NIR to visible up-conversion, infrared luminescence, thermoluminescence and defect centres in Y(2)O(3) : Er phosphor

Er(3+) doped Y(2)O(3) phosphor was prepared by the solution combustion method and characterized using powder x-ray diffraction and energy-dispersive analysis of x-ray mapping studies. Room temperature near infrared (NIR) to green up-conversion (UC) emissions in the region 520-580 nm {((2)H(11/2), (4)S(3/2)) -> (4)I(15/2)} and red UC emissions in the region 650-700 nm ((4)F(9/2) -> (4)I(15/2)) of Er(3+) ions have been observed upon direct excitation to the (4)I(11/2) level using similar to 972 nm laser radiation of nanosecond pulses. The possible mechanisms for the UC processes have been discussed on the basis of the energy level scheme, the pump power dependence as well as based on the temporal evolution. The excited state absorption is observed to be the dominant mechanism for the UC process. Y(2)O(3) : Er exhibits one thermally stimulated luminescence (TSL) peak around 367 degrees C. Electron spin resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TSL peak. Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of at least three distinct centres. One of them (centre I) with principal g-values g(parallel to) = 2.0415 and g(perpendicular to) = 2.0056 is identified as O(2)(-) centre while centre II with an isotropic g-factor 2.0096 is assigned to an F(+)-centre (singly ionized oxygen vacancy). Centre III is also assigned to an F(+)-centre with a small g-factor anisotropy (g(parallel to) = 1.974 and g(perpendicular to) = 1.967). Additional defect centres are observed during thermal annealing experiments and one of them appearing around 330 degrees C grows with the annealing temperature. This centre (assigned to an F(+)-centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and the F-centre appears to correlate with the observed TSL peak in Y2O3 : Er phosphor. The trap depth for this peak has been determined to be 0.97 eV from TSL data.

Diagnostic reference levels for the most frequent radiological examinations carried out in Brazil

Objectives. A large-scale survey of doses to patients undergoing the most frequent radiological examinations was carried out in health services in Sao Paulo (347 radiological examinations per 1 000 inhabitants), the most populous Brazilian state. Methods. A postal dosimetric kit with thermoluminescence dosimeters was used to evaluate the entrance surface dose (ESD) to patients. A stratified sampling technique applied to the national health database furnished important data on the distribution of equipment and the annual number of examinations. Chest, head (skull and sinus), and spine (cervical, thoracic, and lumbar) examinations were included in the trial. A total of 83 rooms and 868 patients were included, and 1 415 values of ESD were measured. Results. The data show large coefficients of variation in tube charge, giving rise to large variations in ESD values. Also, a series of high ESD values associated with unnecessary localizing fluoroscopy were detected. Diagnostic reference levels were determined, based on the 75th percentile (third quartile) of the ESD distributions. For adult patients, the diagnostic reference levels achieved are very similar to those obtained in international surveys. However, the situation is different for pediatric patients: the ESD values found in this survey are twice as large as the international recommendations for chest radiographs of children. Conclusions. Despite the reduced number of ESD values and rooms for the pediatric patient group, it is recommended that practices in chest examinations be revised and that specific national reference doses and image quality be established after a broader survey is carried out.

Thermoluminescence, infrared reflectivity and electron paramagnetic resonance properties of hemimorphite

Silicate mineral hemimorphite has been investigated concerning its TL, IR and EPR properties. A broad TL peak around 180 degrees C and a weaker and narrower peak around 360 degrees C were found in a sample annealed at 600 degrees C for I h and then irradiated. The deconvolution using the CGCD method revealed peaks around 132, 169, 222 and 367 degrees C. The reflectivity measurements showed several bands in the NIR region due to H(2)O, OH and Al-OH complexes. No band was observed in the visible region. The thermal treatments were carried out from similar to 110 to 940 degrees C and dehydration was observed, first causing a diminishing optical absorption in general and the disappearance of water and hydroxyl absorption bands. The EPR spectrum of natural hemimorphite, presented Cu(2+) signals at g = 2.4 and g = 2.1 plus E(1)` signal superposed to Fe(3+) signal around g = 2.0. (C) 2008 Elsevier Ltd. All rights reserved.

