Electron paramagnetic resonance characterization of gamma irradiation damage centers in powder of L-(+)-tartaric acid,N-acetyl-L-alanine and 1-methyl-L-histidine

The electron paramagnetic resonance (EPR) of γ-irradiated powders of l-(+)-tartaric acid, N-acetyl-l-alanine and 1-methyl-l-histidine were investigated at room temperature. Radiation damage centers are attributed to HOOCCH(OH)?(OH)COOH, CH₃?HCOOH and ?CH₂?HCOOH radicals. The spectra were computer-simulated. Hyperfine structure constants and g-values were determined for these three radicals. The unirradiated samples showed no EPR signal. Some spectroscopic properties and suggestions concerning the possible structure of the radicals are discussed in this paper.     

The effect of gamma radiation of amino acid derivatives in the solid state: an EPR study

The spectroscopic features of free radicals produced in gamma irradiation of the N-methyl-dl – alanine, N,N – dimethyl glycine hydrochloride and d – (+) – galactosamine hydrochloride were investigated at room temperature at the dose 15?kGy using EPR technique. The paramagnetic species observed in these compounds were identified as CH₃?HCOOH, ?HOH(CHOH)₃NH₂(CH)₂O, and (CH₃)₂N?HCOOH.HCl, respectively. A comparison with a new paramagnetic species recently observed and characterized in irradiated amino acids indicates that the new radical presented here has a similar structure. In this paper, we have also studied the stability of these compounds at room temperature after irradiation.     

F center production in undoped CaF2 crystals by neutron irradiation at low temperature

We observed that F centers were induced in undoped CaF₂ crystals irradiated by neutrons at 18 K.     

EPR study of radiation-induced radicals in glutaric and amino acid derivatives in solid state

Gamma radiation-induced radicals of 2-methylglutaric acid (2MG), diethyl amino malonate hydrochloride (DEAMHCl), ethyl malonate monoamide have been investigated at room temperature by the electron paramagnetic resonance technique. The type of radicals formed and their room temperature stability were evaluated. Three different radicals have been detected. The free radicals formed in compounds were attributed to the HOOCCH₃?CH₂CH₂ COOH, CH₃?HCO₂CHNH₂COCH₂CH₃ HCl and NH₂COCH₂COO?HCH₃ radicals, respectively. The results were found to be in good agreement with the existing literature data and theoretical predictions conformation.     

The effect of gamma irradiation and shelf aging in air on the oxidation of ultra-high molecular weight polyethylene

This study has investigated the effect of shelf aging, for up to one year in air, on the properties of gamma-irradiated ultra-high molecular weight polyethylene (UHMWPE). A variety of techniques were used to characterize the properties of treated samples. Differential scanning calorimetery (DSC) was used to characterize the morphology. The extent of cross-linking in a polymer network was detected by swelling measurements. The durometer hardness test was used to measure the relative hardness of this material, and changes in density were also measured. Results from all these measurements were combined to explain the changes in the microstructure of the aged, irradiated UHMWPE. This study shows that crystallinity is increased with radiation dose and with aging due to chain scission, which leads to a reduction in the molecular weight of the material. This allows the chains to rearrange to form crystalline regions. Positron annihilation lifetime spectroscopy confirms these conclusions. Fractional free volumes have been deduced from lifetime parameters, which correlate with the data obtained by the other techniques.     

Radiation damage produced in powder of α-(methylamino)isobutyric acid, α -aminoisobutyric acid methyl ester hydrochloride and diethylmalonic acid

The electron paramagnetic resonance spectra of γ-irradiated powders of α-(methylamino)isobutyric acid – CH₃NHC(CH₃)₂COOH, α -aminoisobutyric acid methyl ester hydrochloride – NH₂(CH₃)₂CCOOCH₃ HCl, and diethylmalonic acid – (CH₃CH₂)₂C(COOH)₂ have been investigated at room temperature. It has been found that γ -irradiation produces the (CH₃)₂C˙COOH radical in the first, the (CH₃)₂C˙COOCH₃ radical in the second and the (CH₃CH₂)₂C˙COOH radical in the third compound. The spectra were computer-simulated. The g values and the hyperfine coupling constants of the unpaired electron with the environmental methyl, methylene protons and OH proton were determined. The results were found to be in good agreement with the existing literature data and theoretical predictions.     

