Radical formation in lithium trifluoromethane-sulfonate for ESR dosimetry

Lithium trifluoromethane-sulfonate (Li-TFMS:CF₃SO₃Li) irradiated by γ-rays showed an electron spin resonance (ESR) powder spectrum having the rhombicg-factor ofg _xx = 2.0259 ± 0.0005,g _yy = 2.0112 ± 0.0005 andg _zz = 2.0025 ± 0.0005 and a triplet hyperfine coupling constant ofA _xx/gβ= 0.8 ± 0.15 mT.A _yy andA _zz are not obtained because of the broadened spectrum. The energy levels,g-factor,A _xx/gβ and optical absorption spectrum of several conceivable radicals such as C^⋅F₂SO₃Li, CF₃-S-O^⋅ and CF₃-S-O-O^⋅ have been calculated by softwares MOPAC-V2 and Gaussian-98 based on ROHF (Restricted Hatree-Fock for open shell molecule). The most probable radical was ascribed to CF₃-SO^⋅ from both calculated and experimental results. The response to γ-ray dose and the thermal stability have been studied in addition to the effect of UV illumination for possible use of the signal intensity in ESR dosimetry. The obtained number of free radicals per 100 eV (G-value) was 1.23 ± 0.40.     

Radical pair dynamics observed with pulse-mode product-yield-detected ESR

Three pulse sequences have been employed for laser and microwave-pulse irradiation in the pulse mode product-yield-detected ESR technique to detect the dynamical feature of transient radical pair. In this method, the decrease in spin adduct yield as functions of delay times for irradiation/termination of the microwave pulse after the laser pulse are simulated with the Runge-Kutta method for a detailed reaction model to obtain the rate constants of cage product formation, escape of the radical pair, as well as the hydrogen abstraction reaction. As the representative reaction systems, photoreduction of anthraquinone, anthraquinone-2-sulfonate, and benzophenone in SDS micellar solution were employed. Effects of cyclohexene, added as a hydrogen donor, NaCl and Ethanol, added to change the microviscosity of micelle, on these reaction rate constants have been tested.     

New Possibilities of OD ESR: Vacuum Ultraviolet Generation of Radical Ion Pairs

A new version of the optically detected electron spin resonance (OD ESR) technique using vacuum ultraviolet radiation to generate radical ion pairs is discussed. The technique can be used to study the spin-correlated processes of charge recombination in thin films that can be useful in spintronics. Distinctive features of photoionization and high-energy (including X-ray) ionization are discussed. The first results obtained by the technique in the study of charge recombination in polymeric and liquid crystal films are presented. The results of the concurrent observation of the OD ESR and electron cyclotron resonance (ECR) in the low-pressure gas over the sample are outlined. A possible application of ECR in the context of the OD ESR spectroscopy is suggested.     

ESR Characterizations and Photochemistry of the Free Radical Species from 1,1′-Bi-2-Naphthol and Related Compounds

The ESR spectroscopic investigations on the formation of neutral and anionic radical species from 1,1′-Bi-2-naphthol and 1,1′-Bi-2-phenol at room temperature are reported. The photogeneration of the neutral radicals is accompanied by an unusual kinetic decay in the presence of light. The nature and the structure of the radicals are discussed.     

Radical pair dynamics in anionic micelles with different alkyl chain length as studied by pulse-mode product-yield-detected ESR

Dynamics of the radical pair composed of benzophenone ketyl radical and an alkyl radical of surfactant molecule in the micellar solution were studied by means of the pulse-mode product-yield-detected electron spin resonance (pulse-PYESR) technique. As the surfactants heptyl (C7), nonyl (C9), decyl (C10) and dodecyl (C12) sulfates were employed. Both the escape rate and the recombination rate of the radical pair decreased monotonously with increasing the alkyl-chain length from C7 to C12. A close relation between the escape rate and the critical micellar concentration divided by the aggregation number and also that between the recombination rate and internal viscosity of micelle are pointed out. The pulse-PYESR analysis on the radical pair containing the alkyl radical of surfactant molecule as one of the components is very powerful in extracting the kinetic constants of micelle, since the alkyl sulfate radical is an ideal probe for the micelle molecule.     

Time-Resolved ESR Study on Complex Radical Pairs Formed in the Photolysis of Methylene Blue Included in Water-Soluble Sulfonated Calixarenes

The photochemical reactions of methylene blue (MB) included in water-soluble sulfonated calix[n]arenes (n = 4, 6, 8) are studied using a time-resolved electron spin resonance method. The chemically induced dynamic electron polarization (CIDEP) spectra show the formation of the complex radical pair composed of the MB monocation radical and calixarene (phenoxyl-type) radical. The lifetime and broadened spectral shape are dependent on the size of the calixarene and are due to the longitudinal and transverse relaxation mainly induced by the tumbling motion of the radical pair with the spin dipole–dipole interaction. The pair dissociates in a few hundreds of nanoseconds in cases of n = 6 and 8.     

