Influence of microwave power on EPR spectra of coal macerals

The paper contains a numerical analysis of the electron paramagnetic resonance (EPR) spectra of coal macerals (exinite, vitrinite, inertinite) obtained from Polish medium-rank coal (85.6 wt% C). We determine the lineshapes and the parameters of the component lines, i.e., the intensities and linewidths. As a result, we find that the EPR spectra of the studied macerals are superpositions of broad Gaussian, broad Lorentzian 1 and narrow Lorentzian 3 lines for vitrinite and exinite and two narrow Lorentzian 2 and Lorentzian 3 lines for inertinite. The influence of microwave power on the component lines of the EPR spectrum is studied. A comparison of the results obtained at 223 and 293 K shows that the EPR lines at both temperatures saturate at the same microwave power. It also indicates similar changes of the linewidths with changes of microwave power at both temperatures, a slight increase with increasing microwave power.     

Inversion-recovery detected EPR

Inversion-recovery detected EPR is introduced. This field-swept EPR method is based on a periodically repeated inversion recovery experiment, with detection of the first harmonic of the periodically oscillating transverse magnetization. With inversion-recovery detected EPR, pure absorption spectra are obtained with signal amplitudes depending on the repetition rate of the inverting π pulses and on the strength of the probe field. The technique is particularly well suited for the measurement of broad EPR lines and for separating overlapping spectra of paramagnetic species with different spin-lattice relaxation timesT ₁. The experiment is analyzed theoretically and some of the predicted features are experimentally verified. Inversion-recovery detected EPR spectra of a single crystal, a polycrystalline and a liquid solution sample are presented, and the separation of overlapping spectra is demonstrated.     

EPR谱图模拟软件EasySpin的图形用户界面设计

EasySpin是一款较为流行的电子顺磁共振（EPR）谱图模拟和拟合软件,LabVIEW是一种图形化编程语言开发环境．本文介绍了一款使用LabVIEW为EasySpin设计的图形用户界面LV-EasySpin．LV-EasySpin提供了一种直观的操作方法来实现连续波EPR多组分波谱的可视化模拟和拟合．本文辅以各种模式下的实例进行说明,阐述了LV-EasySpin的设计思路与实现方案,最终希望具有简洁、易操作界面的LV-EasySpin可以降低用户使用EasySpin分析EPR谱图的难度．     

Detection of undistorted continuous wave (CW) electron paramagnetic resonance (EPR) spectra with non-adiabatic rapid sweep (NARS) of the magnetic field

A continuous wave (CW) electron paramagnetic resonance (EPR) spectrum is typically displayed as the first harmonic response to the application of 100 kHz magnetic field modulation, which is used to enhance sensitivity by reducing the level of 1/f noise. However, magnetic field modulation of any amplitude causes spectral broadening and sacrifices EPR spectral intensity by at least a factor of two. In the work presented here, a CW rapid-scan spectroscopic technique that avoids these compromises and also provides a means of avoiding 1/f noise is developed. This technique, termed non-adiabatic rapid sweep (NARS) EPR, consists of repetitively sweeping the polarizing magnetic field in a linear manner over a spectral fragment with a small coil at a repetition rate that is sufficiently high that receiver noise, microwave phase noise, and environmental microphonics, each of which has 1/f characteristics, are overcome. Nevertheless, the rate of sweep is sufficiently slow that adiabatic responses are avoided and the spin system is always close to thermal equilibrium. The repetitively acquired spectra from the spectral fragment are averaged. Under these conditions, undistorted pure absorption spectra are obtained without broadening or loss of signal intensity. A digital filter such as a moving average is applied to remove high frequency noise, which is approximately equivalent in bandwidth to use of an integrating time constant in conventional field modulation with lock-in detection. Nitroxide spectra at L- and X-band are presented.     

Pseudo field modulation in EPR spectroscopy

This paper develops methodology for computer simulation of the effect on an experimental EPR spectrum that would occur if an additional field modulation were applied followed by eventual phase sensitive detection at the modulation frequency or at one its harmonics. The algorithm, which is called pseudomodulation, transforms the digitized spectrum and also filters the noise. If a second harmonic spectrum is desired in order to make subtle changes in curvature more apparent, it is shown that it is always preferable to obtain an experimental second harmonic spectrum. The signals are identical, but because of the filtering properties of the pseudomodulation algorithm, the noise is lower. Pseudomodulation should be applied to simulated spectra prior to fitting a model to data in order more precisely to simulate the experimental signal. It is argued that such fits ought to involve not only first harmonics but also higher harmonics, since the various harmonics are sensitive in different ways to input parameters in the spin Hamiltonian. Application of pseudomodulation to the EPR spectrum of the blue copper-protein azurin is described.     

