from experimental ESR spectra which exhibited five different resonance peaks. Stabilities of the radiolytic intermediates at high temperatures were also investigated through annealing studies performed at 340, 345 and 350 K. Rapid decreases in resonance peak heights above 325 K were considered a manifestation of the unstable character of the radiolytical intermediates at high temperature, although they decayed relatively slowly at room temperature. Seven different mathematical functions have been tried to fit the experimental dose–response data, and a power function of the applied dose was found to describe best the dose–response data.     

Deconvolution of complex EPR spectrum of tooth enamel into three components: native,dosimetric and mechanical

A software was developed on the base of non-linear simulation, which allowed the deconvolution of EPR spectra of tooth enamel into three components: native, radiation- and mechanically induced. The software was designed for the reconstruction of individual absorbed doses by EPR spectra of tooth enamel using the method of additive irradiation of samples. It has been demonstrated with the help of this program that the presence of mechanically induced paramagnetic centers in enamel samples led to an excessive individual absorbed dose reconstructed by EPR spectra of tooth enamel.     

Comparison of intrinsic zero-energy loss and Shirley-type background corrected profiles of XPS spectra for quantitative surface analysis: Study of Cr, Mn and Fe oxides

The intrinsic zero-energy loss profiles of transition metal 2p and 3p XPS spectra for Cr, Mn, and Fe oxides are obtained by spectral deconvolution and compared with Shirley-type background corrected profiles. The metal core level spectra are deconvoluted by O 1s spectra as the response function of each oxide. As the O 1s spectra include intrinsic and extrinsic energy loss parts, the background corrected core level spectra are zero-energy loss spectra. The good agreement of the deconvoluted spectra with the reported spectra obtained by the many body effect theory indicates that the background subtraction method is accurate. A comparison of the deconvoluted with the background corrected spectra of the Shirely-type subtraction reveals that almost all the spectra coincide with each other except for Fe 3p with -Fe₂O₃. The good coincidence of the Shirley-type corrected spectra with the deconvoluted and calculated spectra indicates that Shirley-type background correction can be used for daily quantitative surface analysis.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

The Magnetic Order in Ion Irradiated Graphite

The magnetism of highly oriented pyrolytic graphite(HOPG) induced by ion implantation is investigated with electron spin resonance(ESR) spectroscopy and magnetization measurements.The results indicate that the ESR spectra of the HOPG sample correlate with ion species,incident energy and dose of implantation.The correlation of the ESR spectra and magnetism of the HOPG sample with ~(12)C~+ ion implantation and H~+ ion implantation are studied in detail.The ferromagnetism of the HOPG sample is likely related to the asymmetric L1 line,which may be attributed to the interaction between localized defects and itinerant electrons occupied in the 'impurity'band induced by ion implantation.     

Beta-gradient isochron dating of thin tooth enamel layers using ESR

The theoretical and experimental basis for the development of a new dating technique using beta-gradient isochrons and ESR is presented. For uranium-free portions of enamel adjacent to sediment, we can determine a beta-dose gradient due to sources in the nearest 2 mm layer of the sediment. If the equivalent dose to successive layers of enamel is plotted against the beta dose rate to each layer, an estimate of the age (equal to the slope of the line) that depends only on the environmental beta dose rate can be determined. Experimental methods and results for four teeth are discussed. The significance of this approach lies in its ability to isolate an age estimate that is independent of the uranium uptake model, since only portions of the enamel which are far away enough from internal sources of uranium, such as dentine, are used. In addition, this technique provides a time-averaged estimate of the actual gamma plus cosmic dose rate provided that a reasonable estimate of the average moisture content is used to calculate the environmental beta dose rate.     

Spectral and defect analysis of Cu-doped combustion synthesized new SrAl4O7 phosphor

A simple solution combustion synthesis route for preparation of Cu-doped SrAl₄O₇ has been described. Average particle size of 33 nm and platelet-like morphology has been observed. ESR studies confirm the presence of Cu in polycrystalline SrAl₄O₇. Bright-green luminescence under near-UV irradiation arising due to transition between Cu⁺ levels with microsecond level decay time makes it suitable for application in phosphor converted light emitting diode (LED). TL measurements show broad glow peaks which when deconvoluted indicate activation energies in the range of 0.6-1.1 eV and elucidate the trapping dynamics.