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.     

An EPR study on cytosine irradiated

In this study, paramagnetic centers over the cytosine were formed by photolysis then these centers were investigated using EPR method. EPR signals were not recorded from non‐irradiated the cytosine, but irradiated polycrystalline exhibited complex EPR spectra. For obtaining of cytosine polycrystalline, novel crystallization method was performed on powder cytosine. Effective crystallization conditions were achieved by adjustment of the concentration of the metal ions, chemical solutions, NaCl, KCl, glacial asetic acid, nitric oxide, percloric acid, glutamic acid, and pH of buffer. Cytosine (C₄H₅N₂O) polycrystalline obtained were irradiated with ⁶⁰Co – rays at room temperature for 24 and 72 h. At the sample irradiated for 72 h, the paramagnetic centers were determined between 120 and 450 K by X‐band EPR spectrometer. The spectra were found to be dependent slightly on temperature. Two cation radicals were determined in the structure and these were called Radicals I and II. The g and hyperfine constants were found to be a_H2a = 61 G, a_N2 = 9.39 G, a_N1 = 7.15 G, and g₁=2.0026 for the Radical I; a_H3 = 10.57 G, a_H1 = 3 G, a_N3 = 6.72 G, a_N1 = 5.36 G for, and g₂=2.0034 the Radical II. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and electron paramagnetic resonance study of a nitroxide free radical covalently bonded on aminopropyl-silica gel

A solid spin-labeled material was obtained starting from 2-chloro-3,5-dinitro-N-(4-(2,2,6,6-tetramethyl-piperidine-1-oxyl)-benzamide) and aminopropyl-silica gel. Stability tests showed that even after several months the spin-labeled material had the same properties as immediately after synthesis. EPR properties of the TEMPO-derivatized silica were studied as a function of solvent polarity and temperature. Rotational correlation times were calculated from EPR spectra and correlated with solvent characteristics and temperature. Polar solvents induce a fast motion of the spin-label, clearly seen in the EPR spectra by the apparition of the well-known TEMPO radical triplet. The solid spin-labeled (dry) sample showed a high interspin interaction, which can be disrupted not only by different (liquid) solvents, but also by absorption of different solids, like cyclodextrins, dendrimers or polyethyleneglycols. Also, changes induced by the temperature were studied in the case of toluene wet sample. From 150 to 370 K, the spectrum is changing from a slow motion spectrum type to a fast motion regime. The preparative procedures to obtain the spin-labeled silica as well as some of its parameters are described.     

Electron paramagnetic resonance study of gamma-irradiated potassium hydroquinone monosulfonate single crystal

Gamma-irradiated potassium hydroquinone monosulfonate (PHM) single crystals were investigated between 125 and 300?K using the electron paramagnetic resonance (EPR) technique. Between 125 and 300?K no changes in the spectra have taken place. The spectra were found to be temperature independent. The investigation of EPR spectra of irradiated single crystals of PHM showed the presence of two PHM anion radicals. The g values of the radiation damage centers observed in the PHM single crystal and the hyperfine structure constants of the free electron with nearby protons were obtained.     

An X-band time domain electron paramagnetic resonance spectrometer

A computer-controlled X-band time domain electron paramagnetic resonance (EPR) spectrometer, with a time resolution of the order of 0.5μsec, has been constructed with many of the crucial microwave components designed and fabricated by the Microwave Engineering Group of TIFR. The spectrometer operates either in a microwave power pulsed mode for determination of spin-lattice relaxation times by the saturation recovery technique or in the kinetic mode for determination of the time dependence of EPR signal after laser excitation. It has an automatic frequency control, an automatic phase control and, most importantly, a field-frequency lock which ensures good stability of the EPR line positions enabling signal averaging for extended periods. The constructional details of the spectrometer and its performance in both the modes are described here by reporting results on certain typical systems.     

Electron paramagnetic resonance study of irradiated tetramethyl-4-piperidion

The electron paramagnetic resonance of single crystals of tetramethyl-4-piperidion (TMP; C₉H₁₉NO) has been observed and analysed for different orientations of the crystal in the magnetic field, after being damaged at 300 K by γ-irradiation. The crystals have been investigated between 100 and 450 K. The spectra were found to be temperature dependent. The irradiation of TMP by γ-rays produces radicals at the nitrogen atoms in the molecule. The principal values of the hyperfine coupling tensor of the unpaired electron and the principal values of the g-tensor were determined. The results were found to be in good agreement with the existing literature data and theoretical predictions.     