YAG晶体色心的EPR谱

本文描述了8种YAG样品的室温和77K的EPR谱.从这些谱的参数与光谱的实验数据对照,认为晶体中有三种顺磁性的色心,其中g～2.00和g～1.98两条顺磁谱相应于光谱2×10~4cm~(-1)～3.4×10~4cm~(-1)的吸收带,为YAG基质晶体中的缺陷俘获一个电子构成的电子型缺陷中心;而 g～30.60的顺磁谱线与氧空位和掺杂的金属离子Mg~(2+) 、Cr~(3+)有关,推测为氧空位团或氧空位与金属离子构成的S>1/2的复合顺磁中心缺陷.YAG晶体随着在大气氛中高温退火,氧的进入和金属离子的掺入,造成电子和空间体积的不平衡,从而使晶体色心浓度加大.     

EasySpin, a comprehensive software package for spectral simulation and analysis in EPR

EasySpin, a computational package for spectral simulation and analysis in EPR, is described. It is based on Matlab, a commercial technical computation software. EasySpin provides extensive EPR-related functionality, ranging from elementary spin physics to data analysis. In addition, it provides routines for the simulation of liquid- and solid-state EPR and ENDOR spectra. These simulation functions are built on a series of novel algorithms that enhance scope, speed and accuracy of spectral simulations. Spin systems with an arbitrary number of electron and nuclear spins are supported. The structure of the toolbox as well as the theoretical background underlying its simulation functionality are presented, and some illustrative examples are given.     

Simultaneous acquisition of pulse EPR orientation selective spectra

High resolution pulse EPR methods are usually applied to resolve weak magnetic electron-nuclear or electron-electron interactions that are otherwise unresolved in the EPR spectrum. Complete information regarding different magnetic interactions, namely, principal components and orientation of principal axis system with respect to the molecular frame, can be derived from orientation selective pulsed EPR measurements that are performed at different magnetic field positions within the inhomogeneously broadened EPR spectrum. These experiments are usually carried out consecutively, namely a particular field position is chosen, data are accumulated until the signal to noise ratio is satisfactory, and then the next field position is chosen and data are accumulated. Here we present a new approach for data acquisition of pulsed EPR experiments referred to as parallel acquisition. It is applicable when the spectral width is much broader than the excitation bandwidth of the applied pulse sequence and it is particularly useful for orientation selective pulse EPR experiments. In this approach several pulse EPR measurements are performed within the waiting (repetition) time between consecutive pulse sequences during which spin lattice relaxation takes place. This is achieved by rapidly changing the main magnetic field, B(0), to different values within the EPR spectrum, performing the same experiment on the otherwise idle spins. This scheme represents an efficient utilization of the spectrometer and provides the same spectral information in a shorter time. This approach is demonstrated on W-band orientation selective electron-nuclear double resonance (ENDOR), electron spin echo envelope modulation (ESEEM), electron-electron double resonance (ELDOR)--detected NMR and double electron-electron resonance (DEER) measurements on frozen solutions of nitroxides. We show that a factors of 3-6 reduction in total acquisition time can be obtained, depending on the experiment applied.     

Conformational dynamics of triradical nitroxides as studied by EPR

The EPR spectra of a flexible nitroxide triradical are recorded in a large temperature range. A detailed analysis of the spectral features is performed and the spectra are compared with computer simulations. An excellent agreement with the experimental spectra is obtained by using a dynamic model based on the conformation interconversion of different molecular structures, characterized by the electron exchange interactions between pairs of free radicals. The energy barrier for the interconversion process and the temperature variation of the constant for the equilibrium among the conformations have been obtained. The results show that EPR spectra of nitroxide triradicals spin labelled polymers could be of valuable use for studying subtle details of molecular dynamics.     

Some peculiarities of the EPR spectra of radiation-induced defects in LiF and NaF crystals

To refine the structure of radiation-induced defects, a comparison is made of the EPR spectra of LiF and NaF crystals with various constituent impurities γ-irradiated with different doses, as well as the experimentally measured and calculated intensity distributions of HFS lines in the EPR spectra of these crystals. It is shown that the F-centers, whose model represents an ionized quasimolecule consisting of two metal atoms on each side of a halide vacancy, are responsible for the broad band observed independently of the impurity composition of the crystals and irradiation dose, while the HFS is caused by defects based on interstitial halide atoms. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 455–459, May–June, 1998.     

Absorption line CW EPR using an amplitude modulated longitudinal field

In standard continuous wave electron paramagnetic resonance (CW-EPR) experiments, the first derivative of absorption lines is detected. This type of a line shape is caused by the magnetic field modulation and is usually an undesired feature, since the sensitivity of CW-EPR drastically decreases with increasing linewidth. A new approach is introduced, which allows for the measurement of absorption line EPR spectra in systems with broad inhomogeneous lines. The method makes use of multiple-photon transitions that are induced in spin systems when a transverse microwave and a longitudinal radio frequency field are simultaneously applied. The absorption lines are obtained by using amplitude modulation of the radio frequency field and slight saturation of the spectral lines. The basics of the new approach are discussed and experimental examples are given.     

