Compounds of 6Li and natural Li for EPR dosimetry in photon/neutron mixed radiation fields

Formates and dithionates of 6Li, enriched and 7Li in natural composition of Li offer a possibility to measure the absorbed dose from photons and thermal neutrons in a mixed radiation field for instance at a boron neutron capture therapy (BNCT) facility. Tests with formates and dithionates of enriched 6Li and lithium compounds with natural composition have been performed at the BNCT facility at Studsvik, Sweden. Irradiations have been performed at 3 cm depth in a Perspex phantom in a fluence rate of thermal neutrons 1.8 x 10(9) n cm(-2) s(-1). The compounds were also irradiated in a pure X-ray field from a 4MV linear accelerator at 5 cm depth in a phantom with accurately determined absorbed doses. The signal intensity and shape was investigated within 3 h after the irradiation. A single line spectrum attributed to the CO2- radical was observed after irradiation of lithium formate. An increase in line width occurring after neutron irradiation in comparison with photon irradiation of the 6Li sample was attributed to dipolar broadening between CO2- radicals trapped in the tracks of the alpha particles. A spectrum due to the SO3- radical anion was observed after irradiation of lithium dithionate. The signal amplitude increased using the 6Li in place of the Li with natural composition of isotopes, in studies with low energy X-ray irradiation. Due to the decreased line width, caused by the difference in g(N) and I between the isotopes, the sensitivity with 6Li dithionate may be enhanced by an order of magnitude compared to alanine dosimetry. After comprehensive examination of the different combinations of compounds with different amounts of 6Li and 7Li regarding dosimetry, radiation chemistry and EPR properties these dosimeter material might be used for dose determinations at BNCT treatments and for biomedical experiments. Interesting properties of the radical formation might be visible due to the large difference in ionization density of neutrons compared to photons.     

Ammonium dithionate- a new material for highly sensitive EPR dosimetry

Polycrystalline ammonium dithionate has been examined for its radiation response in the low dose range (<5Gy) using EPR technique. The SO(3)(-) radical ion was detected as a single EPR line with a peak-to-peak derivative width of ca. 0.44mT in irradiated samples and its intensity was found to vary linearly with dose. At equal and moderate settings of microwave power and modulation amplitude ammonium dithionate was at least seven times more sensitive than l-alanine which is the most common EPR dosimeter standard. Pulse experiments were performed on the powder samples to obtain the longitudinal relaxation time. These and microwave saturation experiments served to indicate the optimal microwave power to be applied during measurements as an EPR dosimeter for best sensitivity of this material. It is thus claimed that ammonium dithionate has excellent potential to become an EPR dosimeter with a low limit of the measurable dose for cases where tissue equivalence is not required or can be corrected for.     

EPR study on tomatoes before and after gamma-irradiation

The results from the EPR studies on fresh, air-dried and lyophilized tomato samples before and after gamma-irradiation are reported. Before irradiation fresh and air-dried tomatoes exhibit one singlet EPR line characterized with common g-factor of 2.0048±0.0005, whereas freeze-dried tomato does not show any EPR spectrum. After irradiation, a typical “cellulose-like” triplet EPR spectrum appears in all samples, attributed to cellulose free radicals, generated by gamma-irradiation. It consists of intense central line with g=2.0048±0.0005 and two weak satellite lines separated ca. 3 mT left and right of it. In air-dried and lyophilized tomatoes the “cellulose-like” EPR spectrum is superimposed by an additional partly resolved carbohydrate spectrum. Fading measurements of the radiation-induced EPR signals indicate that the intensity of the EPR spectra of air-dried and freeze-dried tomato are reduced to about 50% after 50 days, whereas those of fresh irradiated tomatoes kept at 4 °C fade completely in 15 days. The reported results unambiguously show that the presence of two satellite lines in the EPR “cellulose-like” spectra of tomato samples can be used for identification of radiation processing.     

