Analyses of the EPR responses of sucrose and L-alpha-alanine radicals induced by C, Ne, and Ar ion irradiations

Using electron paramagnetic resonance (EPR), we investigated the signal responses of sucrose and L-alpha-alanine radicals produced by heavy-ion irradiation with various linear energy transfers (LETs) and absorbed dose. The spin yields for the two compounds showed a linear relation with the absorbed dose, as well as a logarithmic correlation with the LET. A quantitative EPR analysis showed that sucrose was more sensitive to the particle species than that of alanine. Hence, the present EPR results imply that sucrose can be useful as a radiation indicator. Further analysis was carried out for the radical-production cross section, which showed that stable radicals of the two compounds were produced through collisions of several particles with a single molecule.     

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.     

Visualizing the dose distribution and linear energy transfer by 1D and 2D ESR imaging: a potassium dithionate dosimeter irradiated with C6+ and N7+ ions

We report the application of one- and two-dimensional (1D and 2D) spectral-spatial electron spin resonance imaging (ESRI) for visualizing the dose distribution and linear energy transfer (LET) in a potassium dithionate, K2S2O6 (PDT), dosimeter irradiated with the heavy ions C(6+) and N(7+). The ESR spectrum in the irradiated PDT consists of a superposition of two isotropic signals assigned to two *SO3(-) radicals, R1 and R2, with no hyperfine splittings and slightly different g values. The 1D ESRI profiles clearly indicate the spatial penetration of the beams and the location of the sharp maximum dose, the "Bragg peak", detected for each beam. The depth penetrations are different: approximately 2.3 mm for C(6+) and approximately 1.8 mm for N(7+) beams, +/-0.1 mm; beyond these limits, no radicals were detected. 2D spectral-spatial ESRI images reflect both the dose distribution and the spatial dependence of the relative intensities of radicals R1 and R2, an effect that is assigned to the depth variation of the LET. This study has demonstrated that ESRI is a promising new method for dose and LET determination. Of particular interest are applications in the field of radiotherapy with heavy ions, because in this case the Bragg peak is pronounced and the dose can be focused at specific depths while the surrounding areas are protected.     

Study on oxidation of polymers treated by high LET radiation

The oxidation of medical silicone rubber and segmented polyether urethane which were bombarded with 11.2 MeV Si⁺ or F⁺ at the dose of 5 × 10¹⁴ ions/cm² was studied. In XPS measurements, it was found that the oxygen concentration on the surface of the implanted polymeric membranes had been increasing in three months at least. ESR measurement showed that some free radicals existed in these membranes and their quantities decreased with time. Chemical analysis proved that peroxides were generated in the γ irradiated membranes. The reason for the increasing of oxygen concentration was that free radicals combined with oxygen in the air and produced peroxides on the membrane surface. Moreover, in order to demonstrate the radiation mechanism, low LET (γ rays) radiation of such polymeric membranes was carried out for comparison     

Oxidation of gaseous styrene by electron beam irradiation

In this research, the absorbed dose, background gases, relative humidity, and initial concentrations were selected as control factors to discover decomposition characteristics of styrene using electron beam irradiation. It was confirmed that a considerable amount of styrene was removed by primary electrons as well as radicals and ions, which were produced after the electron beam irradiation. Moreover, the removal efficiencies of styrene were observed to rise when the initial concentration was lower, moisture content was higher, and the absorbed dose increased. For instance, 50 ppmv styrene showed extremely high removal efficiency (over 98%) at a condition of 2.5 kGy. A small amount of styrene oxide, benzaldehyde, aerosol, CO, and CO₂ were produced as by-products after EB irradiation.     

The occurrence of free radicals in milled and irradiated paprika as detected by ESR

Ionising radiation and various other types of treatment can induce oxidising processes that give rise to free radicals in materials. This paper reports an ESR study of free radicals in spicy paprika in various phases of grinding and in samples of different particle sizes as functions of the absorbed gamma dose and storage time. In 7th phase of grinding, the ESR intensity first increased and then decreased after conditioning. The ESR intensity increased with increase in the absorbed dose, and then decreased during the 8 weeks of storage. This declining intensity demonstrates the simultaneous presence of free radicals having short and long shelf life in paprika samples.     