Radiation effect studies in single crystal of Trifluoroacetyl-α-Aminoisobutyric acid

In this study, electron paramagnetic resonance of γ-irradiated single crystals of N-Trifluoroacetyl-α-amino isobutyric acid (F₃Ac-Aib-OH) was investigated at room temperature and analyzed for different orientations of the crystal in the magnetic field. The paramagnetic species in N-Trifluoroacetyl-α-aminoisobutyric acid was attributed to the ?F₂-R radical (R= CONHC(CH₃)COOH). Hyperfine coupling constants and g value were also determined. In addition, the single crystal of F₃Ac-Aib-OH was UV-irradiated and paramagnetic species formed was studied at room temperature. The effects of gamma irradiation on fluoroamino acid and stability were discussed.     

Radiation effect studies on some glycine derivatives in solid state

Five glycyl derivatives, glycyl-L-histidine, L-alanyl-glycine, glycine hydrochloride, gly-gly hydrochloride and, gly-gly-glycine in powder form were exposed to 20?kGy doses of ⁶⁰Co gamma radiation to study the effects of ionizing radiation. In these compounds, the paramagnetic centers formed after irradiation were attributed to the R─NHCH─?O^?OH, ?H₂CHNH, H₂NCH₂?O^?OHHCl, NH₂?HCONHCH₂COOHHCl and HNCH₂?O^?OH radicals, respectively. The effect of gamma irradiation to the radical structures and time stability of the radicals were investigated by EPR spectroscopy. The spectra were computer simulated and the hyperfine coupling constants were determined.     

Effect of ϒ- irradiation and study of ϒ-induced physico-chemical changes in high performance thermoset obtained by double cycloaddition of munchnone and bis-maleimide

ABSTRACT

Techniques in polymer synthesis are taking different dimensions in the last few decades. Reversible-deactivation radical polymerization processes resulted in a wide range of polymeric architectures made from an almost infinite reservoir of functional building blocks. The concept of click chemistry revolutionized the way how polymer chemists approached synthetic routes. Among the few reactions that could qualify as click approach; the copper-catalyzed azide–alkyne cycloaddition reaction is in the front place. Whether click or not, cycloadditions are powerful tools for designing polymeric materials in a modular fashion, with a high level of functionality and, sometimes responsiveness. Thus we have developed an efficient synthetic platform for the preparation of a new class of polyimide-based high-performance thermosets (HPTs) based on the double 1,3-dipolar cycloaddition of munchnone with bis-maleimides. It is worth mentioning that this report is the first to deal with the changes in physico-chemical properties of HPTs obtained by cycloaddition reaction due to gamma irradiation. The polymers synthesized by this unique technique were irradiated with gamma doses in the range 10–300?kGy. The consequential effect of gamma radiation and the structural modifications induced on HPTs have been studied and discussed as a function of dose using different characterization techniques such as Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), Field Emission Scanning Electron Microscopy (FESEM) and UV-Vis Spectroscopy.     

Interaction of beam and coated metals at high power continuous irradiation

The beam-matter interaction with various coating effects has received continued attention in the high power laser community. Previous works suggest that coatings promote target damage when compared to beaming on uncoated surface. Three types of paint coatings (acrylic urethane, silicone alkyd and stealth blend) and a water coat on metals (Al, Ti and STS) are irradiated with a CO₂ laser. Both strain and temperature measurements are provided for assessing the instantaneous response characteristics of each coating on different metals. A selective combination of surface coats with metals has been proven to be effective in either preventing or enhancing damage, both thermal and mechanical, associated with focused beaming on a target.     

The study of gamma irradiation effects on poly (glycolic acid)

We have investigated the effects of gamma irradiation on chemical structure, thermal and morphological properties of biodegradable semi-crystalline poly (glycolic acid) (PGA). PGA samples were subjected to irradiation treatment using a ⁶⁰Co gamma source with a delivered dose of 30, 60 and 90?kGy, respectively. Gamma irradiation induces cleavage of PGA main chains forming ～O?H₂ and ?H₂COO～ radicals in both amorphous and crystalline regions. The free radicals formed in the amorphous region abstract atmospheric oxygen and convert them to peroxy radicals. The peroxy radical causes chain scission at the crystal interface through hydrogen abstraction from methylene groups forming the ～?HCOO～ (I) radical. Consequently, the observed electron spin resonance (ESR) doublet of irradiated PGA is assigned to (I). The disappearance of the ESR signal above 190°C indicates that free radicals are formed in the amorphous region and decay below the melting temperature of PGA. Fourier transform infrared and optical absorption studies confirm that the groups are not influenced by gamma irradiation. Differential scanning calorimetry (DSC) studies showed that the melting temperature of PGA decreased from 212°C to 202°C upon irradiation. Degree of crystallinity increased initially and then decreased with an increase in radiation as per DSC and X-ray diffraction studies. Irradiation produced changes in the physical properties of PGA as well as affecting the morphology of the material.     