Dating archeological ceramics from the Valley of Vitor, Arequipa by the TL method

The age of some ancient pottery from the Valley of Vitor in the region of Arequipa, Peru, is determined by the thermoluminescence (TL) method. For dating, a 325 degrees C TL peak was used and irradiation with -dose from 5 to 50Gy was carried out for the additive method, and from 0.4 to 5Gy for the regeneration method. For these dose values, the TL intensity is observed to grow linearly, obtaining an accumulated dose of 1.62 +/- 0.09Gy and 1.36 +/- 0.03Gy for the additive and regeneration methods, respectively. The age (A) of the sample was calculated by the two methods, being A=867 +/- 195 years after Christ (AC) for the additive method and A=1050 +/- 157 years AC for the regeneration method. Both results are within 800-1200 years AC, which is the period of the Wari culture.

Thermoluminescence, electron paramagnetic resonance and optical absorption in natural and synthetic rhodonite crystals

Thermoluminescence, electron paramagnetic resonance and optical absorption properties of rhodonite, a natural silicate mineral, have been investigated and compared to those of synthetic crystal, pure and doped. The TL peaks grow linearly for radiation dose up to 4 kGy, and then saturate. In all the synthetic samples, 140 and 340 degrees C TL peaks are observed; the difference occurs in their relative intensities, but only 340 degrees C peak grows strongly for high doses. Al(2)O(3) and Al(2)O(3) + CaO-doped synthetic samples presented several decades intenser TL compared to that of synthetic samples doped with other impurities. A heating rate of 4 degrees C/s has been used in all the TL readings. The EPR spectrum of natural rhodonite mineral has only one huge signal around g = 2.0 with width extending from 1,000 to 6,000 G. This is due to Mn dipolar interaction, a fact proved by numerical calculation based on Van Vleck dipolar broadening expression. The optical absorption spectrum is rich in absorption bands in near-UV, visible and near-IR intervals. Several bands in the region from 540 to 340 nm are interpreted as being due to Mn(3+) in distorted octahedral environment. A broad and intense band around 1,040 nm is due to Fe(2+). It decays under heating up to 900 degrees C. At this temperature it is reduced by 80% of its original intensity. The pink, natural rhodonite, heated in air starts becoming black at approximately 600 degrees C.

TL, EPR and optical absorption in natural grossular crystal

Grossular is one of six members of silicate Garnet group. Two samples GI and GII have been investigated concerning their luminescence thermally stimulated (TL). EPR and optical absorption and the measurements were carried out to find out whether or not same point defects are responsible for all three properties. Although X-rays diffraction analysis has shown that both GI and GII have practically the same crystal structure of a standard grossular crystal, they presented different behavior in many aspects. The TL glow curve shape, TL response to radiation dose, the effect of annealing at high temperatures before irradiation, the dependence of UV bleaching parameters on peak temperature, all of them differ going from GI to GII. The EPR signals around g = 2.0 as well as at g = 4.3 and 6.0 have much larger intensity in GI than in GII. Very high temperature (> 800 degrees C annealing causes large increase in the bulk background absorption in GI, however, only very little in GII. In the cases of EPR and optical absorption, the difference in their behavior can be attributed to Fe3+ ions; however, in the TL case one cannot and the cause was not found as yet. (C) 2008 Elsevier B.V. All rights reserved.

Thermo luminescence of natural and synthetic diopside

Diopside, a natural silicate mineral of formula CaMgSi2O6, has been investigated concerning its thermoluminescence (TL) and electron paramagnetic resonance (EPR) properties. Glow curves and TL vs. gamma-dose were obtained irradiating natural samples to additional dose varying from 50 to 10,000Gy. Except for a 410 degrees C peak found in the Al-doped artificial diopside, all the other peaks grow linearly with radiation dose, but saturate beyond -1 kGy. To investigate high-temperature effect before irradiation, measurements of TL intensity in samples annealed at 500-900 degrees C and then irradiated to I kGy gamma-dose were carried out. Also the TL emission spectrum has been obtained. To compare with natural diopside, a synthetic pure polycrystal was produced and further those doped with iron, aluminum and manganese were also produced. (c) 2007 Elsevier B.V. All rights reserved.

Can efficiency of the photosensitizer be predicted by its photostability in solution?