Free radical EPR spectroscopy analysis using blind source separation

In this paper, we propose a novel approach for electron paramagnetic resonance (EPR) mixture spectra analysis based on blind source separation (BSS) technique. EPR spectrum of a free radical is often superimposed by overlapping spectra of other species. It is important and challenging to accurately identify and quantify the 'pure' spectra from such mixtures. In this study, an automated BSS method implementing independent component analysis is used to extract the components from mixed EPR spectra that contain overlapping components of different paramagnetic centers. To apply this method, there is no requirement to know the component spectra or the number of components in advance. The method is applied to analyze free radical EPR spectra which are collected from standard chemical system, cultured cell suspense, and ex vivo rat kidneys by spin trapping EPR technique. Results show that the BSS method proposed here is capable of identifying the component EPR spectra from mixtures with unknown compositions. The BSS technique can offer powerful aids in resolving spectral overlapping problems in general EPR spectroscopy analysis.     

EPR spectra of C60 anions

The broad and sharp EPR signals observed in spectra of C₆₀ and C ₆₀ ^3? are summarized and proposed assignments are discussed. The sharp signals in samples of C ₆₀ ^2? are reviewed.     

Time-dependent physical spectra of Gaussian Schell-model pulses

The time-dependent physical spectra introduced by Eberly and Wódkiewicz [J. Opt. Soc. Am. 67 (1977) 1252], observable with a photon-counting detector placed behind a Fabry-Perot filter, are evaluated for a class of temporally partially coherent non-stationary fields known as Gaussian Schell-model plane-wave pulses. Numerical comparisons between source spectra and observed spectra are provided and discussed, and several general features such as initial spectral broadening at the arrival of the pulse and a temporal pulse tail are illustrated. Closed-form approximations are obtained for the time evolution of the observable spectrum by evaluating the leading terms in an appropriate series expansion.     

Radio frequencies in EPR: Conventional and advanced use

This mini-review focuses on various aspects of the application of radio frequency (rf) irradiation in electron paramagnetic resonance (EPR). The development of the electron-nuclear double resonance (ENDOR) technique is briefly described, and we highlight the use of circularly polarized rf fields and pulse ENDOR methodology in one- and two-dimensional experiments. The capability of pulse ENDOR at Q-band is illustrated with interesting experimental examples. Electron spin echo envelope modulation effects induced by an rf field in liquid samples demonstrate another role which rf fields can play. Technical achievements in the design of ENDOR resonators are illustrated by the example of a bridged loop-gap resonator. Finally, the influence of longitudinal rf fields on the dynamics of EPR transitions is explained using a dressed spin resonance treatment.     

Novel sparse component analysis approach to free radical EPR spectra decomposition

Free radicals play important roles in many physiological and pathological pathways in biological systems. These free radicals can be detected and quantified by their EPR spectra. The measured EPR spectra are often mixtures of pure spectra of several different free radicals and other chemicals. Blind source separation can be applied to estimate the pure spectra of interested free radicals. However, since the pure EPR spectra are often not independent of each other, the approach based on independent component analysis (ICA) cannot accurately extract the required spectra. In this paper, a novel sparse component analysis method for blind source separation, which exploits the sparsity of the EPR spectra, is presented to reliably extract the pure source spectra from their mixtures with high accuracy. This method has been applied to the analysis of EPR spectra of superoxide, hydroxyl, and nitric oxide free radicals, for both simulated data and real world ex vivo experiment. Compared to the traditional self-modeling method and our previous ICA-based blind source separation method, the proposed sparse component analysis approach gives much better results and can give perfect separation for mixtures of superoxide spectrum and hydroxyl spectrum in the ideal noise-free case. This method can also be used in other similar applications of quantitative spectroscopy analysis.     

Simulation studies of high-field EPR spectra of spin-labeled lipids in membranes

The high-field (i.e., 94 GHz) membrane EPR spectra of lipids spin labeled in their fatty acid chains have been simulated by using two limiting motional models. The aim was to identify the dynamic origin of the residual (g(xx) - g(yy)) anisotropy observed in the nonaxial EPR spectra of cholesterol-containing membranes. It is concluded that the residual spectral anisotropy arises from in-plane ordering of the lipid chains by cholesterol. The partial averaging of the (g(xx) - g(yy)) anisotropy was best described by restricted axial rotation with a frequency in the region of tau(-1)(R||) approximately 0.5-1 x 10(9) s(-1). Simulations for slower axial rotation of unrestricted amplitude produced less satisfactory fits. In phospholipid membranes not containing cholesterol, the nonaxial anisotropy is completely averaged in the fluid phase and substantially reduced even in the gel phase. The unrestricted axial rotation in the gel phase is of comparable frequency to that of the limited axial rotation in the liquid-ordered phase of membranes containing cholesterol. These results on in-plane ordering by cholesterol in the liquid-ordered phase could be significant for current proposals regarding domain formation in cellular membranes.     

Effect of a weak dimer-dimer interaction on the EPR line shape of polycrystalline samples

The spectroscopic manifestations of a weak interaction between dimers in the EPR spectra of polycrystalline samples are analyzed. It is shown that, under specific conditions, the weak interaction between dimers can be responsible for the additional lines in the EPR spectrum. The appearance of these features is associated with the collapse of the spectral lines in orientations satisfying the condition of exchange narrowing for the components of the fine structure in the spectrum of the dimer.