Effect of gamma rays irradiation on ferroelectric phase transition and domain defect interaction in lead meta niobate single crystal

The objective of our study is to identify the role of gamma rays to control the existing limit of ferroelectric nature of lead meta niobate (PbNb₂O₆) single crystals in terms of domain-defect interaction. The critical value of density of oxygen vacancy sites and average distance between two successive oxygen vacancies, which are responsible for ferroelectric nature in lead niobate single crystal have been calculated. The disappearance of Ferro electricity, which is associated with domain-defect interaction as well as an absence of obeying the Curie-Weiss law have been discussed in gamma rays irradiated lead meta niobate single crystal.     

Fast EPR imaging at 300 MHz using spinning magnetic field gradients

Electron paramagnetic resonance imaging (EPRI) technology has rapidly progressed in the last decade enabling many important applications in the fields of biology and medicine. At frequencies of 300-1200 MHz a range of in vivo applications have been performed. However, the requisite imaging time duration to acquire a given number of projections, limits the use of this technique in many in vivo applications where relatively rapid kinetics occur. Therefore, there has been a great need to develop approaches to accelerate EPRI data acquisition. We report the development of a fast low-frequency EPRI technique using spinning magnetic field gradients (SMFG). Utilizing a 300 MHz CW (continuous wave) EPRI system, SMFG enabled over 10-fold accelerated acquisition of image projections. 2D images with over 200 projections could be acquired in less than 3s and with 20s acquisitions good image quality was obtained on large aqueous free radical samples. This technique should be particularly useful for in vivo studies of free radicals and their metabolism.     

高温退火后非掺杂磷化铟材料的电子辐照缺陷

对不同气氛下高温退火非掺杂磷化铟(InP)材料的电子辐照缺陷进行了研究. 除铁受主外，磷化铁(FeP₂)气氛下退火后的InP中辐照前没有深能级缺陷，而辐照后样品的热激电流谱(TSC)中出现了5个较为明显的缺陷峰，对应的激活能分别为0.23 eV, 0.26 eV, 0.31 eV, 0.37 eV和0.46 eV. 磷(P)气氛下退火后InP中的热生缺陷较多，电子辐照后形成的缺陷具有复合体特征. 与辐照前相比，辐照后样品的载流子浓度和迁移率产生显著变化. 在同样的条件下，经FeP₂ 气氛下高温退火后的InP样品的辐照缺陷恢复速度较快. 根据这些现象分析了缺陷的属性、快速恢复机理和缺陷对材料电学性质的影响. 关键词： 磷化铟 电子辐照 缺陷     

Electron paramagnetic resonance of sonicated powder suspensions in organic solvents

The chemical effects of the acoustic cavitation generated by ultrasound translates into the production of highly reactive radicals. Acoustic cavitation is widely explored in aqueous solutions but it remains poorly studied in organic liquids and in particular in liquid/solid media. However, several heterogeneous catalysis reactions take place in organic solvents.Thus, we sonicated trimethylene glycol and propylene glycol in the presence of silica particles (SiO₂) of different sizes (5–15 nm, 0.2–0.3 µm, 12–26 µm) and amounts (0.5 wt% and 3 wt%) at an ultrasound frequency of 20 kHz to quantify the radicals generated. The spin trap 5,5-dimethyl-1-pyrrolin–N-oxide (DMPO) was used to trap the generated radicals for study by electron paramagnetic resonance (EPR) spectroscopy. We identified the trapped radical as the hydroxyalkyl radical adduct of DMPO, and we quantified it using stable radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as a quantitation standard. The concentration of DMPO spin adducts in solutions containing silica size 12–26 µm was higher than the solution without particles. The presence of these particles increased the concentration of the acoustically generated radicals by a factor of 1.5 (29 µM for 0.5 wt% of SiO₂ size 12–26 µm vs 19 µM for 0 wt%, after 60 min of sonication). Ultrasound produced fewest radicals in solutions with the smallest particles; the concentration of radical adducts was highest for SiO₂ particle size 12–26 µm at 0.5 wt% loading, reaching 29 µM after 60 min sonication. Ultrasound power of 50.6 W produced more radicals than 24.7 W (23 µM and 18 µM, respectively, at 30 min sonication). Increased temperature during sonication generated more radical adducts in the medium (26 µM at 75 °C and 18 µM at 61 °C after 30 min sonication). Acoustic cavitation, in the presence of silica, increased the production of radical species in the studied organic medium.     