Heavy ion radiolysis of liquid pyridine

The radiation chemical yields of the main products produced in liquid pyridine radiolysis (molecular hydrogen and dipyridyl) have been examined as a function of particle linear energy transfer (LET) with protons, helium ions, and carbon ions of a few to 30 MeV and compared to gamma-radiolysis published in a previous work (J. Phys. Chem. A 2005, 109, 461). Anthracene and biphenyl scavenging techniques have been used to clarify the role of the triplet excited state. An increase in triplet scavenger concentration leads to a decrease in pyridine triplet excited state with a concurrent decrease in dipyridyl, but formation of the latter does not primarily involve pyridyl radicals expected to be produced in the decomposition of the triplet excited state. A decrease in the yield of dipyridyl and an increase in molecular hydrogen are observed with increasing track average LET. The dipyridyl yield with 10 MeV carbon ions is 0.20 molecules/100 eV, which is only 16% of that of observed with gamma-rays. The low yield of dipyridyl with carbon ions is attributed to intratrack triplet-triplet (T-T) annihilation processes due to the increase in local triplet excited-state concentrations with increasing LET. An increasing yield of molecular hydrogen with increasing LET is probably due to an increase in the formation and subsequent decay of singlet excited states produced by the T-T annihilation. A complete mechanism for the radiolysis of liquid pyridine is presented.     

Electron spin resonance studies of polycarbonate irradiated by γ-rays and ultraviolet light

Paramagnetic species produced in polycarbonate (PC) by γ- or ultraviolet irradiation were investigated by ESR. In γ-irradiation, scissions of carbonate groups in the main chain occur. ESR spectra (g = 2.003₄) composed of a sharp singlet, some broad singlets, and a small signal with hyperfine structure are obtained, and they are assigned to trapped electrons, positive radical ions, phenoxy-type free radicals, phenyl radicals, and ? O? C₆H₄? C(CH₃)₂ radicals. The G value for total yields of paramagnetic species at 77°K is 1.8. The percentage of CO and CO₂, the dominant gases evolved, is 65.4 and 33.8%, respectively. In ultraviolet irradiation, energy is absorbed selectively at the surface region. The surface region becomes insoluble in methylene chloride because of crosslinking of phenyl groups. The ESR spectrum obtained at 77°K is a broad singlet and assigned to phenoxy-type free radicals, phenyl radicals, and polyenyl-type free radicals. Some differences in effects of γ- and ultraviolet irradiation of PC are discussed.     

ELECTRON SPIN RESONANCE OF γ -IRRADIATED COBALT(III) COMPLEXES; ELECTRONIC AND SPIN STATES OF HOT COBALT(II) IONS

Abstract

ESR investigation of the γ -ray irradiated Co(III) complexes have been carried out. The identification and the classification of the irradiation products on the basis of the ESR signal patterns, and the electronic and the spin states of the products are discussed.

Co(III) complexes are reduced by the γ irradiation into Co(II) complexes, where the produced Co(II) ions have low spin configurations, S = ½. Authors refer to these particular spin states as hot ions.     

FREE RADICALS FROM THE PHOTODECOMPOSITION OF BLEOMYCIN

Abstract— Irradiation of bleomycin with light (λ > 320 nm) leads to a decrease in absorbance at 290 nm, which is suppressed by metal ions and by oxygen. Light-induced oxygen consumption is diminished by the enzymes superoxide dismutase and catalase, implying that toxic reduced species of oxygen (O₂ and H₂O₂) are formed during irradiation. Spin-trapping measurements with 5,5-dimethyl-1-pyrroline-1-oxide and 2-methyl-2-nitrosopropane demonstrated that hydroxyl radical and methyl radical adducts also are generated in the system. In addition, direct ESR measurements have shown that methyl radicals are produced during irradiation of bleomycin solutions at low temperatures, together with radicals probably derived from the bithiazole moiety of the bleomycin. The latter are also produced from irradiation of the model compound bithia. Radical production is diminished by complexation of bleomycin with metal ions.     