ESR Study in Reactive Oxygen Species Free Radical Production of Pinus kesiya var. langbianensis Heartwood Treated with Laccase

Enzymatic oxidation of lignin phenolic hydroxyl groups can enhance the level of autoadhesion between wood fibers or particles depending upon the bonding mechanism of wood-based materials without synthetic adhesives such as urea and phenol formaldehyde. The adhesive effect is caused by an increased number of reactive oxygen groups at the fiber surface. The parameters of laccase-treated wood fibers play vital roles in generating reactive oxygen species (ROS) free radicals. Laccase I (white-rot fungi) and laccase II (Aspergillus sp.) are used to catalyze the oxidation of heartwood powder of Pinus kesiya var. langbianensis in suspension under different pH values, temperatures, treatment times and different laccase concentrations. Electron spin resonance spectroscopy and spin trapping technique were used to detect the ROS free radicals generated in the laccase-treated heartwood powder and it was found that in it the concentration of ROS free radicals was higher than that in the control. Analysis of variance indicates that there was a significant difference between the ROS concentration values of laccase-treated heartwood powder under different pH values, treatment temperatures and times, and laccase dosages for both laccase I and II. Furthermore, the concentration of ROS free radicals generated by laccase I is higher than that generated by laccase II. It was found that the optimum conditions for generation of ROS in laccase-treated heartwood powder by the two kinds of laccase are pH 3.0; treatment temperature, 50 °C; treatment time, 2 h; enzyme concentration, 20 units/g of wood powder. Authors' address: Xinfang Duan, Research Institute of Wood Industry, Chinese Academy of Forestry, Wan Shou Shan, Beijing 100091, People's Republic of China     

ESR microscopy

New spatial imaging methods to determine the microscopic concentration of unpaired electron spins or paramagnetic ions (ESR microscopy methods) have been developed (a) with an intense magnetic field gradient method based on conventional magnetic resonance imaging (MRI) using field gradient coils in a cavity, (b) by scanning the localized magnetic field or modulation field mechanichally or electronically, and (c) by use of the scanning localized microwave field. Some examples of fossil imaging and of microdosimetry in this laboratory are reviewed briefly.     

ESR and ESR microscopy in geosciences and radiation dosimetry

ESR and its microscopic imaging (microscopy) have found new applications in interdisciplinary fields related with geosciences and with radiation dosimetry. Geological, archaeological and forensic dating has been made through paleo-dosimetry of natural radiation and chemical reactions of both radical formation and valency changes. ESR microscopy, especially the simple scanning method has a potentiality to be used in various fields. New applications of ESR are briefly reviewed with some examples.     

Educational experiments on ESR imaging with a portable ESR spectrometer

A light-weight portable electron spin resonance (ESR) spectrometer with the permanent magnet of Nd-B-Fe (Neomax) and field sweep coils was used as a demonstration tool of ESR microscopy for student’s experiments. Educational experiments on one-and two-dimensional ESR imaging are made by inserting field gradient coils or field scanning wire arrays into the cavity using test samples of DPPH. A preliminary work on double frequency modulation is described for two-dimensional imaging using microwire arrays.     

紧凑型电子自旋共振(ESR)仪

描述了一种原创的紧凑型电子自旋共振(ESR)仪.该仪器具备高性能、低成本、简单可靠、结构紧凑、开放构架、多功能模块等一系列特点.分析了ESR谱仪的多个微波单位,研发并通过实验验证了自差ESR谱仪的最优双腔结构,并设计了一种可提供高均匀磁场的电、永磁混合磁体.最后介绍了这种新型紧凑型电子自旋共振仪的主要参数和应用.     

ESR of Reacting Radicals

This paper represents a review of my research that was presented upon receiving the 2012 Zavoisky Award given by the Zavoisky Physical-Technical Institute in Kazan, Tatarstan, Russia. It is my belief that my early experiences gave an important background for experimental research and success in the area of ESR (electron spin resonance). I will describe some of these. In addition, I will give some of my educational experience that displayed how random chance was also important as to what research area I adopted. Much of my research has been with ESR of radicals produced by ionizing radiation and some of the more important observations are described. Among them is the initial discovery of chemically induced dynamic electron polarization (CIDEP). Also mentioned are a treatment of second-order hyperfine splittings and a number of issues regarding radical structure. This work also contributed to spectrometer design for time-resolved experiments. Modified Bloch equations were developed to describe the ESR time dependence. A number of observations on the hydrated electron, e _aq ^? , are described, including the finding of an “inverse” CIDEP when e _aq ^? is present with certain counter radicals. Several more recent studies finally explained this behavior. Two topics not used in the presentation are also included: a determination of the relaxation time of e _aq ^? and a determination of relative radical yields in pulse radiolysis. Finally, two other applications of microwave absorption are described, including a new method for determining the dipole moments of photo-excited molecules.     