激光辐照下高反射镜热变形问题的尺度律

基于热力解耦的热弹性模型,采用常用假设,通过方程分析法,导出了激光辐照下高反射镜热变形问题的尺度律。同时,还发现了对同一模型,当其他条件不变时,变形、温升、应力与激光功率密度之间具有线性关系。数值结果证明了该问题尺度律的成立及线性关系的正确性。该结论是利用缩比模型研究大尺寸反射镜在激光辐照下的热变形问题的依据,且为解决缩比模型设计、辐照条件设计和模型实验数据反推到原型等相关问题提供了参考准则。     

激光辐照下高反射镜热变形问题的尺度律

基于热力解耦的热弹性模型,采用常用假设,通过方程分析法,导出了激光辐照下高反射镜热变形问题的尺度律。同时,还发现了对同一模型,当其他条件不变时,变形、温升、应力与激光功率密度之间具有线性关系。数值结果证明了该问题尺度律的成立及线性关系的正确性。该结论是利用缩比模型研究大尺寸反射镜在激光辐照下的热变形问题的依据,且为解决缩比模型设计、辐照条件设计和模型实验数据反推到原型等相关问题提供了参考准则。     

EPR study of radiation-induced defects in carbonate-containing hydroxyapatite annealed at high temperature

Radiation-induced (γ or UV) paramagnetic defects in carbonate-containing hydroxyapatite (HAP) annealed at high (600–950 °C) temperature were studied by EPR. The complex spectra reveal the presence of different paramagnetic species. Their contributions were found to be strongly dependent on the annealing temperature as well as microwave power, thus, by the adjustment of experimental conditions some of the components can be eliminated that allowed to record EPR spectra caused by no more than two types of paramagnetic defects. All experimental spectra were analyzed using computer simulation. The parameters of the paramagnetic defects detected were determined, and the centers models were discussed. It was found that high-temperature annealing influences essentially the formation of radiation-induced defects in HAP. The СО₃³⁻, О⁻ centers and oxygen vacancy V_O⁻ were shown to be the main stable γ-induced defects in the HAP annealed at high temperatures. New paramagnetic defect with the parameters g_|| = 2.002, g_⊥ = 2.0135 was detected and tentatively identified as an O-related radical. The γ-induced EPR response from СО₃³⁻ radicals was found to be more intense than response from CO₂⁻ in non-annealed HAP. UV-irradiation was found to create smaller amounts of paramagnetic defects in comparison with γ-rays. Besides, oxygen vacancy V_O⁻ was not observed, while two other centers (СО₃⁻ and the center of unknown nature) appear in the UV-induced EPR spectra.     

Defect evolution and photoluminescence in anion-defective alumina single crystals exposed to high doses of gamma-rays

A method of luminescent UV and VUV spectroscopy was used to study the evolution of color centers in anion-defective alumina single crystals exposed to high doses of gamma-radiation. A sharp drop in the intensity of the emission bands and, therefore, the concentration of F⁺ and F-centers associated with the formation of aggregate F₂-type centers was found. The aggregate centers create an additional emission band in the range of (1.8–2.8) eV. When the crystals are exposed to middle and high doses, the photoluminescence (PL) intensity is the highest in the emission band of F₂²⁺-centers, which indicates a high concentration of the aggregates from singly charged oxygen vacancies (of F⁺-centers). When PL of the crystals exposed to high doses is excited with synchrotron radiation of the VUV range, a wide emission band in the red and near infrared (NIR) regions is registered. The centers related presumably to impurity defects, their aggregates and clusters consisting of several oxygen vacancies are responsible for this emission band.