An electron paramagnetic resonance study on irradiated triphenylphosphinselenid single crystal

The single crystals of triphenylphosphinselenid [C₁₈H₁₅PSe] were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to ⁶⁰Co gamma (γ) rays with a dose speed of 0.980 kGy/h at the room temperature for 72 h. The free radical over the sample was observed using electron paramagnetic resonance (EPR)–X band spectrometer. The EPR spectra were recorded between 120 and 400 K. Furthermore, the sample irradiated was rotated in steps of 10° and analyzed for different orientations of the crystal in the magnetic field. Only one radical structure was determined on the molecule. The hyperfine constants of the sample were found to be anisotropic. The average values of these constants and value of g were calculated as following: g=2.007656, a_Se=37.47 G, a_P=27.44 G, a_Ha=17.28 G, and a_Hb=18.16 G.     

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.     

Identification and dosimetry of irradiated walnuts (Juglans regia) using EPR

Electron paramagnetic resonance (EPR) is an easy, fast, and reliable tool for identification of irradiated food. Untreated nuts may encounter hazards of carrying several pathogens or microbial contamination; walnuts are of specific importance due to their nutritional and medicinal values, and hence walnut processing via gamma irradiation is a necessary step. EPR was employed for the identification and dosimetry of Cs-137 gamma-irradiated walnuts (shells and kernels). Several important parameters were studied, such as spectral features, microwave power dependence of signal intensities, and short- and long-term time dependences. Responses of walnut shells and kernels to different radiation doses in the range 0–10 kGy were investigated. Results confirmed that EPR is a suitable tool for the identification and dosimetry of irradiated walnuts using either their shells or only kernels.     

X-band EPR study on benzo[c]cinnoline single crystals

The benzo[c]cinnoline compound has been crystallized in ethanol solution. These crystals have been irradiated with ⁶⁰Coγ-rays at room temperature. The crystals have been investigated by an X-band electron spin resonance (ESR) spectrometer two days after irradiation. Very strong ESR peaks have been observed at the temperatures between 130 and 430 K. However, a line broadening has been observed at 130 K. Also analyses found that EPR specra are temperature-dependent and show anisotropic behaviour.     

Tetravalent vanadium in CaF2 and SrF2 crystals: An EPR study

An EPR study of tetravalent vanadium centers created by room temperature X-irradiation in CaF₂ and SrF₂ is presented. The production efficiency of these centers is enhanced by previous annealing of the samples at 1000 K in air. The symmetry of V⁴⁺ ions is tetragonal and its EPR spectrum can be described by an axial spin Hamiltonian including a Zeeman and hyperfine term with $\text{S =}\text{1}\text{2}$ and $\text{I =}\text{7}\text{2}$ (corresponding to ⁵¹V nuclei). The following values for the spin Hamiltonian parameters are obtained g_∥ = 1.947 ± 0.002, g_⊥ = 1.935 ± 0.005, A_∥ = 500 ± 5 MHz, A_⊥ = 150 ± 10 MHz in the case of SrF₂ and g_∥ = 1.945 ± 0.002, A_∥ = 505 ± 5 MHz and A_⊥ < 200 MHz, in the case of CaF₂. A model for the center including an interstitial O^2? ion is tentatively proposed.     

An electron paramagnetic resonance study of LDPE irradiated with high-energy electron beam

Cross-linking of the polyethylene was performed with a high-energy electron beam. Electron paramagnetic resonance spectroscopy was used to study the lifetime of unpaired electron in the irradiated samples. Time-dependent electrical parameters are investigated for the cross-linked low-density polyethylene. Both dielectric constant and dielectric strength almost remained unchanged, but for short times, the volume resistivity and loss factor increased and decreased, respectively. It is predicted that for lifetime longer than 48 h, the electrical parameters were constant. It is believed that the variation of some electrical properties during time is due to the effects of trapped electrons.     