有机锡化合物光解活泼自由基的ESR研究

本文用自旋捕捉技术与ESR相结合的方法,研究了六种有机锡化合物的光解反应历程。结果表明:有机锡化合物紫外光照时,碳-锡键发生均裂,产生碳中心和锡中心自由基。其中碳中心自由基易被捕捉剂α-苯基-N-特丁基氮氧化物(PBN)或2,3,5,6-四甲基亚硝基苯(ND)所捕获;而锡中心自由基可与菲醌形成稳定的环状加合物。由于环状加合物中配体的不同,产生的空间效应也不同,从而导致加合物中的未偶电子云密度发生变化,给出相异的ESR信号。     

Free radicals formed by addition of antimalaric artemisinin (Qinghaosu,QHS) to human serum: an ESR-spin trapping investigation

The antimalaric drug artemisinin (QHS) is believed to operate through a mechanism initiated with the cleavage of its endoperoxidic bond induced by transition metal ions. An ESR investigation of the reaction of QHS with human serum in the presence of two spin trapping agents has led to the detection of spin adducts of carbon-centred radicals. Experiments carried out replacing the human serum with iron(II) salts led to the observation of the same spin adducts, thus supporting previous suggestions that alsoin vivo the drug operatesvia a radical-based mechanism. UV irradiation of QHS also led to the trapping of transient free radicals.     

Dielectric study of post-irradiation effects in gamma-irradiated polyethylenes

The post-irradiation dielectric behaviour of different polyethylenes (PEs) has been studied by means of dielectric loss (tan δ) analysis over the wide temperature (25–325 K) and frequency (1 kHz–1 MHz) ranges. For this reason, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) samples were previously gamma irradiated in air to absorbed dose of 300 kGy. The irradiated samples were divided into two groups, and for the first one annealing treatment which can substantially reduce the concentration of free radicals were employed. For the second group, e.g. samples stored in air at room temperature after irradiation, post-irradiation evolution in free radical concentration, dielectric relaxation spectra and carbonyl content was investigated as a function of storage time, up to 90 days. Dielectric relaxation behaviour is related to differences in the initial structures of PEs (such as branching, crystallinity, etc.) and to the radiation-induced effects; carbonyl groups that were introduced by irradiation and/or delayed (post-irradiation) oxidation were regarded as tracer groups. Electron spin resonance (ESR), differential scanning calorimetry (DSC), infrared (IR) spectroscopy and gel measurements were used to determine the changes in free radical concentration, crystal fraction, oxidation and degree of network formation, respectively.     

Hydrogen production in γ-ray and helium-ion radiolysis of polyethylene,polypropylene, poly(methyl-methacrylate), and polystyrene

The production of molecular hydrogen in the radiolysis of high-density polyethylene, isotactic polypropylene (PP), poly(methyl-methacrylate) (PMMA), and polystyrene (PS) by γ rays and 5–20-MeV helium ions was investigated. Molecular hydrogen is the dominant gaseous product from these polymers, and the yields with γ rays are 3.3, 2.6, 0.24, and 0.033 molecules per 100 eV of energy absorbed for polyethylene, PP, PMMA, and PS, respectively. The decrease in observed hydrogen is due to increased branching and the chemical nature of the groups on the side chains. There is an increase in hydrogen production with increasing linear energy transfer (LET) from γ rays to helium ions, but the relative increase depends on the polymer type. With incident 5-MeV helium ions, the respective yields of molecular hydrogen are 4.6, 3.2, 0.62, and 0.15 molecules per 100 eV. The increase in molecular hydrogen with increasing LET may be due to changes in the kinetics of hydrogen precursors in the particle tracks. The differences in the relative increases in molecular hydrogen with increasing LET for each of the polymers suggests that self-scavenging reactions may be important for low LET particles. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1656–1661, 2000     

Electron spin resonance detection of radiosterilization of pharmaceuticals: application to four nitrofurans

The detection and dosimetry of radiosterilization of pharmaceuticals is a growing concern to numerous government regulatory agencies worldwide. In the absence of suitable detection methods, attention was focused on electron spin resonance (ESR) spectrometry. This paper reports experimental data on ESR dosimetry of irradiated nitrofurans (nitrofurantoin, nifuroxazide, nifurzide and nifurtoinol). Whereas the ESR spectrum of a non-irradiated sample shows no signal, a signal, that is dependent on the irradiation dose is observed with irradiated samples. The number of free radicals was calculated by comparing the second integral from radiosterilized samples and a Bruker strong pitch reference; the values were in the range 1.1 x 10(18)-1.5 x 10(19) radicals mol-1 (G = 0.003-0.03). In addition to qualitative detection, ESR spectrometry can be used for dose determination. When a bi-exponential function is applied to the variation of the peak-to-peak amplitude versus dose, the function correlates well with the data. However, an exponential function, easier to use than a bi-exponential function, will probably be sufficient for dose determination by retrospective dosimetry. Decay of radicals upon storage was modelled using a bi-exponential function. From this, the time limit from the irradiation (25 kGy) for identification of irradiated nitrofurans by ESR can be evaluated. With regard to the commercial aspects of drugs, radicals should be detected up to 2 years after irradiation. The kinetic decrease makes discrimination between irradiated and non-irradiated nitrofurans possible even after storage for up to 2 years, except for nifurtoinol.     