EPR study of free radicals in non- and gamma-irradiated nutritive supplements containing anthocyanins concentrate from lyophilized red wine

Nutritive supplements Enoviton, Enoviton C and Enoviton CE containing standardized anthocyanins from lyophilized red wine, vitamins (some of them) and excipients were investigated by EPR spectrometry before and after gamma-irradiation. Non-irradiated samples exhibit one singlet line with g=2.0039±0.0002, most probably due to free radicals from anthocyanins. After irradiation with 10 kGy gamma-rays, tablets of Еnoviton, Еnoviton С and Еnoviton СЕ, all exhibit complex EPR signals centered at a g-value of g=2.0034. The EPR spectrum of irradiated Enoviton is different from that of Еnoviton С or Еnoviton СЕ due to the overlap of the spectra of microcrystalline cellulose and the background singlet spectrum present in all tablets with the EPR resonance due to irradiated ascorbic acid (in Еnoviton С and Еnoviton СЕ). Gamma-induced free radicals exhibit long time stability—for a six months period the intensity of central peak decrease with 30–40%.     

The effect of dose on light-sensitivity of radicals in alanine EPR dosimeters

In this work we present a study of light-induced effects on free radicals and their transformations in gamma-irradiated pure L-alanine and in commercially available alanine detectors: rods, pellets and films. Samples irradiated to doses from 2 Gy to 4000 kGy were exposed to light from a fluorescent lamp and to ordinary daylight. The observed changes in EPR spectra of the samples were analyzed with regard to their intensity and shape. The shape analysis was based on numerical decomposition of the measured spectra into model spectra reflecting contributions of R1, R2 and R3 radical populations in the samples. The illumination of alanine dosimeters resulted in significant decrease of the central EPR line and was accompanied by distinct variations in the shape of EPR spectra. The rate of light-induced decay in spectra amplitude was found to be dependent on dose of ionizing radiation--the sensitivity to light was decreasing with increase in dose in all detectors in the 2-5x10(5) Gy dose range. The exposure of gamma-irradiated (to 300 Gy) alanine to normal, diffused daylight resulted in decay of the signal amplitude at rate about 0.5% per week. It was shown that decay in the R1 component was responsible for the observed reduction of the spectra amplitude. The observed increase in R2 contributions in samples exposed to light confirmed a hypothesis of R-->R2 radical transformations promoted by visible light. The reported effects indicate a necessity of protection of irradiated dosimeters from their prolonged exposure to light.     

Preparation and applicability of fresh fruit samples for the identification of radiation treatment by EPR

The results of electron paramagnetic resonance (EPR) study on fresh fruits (whole pulp of pears, apples, peaches, apricots, avocado, kiwi and mango) before and after gamma-irradiation are reported using two drying procedures before EPR investigation. In order to remove water from non-irradiated and irradiated samples of the first batch, the pulp of fresh fruits is pressed, and the solid residue is washed with alcohol and dried at room temperature. The fruits of the second batch are pressed and dried in a standard laboratory oven at 40 °C. The results obtained with both drying procedures are compared. All samples under study show a singlet EPR line with g=2.0048±0.0005 before irradiation. Irradiation gives rise to typical “cellulose-like” EPR spectrum featuring one intensive line with g=2.0048±0.0005 and two very weak satellite lines situated 3 mT at left and right of the central line. Only mango samples show a singlet line after irradiation. The fading kinetics of radiation-induced EPR signal is studied for a period of 50 days after irradiation. When the irradiated fruit samples are stored in their natural state and dried just before each EPR measurement, the satellite lines are measurable for less than 17 days of storage. Irradiated fruit samples, when stored dried, lose for 50 days ca. 40% of their radiation-induced radicals if treated with alcohol or ca. 70% if dried in an oven. The reported results unambiguously show that the presence of the satellite lines in the EPR spectra could be used for identification of radiation processing of fresh fruits, thus extending the validity of European Protocol EN 1787 (2000). Foodstuffs—Detection of Irradiated Food Containing Cellulose by EPR Spectroscopy. European Committee for Standardisation. Brussels for dry herbs.     