爆炸法合成纳米碳集聚体和纳米金刚石的EPR研究

爆炸法合成的纳米碳集聚体和纳米金刚石具有大量的结构缺陷和表面官能团. 电子顺磁共振（EPR）研究表明,它们均含有大量的自由基,而且纳米碳集聚体和纳米金刚石的EPR谱的形状、峰面积、g因子以及线宽ΔH_pp等都存在着较大的差异. 此外,还探讨了制备方法、化学处理条件、粒径大小、表面改性及掺杂对纳米碳集聚体和纳米金刚石的自由基密度的影响.     

Post-annealing effects on EPR response of irradiated nano-structure hydroxyapatite

In this work, the nano-structure hydroxyapatite was synthesized via the hydrolysis method. The produced powders were thermally treatment at different temperatures from 400 to 1200°C. The morphological and chemical analyses were carried out using the Fourier transmission infrared spectroscopy, transmission electron microscopy, and X-ray diffraction system. Then, the samples were irradiated at different absorbed doses from 1 to 80 kGy using ⁶⁰Co γ -ray. Electron paramagnetic resonance (EPR) responses of the samples were measured at room temperature in air. Subsequently, the variations of EPR signal intensities were constructed as the peak-to-peak signal amplitude and results were compared with those of non-annealed samples. The results show that the EPR responses of non-annealed samples are higher rather than other samples and also are saturated at higher doses in comparison with the others.     

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.     

A tunable reentrant resonator with transverse orientation of electric field for in vivo EPR spectroscopy

There has been a need for development of microwave resonator designs optimized to provide high sensitivity and high stability for EPR spectroscopy and imaging measurements of in vivo systems. The design and construction of a novel reentrant resonator with transversely oriented electric field (TERR) and rectangular sample opening cross section for EPR spectroscopy and imaging of in vivo biological samples, such as the whole body of mice and rats, is described. This design with its transversely oriented capacitive element enables wide and simple setting of the center frequency by trimming the dimensions of the capacitive plate over the range 100-900 MHz with unloaded Q values of approximately 1100 at 750 MHz, while the mechanical adjustment mechanism allows smooth continuous frequency tuning in the range +/-50 MHz. This orientation of the capacitive element limits the electric field based loss of resonator Q observed with large lossy samples, and it facilitates the use of capacitive coupling. Both microwave performance data and EPR measurements of aqueous samples demonstrate high sensitivity and stability of the design, which make it well suited for in vivo applications.     

EPR study of deoxygenated high-temperature superconductors

High-T _c superconductors are EPR silent but on a little deoxygenation of the high-T _c materials and their constituents, they yield rich but complex spectra. Spectra of (1) CuO, (2) BaCuO₂, (3) CaCuO₂, (4) Y₂Cu₂O₅, (5) La₂CuO₄, (6) La_2−x M _x CuO₄ (M=Sr, Ba), (7) Y based-123, (8) Bi based-2201, 2212, 2223, (9) Tl based-2223 and (10) Hg based-1212, 1223 have been studied. One thing common to all these materials is the CuO₂ plane which gets fragmented on deoxygenation and the inherent antiferromagnetic coupling is partially destroyed which results in the appearance of the spectra. The spectra recorded have been identified to be due to (1) Cu-monomer, (2) Cu-dimer, (3) Cu-tetramer, (4) Cu-octamer and (5) one signal at very low field which could not be identified because there was no structure in it and may be due to fragments higher than octamers. Very big fragments do not give any spectra because the original AF order probably remains intact in them. It is expected that when the fragments become magnetically isolated from the bulk, they produce EPR spectra. Most of the spectra have been analyzed and their spin-Hamiltonian parameters determined. The spectra of these species vary a little in terms of g-value and fine-structure splitting constant from sample to sample or even in the same sample and this may be attributed to some extra oxygen attachments retained with these species. Most frequently occurring species is the Cu-tetramer, (CuO)₄. As (CuO)₄ represents the unit cell of the all important two-dimensional CuO₂ plane of the high-T _c materials, its spectra have been argued to provide some clue to the mechanism of high-T _c superconductivity. The tetramer (CuO)₄ is a four one-half spin system and is essentially 16-fold degenerate by Heisenberg isotropic exchange, it is split into 6 components: one pentet, three triplets and two singlets. In superconductors the pentet appears to be the ground state and in the non-superconducting constituents the singlets seem to form the ground state as revealed by the temperature variation studies. In the case of La_1.854Sr_0.146CuO₄ we have found the signature of quantum stripe formation. The high-T _c superconductivity theories involving spin bag, antiferromagnetic spin fluctuations and magnons can be explained on the basis of Cu-tetramers.     

