Electron paramagnetic resonance and the thermoluminescence emission mechanism of the 280 degrees C peak in natural andalusite crystal

Samples of natural andalusite (Al(2)SiO(5)) crystal have been investigated in terms of thermoluminescence (TL) and electron paramagnetic resonance (EPR) measurements. The TL glow curves of samples previously annealed at 600 degrees C for 30 min and subsequently gamma-irradiated gave rise to four glow peaks at 150, 210, 280 and 350 degrees C. The EPR spectra of natural samples heat-treated at 600 degrees C for 30 min show signals at g = 5.94 and 2.014 that do not change after gamma irradiation and thermal treatments. However, it was observed that the appearance of a paramagnetic center at g=1.882 for the samples annealed at 600 degrees C for 30 min followed gamma irradiation. This line was attributed to Ti(3+) centers. The EPR signals observed at g=5.94 and 2.014 are due to Fe(3+). Correlations between EPR and TL results of these crystals show that the EPR line at g=1.882 and the TL peak at 280 degrees C can be attributed to the same defect center. (C) 2011 Elsevier B.V. All rights reserved.

Correlation between electron paramagnetic resonance and thermoluminescence in natural sodalite

Samples of natural sodalite, Na(8)Al(6)Si(6)O(24)Cl(2), submitted to gamma irradiation and to thermal treatments, have been investigated using the thermoluminescence (TL) and electron paramagnetic resonance (EPR) techniques. Both, natural and heat-treated samples at 500A degrees C in air for 30 min, present an EPR signal around g = 2.01132 attributed to oxygen hole centers. The EPR spectra of irradiated samples show an intense line at g = 2.0008 superimposed by a hyperfine multiplet of 11 lines due to an O(-) ion in an intermediate position with respect to two adjacent Al nuclei. In the TL measurements, the samples were annealed at 500A degrees C for 30 min and then irradiated with gamma doses varying from 0.001 to 20 kGy. All the samples have shown TL peaks at 110, 230, 270, 365, and 445A degrees C. A correlation between the EPR g = 2.01132 line and the 365A degrees C TL peak was observed. A TL model is proposed in which a Na(+) ion acts as a charge compensator when an Al(3+) ion replaces a Si(4+) lattice ion. The gamma ray destruction of the Al-Na complex provides an electron trapped at the Na and a hole trapped at a non-bridging oxygen ion adjacent to the Al(3+) ion.

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.

Chemical process to separate iron oxides particles in pottery sample for EPR dating

Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na(G)(H(2)W(12)O(40))center dot H(2)O] becomes useful. However, the sodium polytungstate is very expensive in Brazil: hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCI, HNO(3) and H(2)O(2) for 4 h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g= 2.00 region, possibly due to a radical of (SiO(3))(3-), mixed with signal of remaining iron [M. lkeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under -gamma-irradiation. However, still due to iron influence, the additive method yielded too old age-value. Since annealing at 300 degrees C, Toyoda and Ikeya IS. Toyoda, M. Ikeya, Geochem. J. 25 (1991) 427-445] states that E `(1)-signal with maximum intensity is obtained, while annealing at 400 degrees C E`(1)-signal is completely eliminated, the subtraction of the second one from 300 degrees C heat-treated sample isolate E`(1)-like signal. Since this is radiation dose-dependent, we show that now EPR dating becomes possible. (C) 2008 Elsevier B.V. All rights reserved.

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.