An international intercomparison on “self-calibrated” alanine EPR dosimeters

The results, obtained by six independent electron paramagnetic resonance (EPR) laboratories, of the dose response coefficients (K_dr) of “self-calibrated” solid-state EPR dosimeters containing alanine as a radiation-sensitive material and Mn²⁺/MgO as an internal reference material, are reported. The intercomparison trial was divided into three steps. It started with the distribution of dosimeters among the participating EPR laboratories with the purpose of irradiating them with known doses of γ-rays and to estimate the K_dr. The percentage standard deviation (PSD) of the K_dr obtained at individual labs was in the range of 1.4–4.6%. The interlaboratory PSD of the K_dr was 8%, primarily pointing to variations in irradiation procedures and EPR spectrometer settings. Further investigations showed that the main source of the interlaboratory PSD is differences in the calibrations of irradiators and settings of EPR acquisition parameters. In order to provide reproducible estimates of the K_dr, low microwave power and modulation amplitude using a combination of sweep time and time constant that gives a distortion-free EPR spectrum should be utilized. In the third step following such a procedure, measuring the same irradiated alanine dosimeter at the respective laboratories, spectrometers (12 instruments of 6 different models and 3 producers) and 10 operators gave an interlaboratory PSD of 3.1%. In conclusion, EPR dosimetry using “self-calibrated” alanine dosimeters may be used as a secondary standard, although a careful calibration of the EPR spectrometer must be performed in order to further reduce the uncertainty.     

Electron paramagnetic resonance spectroscopy of γ-irradiated cellulose and related compounds

EPR studies were carried out on different irradiated cellulosic materials. The shape of the EPR spectrum was found to depend upon the fine structure of cellulose. The peak-to-peak distances of the large peaks on the differential curves were found to be 23.3 and 24.8 gauss, respectively, for the amorphous and recrystallized cellulose. The number of free radicals present per unit weight in the recrystallized cellulose and in the amorphous cellulose were found to be in the ratio of 2.1:1. The EPR spectrum of a sample of irradiated cotton crystallites which was soaked in acetone before being dried was markedly symmetrical, in contrast to the EPR spectra of samples of cotton linters and of cotton crystallites dried from water, and was considered to be a reflection of the lower intermolecular bonding in the former. For corresponding doses, the free radicals on cotton crystallites have the highest g value, followed by cotton linters, followed by regenerated cellulose I. The g value decreased as the irradiation dose was increased.     

EPR spectra induced by gamma-irradiation of some dry medical herbs

The radiation-induced EPR spectra in some medical herbs are reported. The samples studied are: (i) leaves of nettle, common balm, peppermint and thyme; (ii) stalks of common balm, thyme, milfoil, yarrow and marigold; (iii) blossoms of yarrow and marigold; (iv) blossoms and leaves of hawthorn and tutsan; and (v) roots of common valerian, nettle, elecampane (black and white), restharrows and carlina. Before irradiation all samples exhibit one weak anisotropic singlet EPR line with effective g-value of 2.0050±0.0002. The radiation-induced spectra fall into three groups. EPR spectra of irradiated blossoms of yarrow and marigold, stalks of common balm, thyme, tutsan and yarrow as well as roots of common valerian, nettle and elecampane (black and white) show “cellulose-like” EPR spectrum typical for irradiated plants. It is characterized by one intense central line with g=2.0050±0.0005 and two weak satellite lines situated ca. 30 G left and right to it. EPR spectra of gamma-irradiated restharrows and carlina are complex. They may be represented by one triplet corresponding to the “cellulose-like” EPR spectrum, one relatively intense singlet, situated in the center of the spectrum, and five weak additional satellite lines left and right to the center. The last spectrum was assigned as “carbohydrate-like” type. Only one intense EPR singlet with g=2.0048±0.0005 was recorded after irradiation of leaves of nettle and common balm. The lifetime of the radiation-induced EPR spectra was followed for a period of 3 months.     