EPR spectra of γ-irradiated hydrated barium dithionate single crystals

EPR spectra of barium dithionate hydrate single crystals γ-irradiated at low (80 Gy) and high (10 kGy) doses are studied. Four lines, the strongest of which is due to the SO₃⁻ radical, are observed in the EPR spectrum of the low-irradiated samples. Another line seems to belong to SO₂⁻. The strong line and weak lines with hyperfine structure and lines for pairs of closely spaced SO₃⁻ centers with a strong angular dependence are observed at high irradiation doses. The main values of the SO₃⁻ hyperfine coupling tensor and the dipole-dipole coupling constants of the SO₃⁻ pairs are determined. A quantum-chemical calculation of the electronic structure of isolated SO₃⁻ and SO₂⁻ radicals is performed. Values of the g tensors and hyperfine couplings are calculated. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 18–22, January–February, 2008.     

Sensitivity of whole human teeth to fast neutrons and gamma-rays estimated by L-band EPR spectroscopy

This paper reports the first attempt to use L-band spectroscopy for estimating the sensitivity of whole teeth to fast neutrons and gamma-rays. Three teeth were successively irradiated first with fast neutrons with a wide energy spectrum (mean energy around 30 MeV) up to 160 Gy and then with gamma-rays up to 14 Gy. After each irradiation, L-band (1 GHz) EPR spectra of each whole tooth surrounded by the surface–coil resonator were recorded, yielding a single composite line principally due to CO₂⁻ and native radicals. The sensitivities are estimated by the slopes of the linear dose response curves of the dosimetric CO₂⁻ radicals. The ratios of the gamma/neutron sensitivities were found to be in the range 8–9 (±2) for the three teeth.     

Application of magnetic field over-modulation for improved EPR linewidth measurements using probes with Lorentzian lineshape

Magnetic field modulation in CW electron paramagnetic resonance (EPR) is used for signal detection. However, it can also distort signal lineshape. In experiments where the linewidth information is of particular importance, small modulation amplitude is usually used to limit the lineshape distortion. The use of small modulation amplitude, however, results in low signal-to-noise ratio and therefore affects the precision of linewidth measurements. Recently, a new spectral simulation model has been developed enabling accurate fitting of modulation-broadened EPR spectra in liquids. Since the use of large modulation amplitude (over-modulation) can significantly enhance the EPR signal, the precision of linewidth measurements is therefore greatly improved. We investigated the over-modulation technique in EPR oximetry experiments using the oxygen-sensing probe lithium octa-n-butoxy-substitued naphthalocyanine (LiNc-BuO). Modulation amplitudes 2-18 times the intrinsic linewidth of the probe were applied to increase the spectral signal-to-noise ratio. The intrinsic linewidth of the probe at different oxygen concentrations was accurately extracted through curve fitting from the enhanced spectra. Thus, we demonstrated that the over-modulation model is also applicable to particulate oxygen-sensing probes such as LiNc-BuO and that the lineshape broadening induced by oxygen is separable from that induced by over-modulation. Therefore, the over-modulation technique can be used to enhance sensitivity and improve linewidth measurements for EPR oximetry with particulate oxygen-sensing probes with Lorentzian lineshape. It should be particularly useful for in vivo oxygen measurements, in which direct linewidth measurements may not be feasible due to inadequate signal-to-noise ratio.     