We have investigated a possible correlation between the photostability and photodynamic efficacy for different photosensitizers; hematoporphyrin derivatives and chlorines. To perform such analysis, we combined the depth of necrosis (d (nec)) measurement, expressed by the light threshold dose and a photodegradation parameter, measured from investigation of photosensitizer degradation in solution. The d (nec) analysis allows us to determine the light threshold dose and compare its value with the existent results in the literature. The use of simple models to understand basic features of Photodynamic Therapy (PDT) may contribute to the solid establishment of dosimetry in PDT, enhancing its use in the clinical management of cancers and others lesions. Using hematoporphyrin derivatives and chlorines photosensitizers we investigated their properties related to the photodegradation in solution and the light threshold dose (D (th)) in rat livers.

Influence of pH on the phototransformation process of PhotogemA (R)

PhotogemA (R) is a hematoporphyrin derivative that has been used as a photosensitizer in experimental and clinical Photodynamic Therapy (PDT) in Brazil. Photosensitizers are degraded under illumination. This process, usually called photobleaching, can be monitored by decreasing in fluorescence intensities and includes the following photoprocesses: photodegradation, phototransformation, and photorelocalization. Photobleaching of hematoporphyrin-type sensitizers during illumination in aqueous solution is related not only to photodegradation but is also followed by the formation of photoproducts with a new fluorescence band at around 640-650 nm and with increased light absorption in the red spectral region at 640 nm. In this study, the influence of pH on the phototransformation process was investigated. PhotogemA (R) solutions, 40 mu g/ml, were irradiated at 514 nm with intensity of 100 mW/cm(2) for 20 min with different pH environments. The controls were performed with the samples in the absence of light. The PhotogemA (R) photodegradation is dependent on the pH. The behavior of photodegradation and photoproducts formation (monitored at 640 nm) is distinct and depends on the photosensitizer concentration. The processes of degradation and photoproducts formation were monitored with Photogemin the concentration of 40 mu g/mL since that demonstrated the best visualization of both processes. While below pH 5 the photodegradation occurred, there was no detectable presence of photoproducts. The increase of pH led to increase of photoproducts formation rate with photodegradation reaching the highest value at pH 10. The increase of photoproducts formation and instability of PhotogemA (R) from pH 6 to pH 10 are in agreement with the desired properties of an ideal photosensitizer since there are significant differences in pH between normal (7.0 < pH < 8.6) and tumor (5.8 < pH < 7.9) tissues. It is important to know the effect of pH in the process of phototransformation (degradation and photoproduct formation) of the molecule since low pH values promotes increase in the proportion of aggregates species in solution and high pH values promotes increase in the proportion of monomeric species. There must be an ideal pH interval which favors the phototransformation process that is correlated with the singlet oxygen formation responsible by the photodynamic effect. These differences in pH between normal and tumor cells can explain the presence of photosensitizers in target tumor cells, making PDT a selective therapy.

Phototransformation of hematoporphyrin in aqueous solution: Anomalous behavior at low oxygen concentration

The photoactivation of a photosensitizer is the initial step in photodynamic therapy (PDT) where photochemical reactions result in the production of reactive oxygen species and eventually cell death. In addition to oxidizing biomolecules, some of these photochemical reactions lead to photosensitizer degradation at a rate dependent on the oxygen concentration among other factors. We investigated photodegradation of Photogem A (R) (28 mu M), a hematoporphyrin derivative, at different oxygen concentrations (9.4 to 625.0 mu M) in aqueous solution. The degradation was monitored by fluorescence spectroscopy. The degradation rate (M/s) increases as the oxygen concentration increases when the molar ratio of oxygen to PhotogemA (R) is greater than 1. At lower oxygen concentrations (< 25 mu M) an inversion of this behavior was observed. The data do not fit a simple kinetic model of first-order dependence on oxygen concentration. This inversion of the degradation rate at low oxygen concentration has not previously been demonstrated and highlights the relationship between photosensitizer and oxygen concentrations in determining the photobleaching mechanism(s). The findings demonstrate that current models for photobleaching are insufficient to explain completely the effects at low oxygen concentration.

Thermoluminescent and optical absorption properties of neodymium doped yttrium aluminoborate and yttrium calcium borate glasses

Neodymium doped yttrium aluminoborate and yttrium calcium borate glasses were prepared by the conventional melting-quenching technique with neodymium concentration varying from 0.10 to 1.0 mol%. The obtained glasses present a wide transparency in the UV-visible region (till 240 nm). The thermoluminescent (TL) emission of beta-irradiated samples was measured, showing a broad peak at similar to 240 degrees C with intensities related to the Nd(3+) content, for both glasses. Calcium borate glass samples are about one order of magnitude less luminescent than the aluminoborate glasses. Probably the presence of Ca(2+), instead of Al(3+) and Y(3+) in the matrix, inhibits the production of the intrinsic hole centers. connected to boron and oxygen, known in the literature to act as luminescent centers in TL emission of borate glasses. We suggest that Nd(3+) ions act as electron trapping centers in both glass matrices, as they modify the temperature of emission and the light intensity. Also, the Nd:YAIB glass can be used as a dosimeter in various applications, including radiotherapy. but the sensitivity of this material to neutron should be checked. (C) 2008 Elsevier B.V. All rights reserved.