Electron paramagnetic resonance study of 3,4,5-trimethoxytetraphenyl porphyrinoxovanadium (IV) complex

3,4,5-Trimetoxytetraphenylporphyrinoxovanadium (IV) complex (3,4,5-TMVOTPP) was synthesized by a new one pot synthetic method. The complex was studied in the form of single crystal, powder (polycrystalline state), solution and frozen solution (glassy state) by electron paramagnetic resonance (EPR) between room temperature (RT) and liquid nitrogen temperature (LNT). Interestingly a well-resolved octet in the EPR spectrum at RT is observed in the pure paramagnetic state of the crystal. This observation is attributed to a greatly reduced dipolar interaction between paramagnetic vanadyl ions due to the large size of the molecule and the resultant stacking in the crystalline state. The line width of the EPR signals in single crystal at RT is approximately 3.3 mT which is more than the usual line width in diluted paramagnets ( approximately 1.5 mT) and is attributed to some kind of broadening effect akin to slow motion broadening. The line width in solvents is more than the crystal value but decreases appreciably at low temperatures. The decrease in line width at low temperature is attributed to the increase in spin-lattice-relaxation time and quenching of RT broadening motion. Only one octet is observed in the crystal EPR spectra which suggests only one formula unit per unit cell or a parallel/antiparallel ordering of V=O vectors in case the formula units per unit cell are more than one. This result needs verification by a detailed X-ray investigation. The crystalline field symmetry around the V(4+) metal ion is revealed to be axial by the observed angular dependence of the EPR spectrum and the powder EPR spectrum. No super hyperfine splitting of the hyperfine lines of the vanadyl ion is observed in solid state or diluted glass up to liquid nitrogen temperature. This suggests an expected weak in-plane pi-bonding with ligands. The spin Hamiltonian parameters for vanadyl ion in crystal, powder, diluted solutions and frozen glasses are evaluated and discussed.     

The use of simulation in the EPR spin probe technique for detection of irradiated seeds

An electron paramagnetic resonance (EPR) spin probe study of irradiated wheat seeds was performed depending on irradiation dose. The structural changes in the membrane integrity were followed using aqueous solutions of 4-hydroxy-TEMPO (TANOL) spin probe and a line broadening material. In the studies dry seed embryos were kept in these solutions for 150 min. The spectra were recorded at various times of air drying process. The simulation of these spectra indicated a decrease in the water content of the embryos depending on the increasing irradiation dose. This indicates the increase in the permeability of the membranes as a result of the radiation damage. From the decay curves it is possible to determine about irradiation dose, however, this approach is not very successful at close irradiation doses.     

Enhanced sensitivity of lithium dithionates doped with rhodium and nickel for EPR dosimetry

Electron paramagnetic resonance (EPR) studies of X-irradiated lithium dithionate, Li(2)S(2)O(6) x 2H(2)O, doped with Ni and Rh have shown that these impurities enhance the yield of radicals formed by X-irradiation at room temperature. The signal in the doped samples, measured peak-to-peak of the single EPR derivative line attributed to the SO(3)(-) anion was about 3-4 times that of the pure lithium dithionate and more than 10 times stronger than the alanine signal. These impurities also shortened the spin-lattice relaxation time, T(1), which gives the possibility to measure the doped samples at a higher microwave power. This implies that sensitivity could be further enhanced in the already sensitive EPR dosimeter material lithium dithionate.     