Time-resolved electron paramagnetic resonance of radical pair intermediates in cryptochromes

Electron transfer plays a key role in many biological systems, including core complexes of photosynthesis and respiration. As this involves unpaired electron spins, electron paramagnetic resonance (EPR) is the method of choice to investigate such processes. Systems that show photo-induced charge separation and electron transfer are of particular interest, as here the processes can easily be synchronised to the experiment and therefore followed directly over its time course. One particular class of proteins, the cryptochromes, showing charge separation and in turn spin-correlated radical pairs upon excitation with blue light, have been investigated by time-resolved EPR spectroscopy in great detail and the results obtained so far are summarised in this contribution. Highlights include the first observation of spin-correlated radical pairs in these proteins, a fact with great impact on the proposed role as key part of a magnetic compass of migratory birds, as well as the assignment of the radical-pair partners and the unravelling of alternative and unexpected electron transfer pathways in these proteins, giving new insights into aspects of biological electron transfer itself.     

Egyptian limestone for gamma dosimetry: an electron paramagnetic resonance study

The electron paramagnetic resonance (EPR) properties of limestone from a certain Egyptian site were investigated in order to propose an efficient and low-cost gamma dosimeter. Radiation-induced free radicals were of one type which was produced in the limestone samples at g=2.0066 after exposure to gamma radiation (⁶⁰Co). EPR spectrum was recorded and analyzed. The microwave power saturation curve and the effect of changing modulation amplitude on peak-to- peak signal height were investigated. The response of limestone to different radiation doses (0.5–20 kGy) was studied. Except for the decrease in signal intensities during the first five hours following irradiation, over the period of two months fair stabilities of signal intensities were noticed. From the current results, it is possible to conclude that natural limestone may be a suitable material for radiation dosimetry in the range of irradiation processing.     

Finite size effects in ZnO nanoparticles: An electron paramagnetic resonance (EPR) analysis

ZnO nanoparticles were synthesized by solid coprecipitation method with consecutive high energy ball milling procedure. By reducing the particle size of ZnO to nano dimensions strong nano‐size effects were observed. In order to characterize the ZnO defect structure, EPR has been applied. It was observed that below 50 nm the surface defects play a dominant role in the electronic properties of ZnO. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An electron paramagnetic resonance and density-functional theory study on the methyl isotropic hyperfine coupling constants in gamma-irradiated 2,6-di-tert-butyl-4-methylphenol

Single crystal of gammairradiated 2,6-di-tert-butyl-4-methylphenol (BHT) was investigated using an electron paramagnetic resonance (EPR) technique at different orientations in the magnetic field at room temperatures. Taking into consideration the chemical structure and the experimental spectra of the irradiated single crystal of BHT, we assumed that one phenoxyltype paramagnetic species was produced having an unpaired electron localized at the methyl fragment side of the phenyl ring. Depending on this assumption, one possible radical was modeled using the B3LYP/6-311+G(d) level of density-functional theory. EPR parameters were calculated for these modeled radical using the B3LYP/TZVP and B3LYP/EPR-III level. The averaged value of isotropic hydrogen hyperfine coupling constants of rotating methyl functional group of phenoxyl radical is calculated for the first time. Theoretically calculated values of the modeled radical are in reasonably good agreement with the experimental data determined from the spectra (differences in averaged coupling constant values smaller than 5%, and differences in isotropic g values fall into 1 ppt).     

On the analysis of broad Dysonian electron paramagnetic resonance spectra

We analyze the equation used for simulating the lineshapes of broad electron paramagnetic resonance spectra in conducting samples (i.e., broad Dysonian lineshapes) where it becomes necessary to include the effects of both clockwise and counterclockwise rotating components of the microwave magnetic field. Using symmetry arguments, we propose a modification to the equation. We show that the modified equation fits the experimental results better than the equation used in literature.     