ESR studies of sepiolites

The electron spin resonance (ESR) spectra for each beige and brown sepiolites from Polatli-Ankara, Turkey, a clay mineral of Mg₈Si₁₂O₃₀(OH)₄(OH₂)₄(H₂O)₈, at 77 K have their own single characteristic peak atg ≈ 1.99, which begins to anneal from 437 and 536°C, respectively. The sextet lines of Mn²⁺ were also observed in addition to two peaks (g = 4.4 and 5.0) associated with Fe³⁺. A high-quality sepiolite called “meerschaum” from Sepetci-Eskisehir, Turkey, has two characteristic peaks atg ≈ 1.99, which begins to anneal from 419°C, and atg ≈ 2.03. ESR intensities of the signal atg ≈ 1.99 for beige, brown sepiolites and meerschaum are enhanced by γ-ray irradiation to give equivalent dosesD _E = 11.8 ± 3.4, 4.7 ± 2.3 and 4.6 ± 1.2 kGy, respectively. The ESR ages obtained by assessing the annual dose rate from the content of²³⁸U,²³²Th and⁴⁰K determined by γ-ray spectroscopy are 1.8 ± 0.8, 0.7 ± 0.5 and 0.9 ± 0.2 Ma, respectively, falling into the Pliocene Epoch in geological time scale in agreement with the stratigraphy.     

卷积差技术在ESR和ESR成像中的应用

该文将卷积差技术应用于提高ESR谱的分辨率和在ESR成像过程中扣除固有线宽介绍了卷积差过程,对比了卷积差前后ESR谱的变化.     

ESR response of gamma-irradiated sulfamethazine

In the present work, characteristic features of the radiolytical intermediates produced in gamma-irradiated solid sulfamethazine (SMH) were investigated by electron spin resonance (ESR) spectroscopy. The heights of the resonance peaks, measured with respect to the spectrum baseline, were used to monitor microwave saturation, temperature and time-dependent kinetic features of the radical species contributing to the formation of recorded experimental ESR spectra. Three species having different spectroscopic and kinetic features were observed to be produced in gamma-irradiated SMH. SO₂, which is the most sensitive group of radiation in the SMH molecule, was found to be at the origin of radiation-produced ionic radical species. Based on the experimental results derived from the present study, the applicability of ESR spectroscopy to radiosterilization of SMH was discussed. In the dose range of interest (0.5–10 kGy), the radiation yield of solid SMH was calculated to be very low (G=0.45) compared with those obtained for sulfonamide aqueous solutions (G=3.5–5.1). Based on these findings, it was concluded that SMH and SMH-containing drugs could be safely sterilized by gamma radiation and that ESR spectroscopy could be successfully used as a potential technique for monitoring their radiosterilization.     

ESR studies of diamond powders

The ESR spectrum of two defect centres were observed in finely ground diamond powders (0.5 to 30 μm size). The one centre has been seen before in irradiated and annealed single crystals of natural diamonds (the O₁ centre) while the second one has only been seen in synthetic diamonds grown from a nickel-iron melt and is only observable below 250 K. From the study of the variation of the intensity of these lines with size of particles it could be concluded that the O₁ centre lies just beneath the surface of these particles and the S centre at least 0.5 μm below the surface.     

谱-空间2D ESR成像

在Bruker ER 200D ESR 谱仪上安装一套自制的谱-空间2D ESR成像系统,这套系统由一对梯度场线圈、电源、微机及图像重建程序组成. 用滤波反投影图像重建方法,实现了两种自由基样品的谱-空间2D ESR成像,由2D 图像得到样品中自由基的自旋密度空间分布及相应的波谱参数. 讨论了成像参数与图像精度的关系.     

ESR study of fullerene black

Fullerene black before and after annealing at 850°C has been studied by electron spin resonance (ESR). For initial fullerene black, the ESR line exhibits wide wings and its shape is caused by magnetic dipole-dipole interactions between radicals localized randomly on the carbon surface. Dioxygen decreases reversibly the amplitude of the ESR line without changes in its shape, width (0.19 mT) andg-factor (2.0022). This is explained by the assumption that dioxygen molecules adsorbed on the surface broaden strongly ESR lines only of neighboring radicals. For annealed fullerene black, the ESR line is Lorentzian, dioxygen reversibly broadens the line, and theg-factor decreases with the broadening of the line by dioxygen. This is explained by radical-radical and radical-dioxygen spin exchange interactions via conjugated bonds formed in the course of annealing. Flattening of curved carbon surfaces after annealing explains in a uniform way changes in parameters of ESR lines and in reactivity and catalytic activity of fullerene black.