Synthesis, spectroscopic characterization and radiosensitizing properties of acetato-bridged copper(II) complexes with 5-nitroimidazole drugs

Three novel acetato-bridged dinuclear copper(II) complexes with 5-nitroimidazoles (CuAcNtrim) and the known copper-acetato-metronidazole have been prepared by an environment-friendly route and spectroscopically characterized. The CuAcNtrim compounds of formula [Cu(2)(mu-O(2)CCH(3))(4)Ntrim(2)], where Ntrim = metronidazole (1), secnidazole (2), tinidazole (3) or nimorazole (4), exhibit dimeric copper-acetato paddle-wheel structures with Ntrim axial ligands coordinated to copper(II) ions through the N(3) atoms of the imidazole rings. EPR data indicate antiferromagnetic behavior for this novel series of copper complexes. The constant coupling has been found to decrease along with the increasing of basicity of the Ntrim axial ligand. The CuAcNtrim complexes and the correspondent Ntrim parent drugs have shown radiosensitizer properties for Hep2 (human larynx cancer) cell line in vitro. The best enhancement of radiosensitizer activity upon coordination of the Ntrim drug to copper(II) has been found for the nimorazole compound which has the strongest Cu-Ntrim bond and exhibits the highest lipophilicity within the series of CuAcNtrim complexes. (C) 2010 Elsevier B.V. All rights reserved.

Response of oriental fruit moth, Grapholita molesta (Busck) (Lepidoptera: Tortricidae), eggs to gamma radiation

As insects increase in radiotolerance as they develop and usually several developmental stages of the pest may be present in the fresh shipped commodity, it is important to know the radiation susceptibility of the stages of the target insect before the establishment of ionizing radiation quarantine treatments. This study was performed to determine the radiotolerance of eggs of the oriental fruit moth, Grapholita molesta (Busck) (Lepidoptera: Tortricidae), to gamma radiation. This species is considered as one of the most serious worldwide pests for temperate fruits, especially peaches. Eggs (12 h old) were exposed to 0 (control), 25, 35, 50, 75, 100, 125 and 150 Gy of gamma radiation. Surviving larvae were allowed to feed on an artificial diet. Three days after irradiation, it was verified that larvae`s cephalic capsules were significantly affected by gamma radiation, and the estimated mean LD(90) and LD(99) were 66.3 Gy and 125.8 Gy, respectively. Oriental fruit moth eggs revealed to be quite radiosensitive and very low doses as 50 Gy were sufficient to disrupt G. molesta embryogenesis. At 25 Gy, only male adults originated from the surviving larvae and, after mating with untreated fertile females, shown to be sterile. (C) 2010 Elsevier Ltd. All rights reserved.

Effect of the Gamma Radiation Dose Rate on Psychrotrophic Bacteria, Thiobarbituric Acid Reactive Substances, and Sensory Characteristics of Mechanically Deboned Chicken Meat

Frozen samples of mechanically deboned chicken meat (MDCM) with skin were irradiated with gamma radiation doses of 0.0 kGy (control) and 3 kGy at 2 different radiation dose rates: 0.32 kGy/h (3 kGy) and 4.04 kGy/h (3 kGy). Batches of irradiated and control samples were evaluated during 11 d of refrigerated (2 +/- 1 degrees C) storage for the following parameters: total psychrotrophic bacteria count, thiobarbituric acid reactive substances (TBARS), evaluation of objective color (L*, a*, and b*) and a sensory evaluation (irradiated odor, oxidized odor, pink and brown colors). No statistical difference (P > 0.05) was found amongst the TBARS values obtained for the MDCM samples irradiated with dose rates of 0.32 and 4.04 kGy/h. There was a significant increase (P < 0.05) in the psychrotrophic bacterial count as from the 7th day of refrigerated storage, for the MDCM samples irradiated at the dose rate of 4.04 kGy/h. With respect to the attribute of oxidized odor, the samples irradiated with a dose rate of 0.32 kGy/h showed a stronger intensity and were significantly different (P < 0.05) from the sample irradiated with a dose rate of 4.04 kGy/h on days 0 and 2 of refrigerated storage. Irradiation with a dose rate of 4.04 kGy/h (3 kGy) was shown to be the best condition for the processing of MDCM according to the evaluation of all the variables, under the conditions of this study. Practical Application The results obtained for the application of different dose rates of ionizing radiation to mechanically deboned chicken meat will provide the food industry with information concerning the definition of the best processing conditions to maximize the sensory and food quality.