The continuous wave electron paramagnetic resonance experiment revisited

When the modulation frequency used in continuous wave electron paramagnetic resonance (cw EPR) spectroscopy exceeds the linewidth, modulation sidebands appear in the spectrum. It is shown theoretically and experimentally that these sidebands are actually multiple photon transitions, sigma(+)+kxpi, where one microwave (mw) sigma(+) photon is absorbed from the mw radiation field and an arbitrary number k of radio frequency (rf) pi photons are absorbed from or emitted to the modulation rf field. Furthermore, it is demonstrated that both the derivative shape of the lines in standard cw EPR spectra and the distortions due to overmodulation are caused by the unresolved sideband pattern of these lines. The single-photon transition does not even give a contribution to the first-harmonic cw EPR signal. Multiple photon transitions are described semiclassically in a toggling frame and their existence is proven using second quantization. With the toggling frame approach and perturbation theory an effective Hamiltonian for an arbitrary sideband transition is derived. Based on the effective Hamiltonians an expression for the steady-state density operator in the singly rotating frame is derived, completely describing all sidebands in all modulation frequency harmonics of the cw EPR signal. The relative intensities of the sidebands are found to depend in a very sensitive way on the actual rf amplitude and the saturation of single sidebands is shown to depend strongly on the effective field amplitude of the multiple photon transitions. By comparison with the analogous solutions for frequency-modulation EPR it is shown that the field-modulation and the frequency-modulation technique are not equivalent. The experimental data fully verify the theoretical predictions with respect to intensities and lineshapes.     

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.     

Electron paramagnetic resonance of a nitrogen-related centre in electron irradiated silicon

The observation by electron paramagnetic resonance of a centre related to nitrogen as an impurity in silicon is reported. While all previously reported nitrogen-related centres in silicon were produced by nitrogen implantation, the present centre is observed after electron irridiation of aluminium-doped silicon at low temperatures. We tentatively identify the observed spectrum, labeled Si-NL26, with neutral interstitial nitrogen. Possible models for the incorporation of nitrogen in silicon, before the irradiation, after the irradiation and after thermal anneal, are discussed.     

Electron paramagnetic resonance imaging using magnetic-field-gradient spinning

A novel X-band CW EPR imaging has been developed using magnetic-field-gradient (MFG) spinning to obtain spatial distributions of electron paramagnetic species. Spinning MFG EPR imaging for 65 projection spectra required just 55 s while conventional imaging took 11 min 40 s, that is, the acquisition time for the new system is one order of magnitude shorter than that for conventional EPR imaging. Spinning MFG EPR imaging allows one to measure reconstructed images in an interactive manner where resolution and condition can be changed quickly.     

Systematic approach to cutoff frequency selection in continuous-wave electron paramagnetic resonance imaging

This article describes a systematic method for determining the cutoff frequency of the low-pass window function that is used for deconvolution in two-dimensional continuous-wave electron paramagnetic resonance (EPR) imaging. An evaluation function for the criterion used to select the cutoff frequency is proposed, and is the product of the effective width of the point spread function for a localized point signal and the noise amplitude of a resultant EPR image. The present method was applied to EPR imaging for a phantom, and the result of cutoff frequency selection was compared with that based on a previously reported method for the same projection data set. The evaluation function has a global minimum point that gives the appropriate cutoff frequency. Images with reasonably good resolution and noise suppression can be obtained from projections with an automatically selected cutoff frequency based on the present method.     

The optical and paramagnetic absorption spectra of MgO:Mn single crystals irradiated in a reactor

The optical and paramagnetic absorption spectra of MgO:Mn crystals of different origin, irradiated in a reactor, have been investigated. It is found that, in spite of only a small amount of Mn²⁺ impurity ions in the investigated crystals, their influence on the efficiency of formation and accumulation of F⁺-centers is dominant. The dependence of the number of F⁺-centers both on irradiation dose and on manganese concentration is studied.     

A study of the firing temperature of archeological pottery by X-ray diffraction and electron paramagnetic resonance

A fragment of an archeological funerary urn from Campos dos Goytacazes, Brazil, was studied using electron paramagnetic resonance (EPR) and X-ray diffraction (XRD). The thermal stability of all paramagnetic species was studied with isothermal treatment. In the present study, the iron signal (Fe³⁺) cannot be used as a firing temperature reference for archeological pottery. The intensification of this signal with temperature is a consequence of Fe²⁺ oxidation, but this reaction occurs in a short-lived treatment at high temperature or in an extended treatment at lower temperature. However, the iron signal and three other paramagnetic species indicate that the urn was fired for an extended time (up to three days). The thermal stability of the three paramagnetic species indicates a firing temperature of around 500 °C in the inner layer, between 400 and 500 °C in the middle layer, and between 500 and 800 °C in the outer layer. The presence of kaolinite structures only in the middle portion is consistent with the temperature values estimated. A firing method for the funerary archeological urn is suggested.