EPR study of neutron irradiated Ge-S glasses

The results of EPR measurements on neutron irradiated Ge-S glasses doped by Mn are presented. It has been found that the integrated neutron flux from 1·1 × 10¹⁵ n. cm^–2 to 1·5× × 10¹⁷n. cm^–2 has no detectable effect on the nearest neighbour surroundings of Mn²⁺ probing ions but increases the intensity of all EPR lines. A new EPR line was detected in Mn-doped Ge-S glasses irradiated with the highest neutron dose of 1·5 × 10¹⁷ n. cm^–2.     

Paramagnetic frenkel defects in irradiated alkali-haloid crystals

In the EPR spectra of γ-irradiated NaF,⁶LiF, and LiF crystals with natural content of isotopes (independent of the impurity composition), the hyperfine structure (HFS) is observed against the background of a broad band. Absorption saturation in the system of defects responsible for the HFS and the broadband occurs at widely different power levels of microwave radiation, and broad band suppression takes place at registration in quadrature. The experimentally measured intensity distribution and the number of EPR lines in the⁶LiF crystal correlate with the calculated data when the spin interaction of an unpaired electron with 14 equaivalent fluorine nuclei is taken into account. A model of major radiation-induced paramagnetic defects in the form of Frenkel pairs, in which one component (the negatively charged quasi-molecule consisting of two halogen atoms) can be responsible for the HFS and the other component (F-center) for the broad band in the EPR spectrum, is proposed.     

紫草素与胞嘧啶相互作用的理论研究

采用密度泛函理论的M06方法在6-311++G**基组水平下对紫草素-胞嘧啶复合物进行了结构优化,得到了14个稳定的紫草素-胞嘧啶复合物。我们还应用了分子中的原子(AIM)理论和自然键轨道(NBO)理论对这14个复合物中的氢键的性质和特征进行了分析。通过基组重叠误差(BSSE)校正后的相互作用能、成键临界点电荷密度、二阶稳定化能的计算和分析,发现复合物1的结构是最稳定的。     

Progressive EPR imaging with adaptive projection acquisition

Continuous wave electron paramagnetic resonance imaging (EPRI) of living biological systems requires rapid acquisition and visualization of free radical images. In the commonly used multiple-stage back-projection image reconstruction algorithm, the EPR image cannot be reconstructed until a complete set of projections is collected. If the data acquisition is incomplete, the previously acquired incomplete data set is no longer useful. In this work, a 3-dimensional progressive EPRI technique was implemented based on inverse Radon transform in which a 3-dimensional EPR image is acquired and reconstructed gradually from low resolution to high resolution. An adaptive data acquisition strategy is proposed to determine the significance of projections and acquire them in an order from the most significant to the least significant. The image acquisition can be terminated at any time if further collection of projections does not improve the image resolution distinctly, providing flexibility to trade image quality with imaging time. The progressive imaging technique was validated using computer simulations as well as imaging experiments. The adaptive acquisition uses 50-70% less projections as compared to the regular acquisition. In conclusion, adaptive data acquisition with progressive image reconstruction should be very useful for the accelerated acquisition and visualization of free radical distribution.     

煤镜质组热解的电子顺磁共振研究

基于煤燃烧和自燃研究在煤矿生产安全以及煤炭资源的高效利用等实际生产和生活中的重要性,探讨了煤岩显微组分镜质组在有氧条件下热解的自由基反应. 采用电子顺磁共振技术对煤镜质组在有氧条件下300 ℃~450 ℃的加热分解产物及未加热处理常温下的镜质组样品做电子顺磁共振研究,得到300 ℃、350 ℃、400 ℃、450 ℃时其产物在常温下（25 ℃）时的电子顺磁共振信号,并对随加热温度不同,信号的产生和变化原因做了分析,研究结果表明煤镜质组在加热过程中有顺磁中心的浓度和顺磁中心成分的改变,该文中把它归因于镜质组的不同有机成分在不同温度下分解产生的自由基.