Evaluation of gamma-radiation on green tea odor volatiles

The aim of this study was to evaluate the gamma radiation effects on green tea odor volatiles in green tea at doses of 0, 5, 10, 15 and 20 kGy. The volatile organic compounds were extracted by hydrodistillation and analyzed by GC/MS. The green tea had a large influence on radiation effects, increasing the identified volatiles in relation to control samples. The dose of 10 kGy was responsible to form the majority of new odor compounds following by 5 and 20 kGy. However, the dose of 5 kGy was the dose that degraded the majority of volatiles in non-irradiated samples, following by 20 kGy. The dose of 15 kGy showed has no effect on odor volatiles. The gamma radiation, at dose up to 20 kGy, showed statistically no difference between irradiated and non irradiated green tea on odors compounds. (C) 2010 Elsevier Ltd. All rights reserved.

Influence of gamma radiation onto polymeric matrix with papain

Papain is a proteolytic enzyme that has been widely used as debridement agent for scars and wound healing treatment. However, papain presents low stability, which limits its use to extemporaneous or short shelf-life formulations. The purpose of this study was to entrap papain into a polymeric matrix in order to obtain a drug delivery system that could be used as medical device. Since these systems must be sterile, gamma radiation is an interesting option and presents advantages in relation to conventional agents: no radioactive residues are formed: the product can be sterilized inside the final packaging and has an excellent reliability. The normative reference for the establishment of the sterilizing dose determines 25 kGy as the inactivation dose for viable microorganisms. A silicone dispersion was selected to prepare membranes containing 2% (w/w) papain. Irradiated and non-irradiated membranes were simultaneously assessed in order to verify whether gamma radiation interferes with the drug-releasing profile. Results showed that irradiation does not affect significantly papain release and its activity. Therefore papain shows radioresistance in the irradiation conditions applied. In conclusion, gamma radiation can be easily used as sterilizing agent without affecting the papain release profile and its activity onto the biocompatible device is studied. (C) 2009 Elsevier Ltd. All rights reserved.

gamma-Radiation induces apoptosis via sarcoplasmatic reticulum in guinea pig ileum smooth muscle cells

We investigated the effects of gamma-radiation on cells isolated from the longitudinal smooth muscle layer of the guinea pig ileum, a relatively radioresistant tissue. Single doses (up to 50 Gy) reduced the amount of sarcoplasmatic reticulum and condensed the myofibrils, as shown by electron microscopy 3 days post-irradiation. After that, contractility of smooth muscle strips was reduced. Ca(2+) handling was altered after irradiation, as shown in fura-2 loaded cells, with elevated basal intracellular Ca(2+), reduced amount of intrareticular Ca(2+), and reduced capacitive Ca(2+) entry. Radiation also induced apoptosis, judged from flow cytometry of cells loaded with proprium iodide. Electron microscopy showed that radiation caused condensation of chromatin in dense masses around the nuclear envelope, the presence of apoptotic bodies, fragmentation of the nucleus, detachment of cells from their neighbors, and reductions in cell volume. Radiation also caused activation of caspase 12. Apoptosis was reduced by the administration of the caspase inhibitor Z-Val-Ala-Asp-fluoromethyl-ketone methyl ester (Z-VAD-FIVIK) during the 3 day period after irradiation, and by the chelator of intracellular Ca(2+), 1,2-bis(o-aminophenoxy)ethane-N,N,N`,N`-tetraacetic acid (BAPTA), from 1 h before until 2 h after irradiation. BAPTA also reduced the effects of radiation on contractility, basal intracellular Ca(2+), amount of intrareticular Ca(2+), capacitative Ca(2+) entry, and apoptosis. In conclusion, the effects of gamma radiation on contractility, Ca(2+) handling, and apoptosis appear due to a toxic action of intracellular Ca(2+). Ca(2+)-induced damage to the sarcoplasmatic reticulum seems a key event in impaired Ca(2+) handling and apoptosis induced by gamma-radiation. (c) 2008 Elsevier B.V. All rights reserved.