Thermal-induced conversion of maleic and fumaric acid anion radicals in poly(methyl methacrylate)

Thermal-induced conversion of maleic and fumaric acid anion radicals produced by γ irradiation at 77 K in poly(methyl methacrylate) (PMMA) was studied by electron spin resonance (ESR) and optical absorption spectroscopic measurements. The ESR spectra of these acid anion radicals change into two-line spectra with a line separation of ca. 10 G by thermal annealing. This spectrum is assigned to a protonated radical of each acid anion radical. Anion radicals of the solutes are relatively stable below the γ transition point of PMMA and the conversion reaction takes place near this point. This means that the molecular motion of matrix molecule affects the radical conversion reaction.     

含氟烷基氧杂磺酸钾盐快速电子辐照自由基衰变

本文报导了用电子自旋共振谱研究一些含氟烷基氧杂磺酸钾盐经快速电子辐照后自由基衰变的情况。真空辐照和空气中辐照的剂量均为7.2×10~6rad。辐照后的全氟和多氟化合物于室温下放置2～12天后,其自由基浓度为10~(18)spin No./g,放置88天后,自由基浓度与前相同,基本无变化。而十二烷基磺酸钠辐照后生成的自由基,在室温下却很快衰变。辐照后生成的自由基具有反应活性,可以引发苯乙烯的聚合反应。     

高密度聚乙烯粉末的电子束辐射接枝

高密度聚乙烯粉末的电子束辐射接枝王勇，黄劲，李瑞海（成都科技大学纺织工学院，成都６１００６５）（成都科技大学高分子材料系６１００６５）关键词：ＨＤＰＥ粉末，电子束辐射，接枝聚合本文采用电子束予辐射法使聚乙烯粉末表面产生活性中心，然后通过液－固相接枝共...     

DETECTION OF ACTIVE RADICALS FORMED DURING THE SONOLYSIS OF POLYMERS

Active radicals formed during the sonolysis of PVK (polyvinyl carbazole) and PMMA (polymethylmethacrylate) have been studied with the combination of spin thepping technique and ESR spectroscopy-The results show that: 1. For PVK, radicals CA and--CH_2--CH--are produced during the ultrasonic irradiationand only the later can be trapped by MNP. 2. For PMMA, radicals --C and --CH_2 are grnerated by sonolysis and both can be trappedby ND.     

ESR and spin trapping of free radicals produced in poly U and poly A using the boron-neutron capture reaction

Powdered samples of poly U and poly A containing sodium tetraborate and controls without tetraborate were irradiated at room temperature with thermal neutrons. Radical formation occurred only in the samples containing tetraborate. Thermal neutrons interact with ¹⁰B (10% naturally occurring in tetraborate) via the boron-neutron capture reaction. This reaction generates α particles and ⁷Li ions with mean kinetic energies of 1.48 and 0.85 MeV, respectively. The identification and location of the free radicals produced by the interaction of these particles with poly U and poly A, was determined by ESR and spin trapping using the spin trap 2-methyl-2-nitrosopropane (MNP). Following dissolution of irradiated poly U in an MNP solution, the spin trapped poly U was hydrolyzed with base (NaOH, pH 12.6). On readjusting the pH to pH 7.5 the spin adduct ESR spectrum showed that in poly U, radical formation occurs at the C(6) carbon of the uracil residues. For poly A the solid state ESR spectrum suggests that radicals are formed at the N(3) and/or N(7) nitrogens and at the C(4) and/or C(5) carbons. However, only the C(5) carbon-centered radicals were spin trapped. In addition, the results for poly A indicate that sugar-phosphate backbone is disrupted by the α particles and ⁷Li ions. The nature of this interactions is still unclear.