Thermoluminescence, structural and magnetic properties of a Li(2)O-B(2)O(3)-Al(2)O(3) glass system doped with LiF and TiO(2)

A Li(2)O-B(2)O(3)-Al(2)O(3) glass system, un-doped and doped with LiF, and/or TiO(2) was synthesized by the fusion method and its physical properties were investigated by thermoluminescence (TL), X-ray diffraction (XRD), electron paramagnetic resonance (EPR), atomic force microscopy (AFM) and differential thermal analysis (DTA). The samples were subjected to gamma-rays from a colbalt-60 ((60)Co) source. These techniques provided evidence of LiF and LiF doped with Ti crystal formation in the glass system. A TL glow peak at about 433 K was sensitive to (60)Co gamma-rays and showed good linearity with doses and consequently could be used to quantify radiation doses. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Dosimetric properties of UV irradiated calcium co-doped borate glass-ceramic

The thermoluminescence (TL) response of Dy and Li doped 20CaB(4)O(7)-80CaB(2)O(4) (Wt%) glass-ceramic irradiated with ultraviolet (UV) radiation was studied. In order to act as TL activator ions, the Dy and Li ions were included in the matrix during the melting process to increase its TL efficiency. A single crystalline CaB2O4 phase was present in the glass-ceramic as determined by X-ray diffraction (XRD). The glass-ceramic 20CaB(4)O(7)-80CaB(2)O(4):Dy,Li wt% (named 20CBO7:Dy,Li) is a newly prepared TL material. Its thermoluminescent dosimetric characteristics have shown a linear response under UV radiation exposure and a good TL signal reproducibility, thus proving to be a promising material for using as an ultraviolet radiation dosimeter. (C) 2007 Elsevier B.V. All rights reserved.

Aggregation susceptibility on phototransformation of hematoporphyrin derivatives

Photosensitizers used in PDT suffer degradation by light. In this work, photobleaching of Photogem((R)) (PG), Photofrin((R)) (PF), and Photosan((R)) (PS), hematoporphyrin derivatives, were induced by light in the presence or absence of 1% Triton X-100. The degradation efficiency in the absence of 1% Triton X-100 follows the sequence: Pf > PF > Ps, which means that PF presented a greater degradation than PF and PS. Forever, in the presence of the surfactant the degradation efficiency is different: PF congruent to PS > PF. Besides aggregation susceptibility, studies in cell culture (tumor and non tumor cells) and in animals (depth of necrosis) were performed, trying to correlate the stability of these photosensitizers with their photodynamic effect. The results suggest that PF presents higher light induced photo-cytotoxicity than PF and PS for both types of cells. For the depth of necrosis studies, more aggregated photosensitizer showed a longer time to accumulate in liver (30 min for PG, 120 h for PF and 720 h for PS). The, to establish an ideal dosimetry in PDT, one must consider the intrinsic physical chemistry characteristics of the photosensitizer as well as their ability to undergo photobleaching.

Experimental evidence and model explanation for cell population characteristics modification when applying sequential photodynamic therapy

We present experimental evidence of the existence of cell variability in terms of threshold light dose for Hep G2 (liver cancer cells) cultured. Using a theoretical model to describe the effects caused by successive photodynamic therapy (PDT) sessions, and based on the consequences of a partial response we introduce the threshold dose distribution concept within a tumor. The experimental model consists in a stack of flasks, and simulates subsequent layers of a tissue exposed to PDT application. The result indicates that cells from the same culture could respond in different ways to similar PDT induced-damages. Moreover, the consequence is a partial killing of the cells submitted to PDT, and the death fraction decreased at each in vitro PDT session. To demonstrate the occurrence of cell population modification as a response to PDT, we constructed a simple theoretical model and assumed that the threshold dose distribution for a cell population of a tumor is represented by a modified Gaussian distribution.