Evaluation of phenolic compounds in mate (Ilex paraguariensis) processed by gamma radiation

The radiation food processing has been demonstrating great effectiveness in the attack of pathogenic agents, while little compromising nutritional value and sensorial properties of foods. The mate (Ilex paraguariensis), widely consumed product in South America, generally in the form of infusions with hot or cold water, calls of chimarrao or terere, it is cited in literature as one of the best sources phenolic compounds. The antioxidants action of these constituent has been related to the protection of the organism against the free radicals, generated in alive, currently responsible for the sprouting of some degenerative illness as cancer, arteriosclerosis, rheumatic arthritis and cardiovascular clutters among others. The objective of that work was to evaluate the action of the processing for gamma radiation in phenolic compounds of terere beverage in the doses of 0, 3, 5, 7 and 10 kGy. The observed results do not demonstrate significant alterations in phenolic compounds of terere beverage processed by gamma radiation. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

Use of PCR for detecting Aspergillus flavus in maize treated by gamma radiation process

The aim of this study was to verify the effects of gamma radiation process on the fungal DNA and the application of PCR in the detection of Aspergillus flavus in irradiated maize grains. The samples were inoculated with a toxigenic strain and incubated under controlled conditions of relative humidity, water activity, and temperature for 15 days. After incubation, the samples were treated with gamma radiation with doses of 5 and 10 kGy and individually analyzed. The use of PCR technique showed the presence of DNA bands of Aspergillus flavus in all irradiated samples that showed no fungal growth in agar medium.

Evaluation of Fungal Burden and Aflatoxin Presence in Packed Medicinal Plants Treated by Gamma Radiation

This study was developed to evaluate the fungal burden, toxigenic molds, and mycotoxin contamination and to verify the effects of gamma radiation in four kinds of medicinal plants stored before and after 30 days of irradiation treatment. Eighty samples of medicinal plants (Peumus boldus, Camellia sinensis, Maytenus ilicifolia. and Cassia angustifolia) purchased from drugstores, wholesale, and open-air markets in Sao Paulo city, Brazil, were analyzed. The samples were treated using a (60)Co gamma ray source (Gammacell) with doses of 5 and 10 kGy. Nonirradiated samples were used as controls of fungal isolates. For enumeration of fungi on medicinal plants, serial dilutions of the samples were plated in duplicate onto dichloran 18% glycerol agar. The control samples revealed a high burden of molds, including toxigenic fungi. The process of gamma radiation was effective in reducing the number of CFU per gram in all irradiated samples of medicinal plants after 30 days of storage, using a dose of 10 kGy and maintaining samples in a protective package. No aflatoxins were detected. Gamma radiation treatment can be used as an effective method for preventing fungal deterioration of medicinal plants subject to long-term storage.

Effects of gamma radiation on the growth of Alternaria alternata and on the production of alternariol and alternariol monomethyl ether in sunflower seeds

The objective of the present study was to evaluate the effects of different gamma radiation doses on the growth of Alternaria alternata and on the production of toxins alternariol (AOH), and alternariol monomethyl ether (AME) in sunflower seed samples. After irradiation with 2, 5 and 7 kGy, the spore mass was resuspended in sterile distilled water and the suspension was inoculated into sunflower seeds. The number of colony-forming units per gram (CFU/g) was determined after culture on Dichloran Rose Bengal Chloramphenicol and Dichloran Chloramphenicol Malt Extract Agar. The presence of AOH and AME was investigated by liquid chromatography coupled to mass spectrometry. The radiation doses used resulted in a reduction of the number of A. alternata CFU/g and of AOH and AME levels when compared to the nonirradiated control group. Maximum reduction of the fungus (98.5%) and toxins (99.9%) was observed at a dose of 7 and 5 kGy, respectively. Under the present conditions, gamma radiation was found to be an alternative for the control of A. alternata and, consequently, of AOH and AME production in sunflower seeds. (C) 2009 Elsevier Ltd. All rights reserved.