Synthesis, structure, and X-band (9.5 GHz) EPR characterization of the new series of pH-sensitive spin probes: N,N-disubstituted 4-amino-2,2,5,5-tetramethyl-3-imidazoline 1-oxyls

[reaction: see text] An approach to the synthesis of new imidazoline nitroxides bearing an N',N'-disubstituted amidine group is reported. The approach is based on the alkylation of diamagnetic 4-R-amino-1,2,2,5,5-pentamethyl-3-imidazolines with bromoacetic acid ethyl ester; the products of alkylation are further oxidized to the corresponding nitroxides. The approach allows a variety of functional groups to be introduced into the nitroxide molecule structure. Alkylation with bromoacetic acid ethyl ester was found to proceed with high regioselectivity and afford the products of exo-alkylation. The regiochemical assignment is made on the basis of 13C NMR spectra and confirmed by X-ray diffraction study. All of the nitroxides synthesized here were shown to have pH-dependent EPR spectra with pKa ranging from 3.5 to 6.2. For nitroxides 13 bearing the carboxylic group remote to the nitroxide moiety, the changes in isotropic magnetic parameters of EPR spectra due to reversible deprotonation of the carboxylic group were found to be small. For these nitroxides, we demonstrate an alternative approach for pKa determination that is based on measuring the peak-to-peak line width of the EPR spectrum in the presence of the paramagnetic broadening agent potassium ferricyanide. The partition coefficients of nitroxides in octanol/H2O and octanol/phosphate buffer solution mixtures were measured to reveal a range of their lipophilicities.     

Electron self-exchange kinetics determined by MARY spectroscopy: theory and experiment

The electron self-exchange between a neutral molecule and its charged radical, which is part of a spin-correlated radical ion pair, gives rise to line width effects in the fluorescence-detected MARY (magnetic field effect on reaction yield) spectrum similar to those observed in EPR spectroscopy. An increasing self-exchange rate (i.e., a higher concentration of the neutral molecule) leads to broadening and subsequent narrowing of the spectrum. Along with a series of MARY spectra recorded for several systems (the fluorophores pyrene, pyrene-d(10) and N-methylcarbazole in combination with 1,2- and 1,4-dicyanobenzene) in various solvents, a theoretical model is developed that describes the spin evolution and the diffusive recombination of the radical pair under the influence of the external magnetic field and electron self-exchange, thereby allowing the simulation of MARY spectra of the systems investigated experimentally. The spin evolution of the radicals in the pair is calculated separately using spin correlation tensors, thereby allowing rigorous quantum mechanical calculations for real spin systems. It is shown that the combination of these simulations with high resolution, low noise experimental spectra makes the MARY technique a novel, quantitative method for the determination of self-exchange rate constants. In comparison to a simple analytical formula which estimates the self-exchange rate constant from the slope of the linear part of a line width vs concentration plot, the simulation method yields more reliable and accurate results. The correctness of the results obtained by the MARY method is proved by a comparison with corresponding data from the well-established EPR line broadening technique. With its less stringent restrictions on radical lifetime and stability, the MARY technique provides an alternative to the classical EPR method, in particular for systems involving short-lived and unstable radicals.     

Properties of the ammonium tartrate/EPR dosimeter

The EPR response of γ-irradiated ammonium tartrate on the absorbed dose of γ-rays up to 22 kGy as well as the changes in the shape of the EPR spectrum upon applied modulation amplitude and microwave power are reported. Also the possibility to use ammonium tartrate together with Mn²⁺ magnetically diluted in MgO as an internal reference material is evaluated. The influence of the microwave power and the modulation amplitude on their dose response is investigated. The results show that the radiation-induced EPR spectrum of ammonium tartrate, obtained at a low microwave power is complex consisting several patterns and is more easily saturated than the Mn²⁺ EPR spectrum. In this case the following settings of the EPR parameters are recommended: H_mod⩽0.05 mT and 10⩽P_MW⩽13 mW. Using these parameters the dosimeters can be considered for use in intercomparisons.     

Sucrose radical-production cross-section regarding heavy-ion irradiation

We investigated the sucrose radical-production cross-section induced by heavy-ion irradiation. L-alanine was also used in order to compare radical yield and cross-section. The stable free radicals after irradiation were analyzed by electron paramagnetic resonance (EPR). The radical yield obtained by the irradiated samples had a logarithmic correlation with the LET (linear energy transfer). Quantitative EPR analyses showed that radical productions for sucrose and L-alanine vary both by different particle irradiation and the LET under the same absorbed dose. Furthermore, the cross-sections of radical productions for samples were calculated. Both cross-sections for C ions irradiation under LET 30 keV/microm at 50 Gy dose were approximately 3.0x10(-9) microm(2), taking account of the molecular areas of the samples. The values of the cross-sections imply that multiple ionizing particles involve producing stable radicals.     

EPR investigation of the gamma radiation response of different types of glasses

Several types of laboratory glasses such as: "Jena", "Rasotherm", "Thüring" as well as window and windscreen glasses were studied by the method of EPR spectroscopy as possible emergency radiation dosimeters for gamma-ray irradiation. The most appropriate values of modulation amplitude and microwave power were found to obtain best sensitivity for the measured signals. Dose measurements have shown a linear dependence between the EPR signal intensity of radiation created defects in glasses and applied dose in the dose range 50-500 Gy. "Thüring" glass was found to be the most sensitive sample to radiation. The magnitude of window glass absorbed dose was evaluated as the difference between the intensity of its EPR signal recorded after irradiation and the background signal, obtained after thermal relaxation of the former.     

EPR investigation of some traditional oriental irradiated spices

The 9.50 GHz electron paramagnetic resonance (EPR) spectra of unirradiated and ⁶⁰Co γ-ray irradiated cardamom (Elettaria cardamomum L. Maton, Zingiberaceae), ginger ((Zingiber officinale Rosc., Zingiberaceae), and saffron (Crocus sativus L., Iridaceae) have been investigated at room temperature. All unirradiated spices presented a weak resonance line with g-factors around free-electron ones. After γ-ray irradiation at an absorbed dose of up to 11.3 kGy, the presence of EPR spectra whose amplitude increase monotonously with the absorbed dose has been noticed with all spices. A 100 °C isothermal annealing of 11.3 kGy irradiated samples has shown a differential reduction of amplitude of various components that compose initial spectra, but even after 3.6 h of thermal treatment, the remaining amplitude represents no less then 30% of the initial ones. The same peculiarities have been noticed after 83 days storage at room temperature but after 340 days storage at ambient conditions only irradiated ginger displays a weak signal that differs from those of unirradiated sample. All these factors could be taken into account in establishing at which extent the EPR is suitable to evidence any irradiation treatment applied to these spices.     

Analysis of electron spin resonance spectra of irradiated gingers: Organic radical components derived from carbohydrates

Electron spin resonance (ESR) spectral characterizations of gingers irradiated with electron beam were studied. Complex asymmetrical spectra (near g=2.005) with major spectral components (line width=2.4 mT) and minor signals (at 6 mT apart) were observed in irradiated gingers. The spectral intensity decreased considerably 30 days after irradiation, and continued to decrease steadily thereafter. The spectra simulated on the basis of characteristics of free radical components derived from carbohydrates in gingers are in good agreement with the observed spectra. Analysis showed that shortly after irradiation the major radical components of gingers were composed of radical species derived from amylose and cellulose, and the amylose radicals subsequently decreased considerably. At 30 days after irradiation, the major radical components of gingers were composed of radical species derived from cellulose, glucose, fructose or sucrose.     

Study of dosimetric properties of acetylsalicylic acid in pharmaceutical preparations by EPR spectroscopy

Electron paramagnetic resonance (EPR) was used to investigate the dosimetric properties of two pharmaceutical preparations containing acetylsalicylic acid, Aspirin® and Cafiaspirin®. The EPR spectra of the irradiated samples were found to have an asymmetric absorption characterized by a major resonance at g = 2.0033. Dose response was investigated between dose ranges of 2 to 95 kGy for ⁶⁰Co-gamma rays. Fading characteristics and dependence on temperature irradiation were also studied. We suggest that commercial Aspirin® and Cafiaspirin® tablets can be used as dosimeters in the case of a short accident.