High Spatial Resolution Multi-Site EPR Oximetry: The Use of a Convolution-Based Fitting Method

We describe a new method to enhance the spatial resolution of multi-site electron paramagnetic resonance (EPR) oximetry. The method is suitable for any shape (density distribution function) of a solid paramagnetic material implanted in tissue. It corrects distortions of lineshapes caused by the gradient and thus overcomes limitations of previous multi-site EPR oximetry methods that restricted the ratio of the particle size to the distance between sites. The new method is based on consecutive applications of magnetic field gradients with the same direction but with a different magnitude and uses a convolution-based fitting algorithm to derive Lorentzian EPR linewidths of each individual peak of the EPR spectrum. The method is applicable for any particulate EPR oxygen sensitive materials whose EPR spectra can be approximated by a Lorentzian function or a superposition of Lorentzian functions. By incorporating this model of the lineshape in the data processing, we are able to decrease significantly the number of parameters needed for the calculations and to recover the oxygen concentration, even from quite noisy spectra. We (i) describe our method and the data-processing algorithm, (ii) demonstrate our approach in model and in vivo experiments, and (iii) discuss the limitations.     

采用曲线拟合方法进行EPR波谱基线校正

提供了一种以曲线拟合方式进行的EPR波谱基线校正的简单方法.程序置于486微机上,采用C⁺⁺语言编写,在Windws环境下运行.使用菜单、模块化方式.操作简单,快捷.在联机进行数据采集时尤为方便.本程序对需要进行基线校正的谱线,只需使用鼠标器在实验谱上选择一定的数据点,通过程序运算,比较,验算即可得到较好的基线校正.     

Distance measurements in the borderline region of applicability of CW EPR and DEER: a model study on a homologous series of spin-labelled peptides

Inter-spin distances between 1 nm and 4.5 nm are measured by continuous wave (CW) and pulsed electron paramagnetic resonance (EPR) methods for a series of nitroxide-spin-labelled peptides. The upper distance limit for measuring dipolar coupling by the broadening of the CW spectrum and the lower distance limit for the present optimally-adjusted double electron electron resonance (DEER) set-up are determined and found to be both around 1.6-1.9 nm. The methods for determining distances and corresponding distributions from CW spectral line broadening are reviewed and further developed. Also, the work shows that a correction factor is required for the analysis of inter-spin distances below approximately 2 nm for DEER measurements and this is calculated using the density matrix formalism.     

Fitting of deuterium quadrupole echo spectra with multiple motional models

Dynamic information is generally extracted from deuterium quadrupole echo spectra by matching a spectrum calculated for a particular motional model to the experimental spectrum. In this work, a set of computer programs has been written to facilitate fitting of calculated spectra to experimental spectra that represent from one to five motional models. The fitting program requires pre-calculated libraries of spectra for the models of interest, and accomplishes the fitting either by a systematic method or by simulated annealing. The systematic method is convenient for fitting with one or two motional models, but the simulated annealing method is faster for two or more models, if the libraries are made up of hundreds of spectra. The parameter Q, with the standard deviation of the spectral points estimated as the standard deviation of the baseline noise, provides a stringent measure of goodness of fit. Acceptable fits of experimental data as judged by this criterion have not been found, even in the case of ring flip motion in phenylalanine-d(5) in which the fit may be judged acceptable by eye. An example of fitting with isotropic and methyl rotation motional models of alanine-d(3), which have distinct spectral patterns, shows that it is possible to obtain reasonably accurate estimates of the relative amounts of deuterium representing the different models, even from poorly fitted spectra.     

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.     

FID detection of EPR and ENDOR spectra at high microwave frequencies

High-frequency pulsed EPR spectroscopy allows FID detection of EPR spectra owing to the short dead time that can be achieved. This FID detection is particularly attractive for EPR and ENDOR spectroscopy of paramagnetic species that exhibit inhomogeneously broadened EPR lines and short dephasing times. Experiments are reported for the metalloprotein azurin at 275 GHz.     

Recent applications of EPR and spin trapping to sonochemical studies of organic liquids and aqueous solutions

In this paper we review some of our recent applications of the EPR spin trapping technique to sonochemical studies which include identification of radicals formed in organic liquids and aqueous mixtures of organic liquids, estimation of temperatures of sonochemical regions in mixtures of deuterated and non-deuterated solvents, and the identification of reactive radical intermediates which may play a role in synergistic cell killing by ultrasound and drugs (sonodynamic interactions).     

用光谱和EPR谱确定CsMgBr3:Ni2+的局域结构

本文采用半自洽场(semi-SCF)自由Ni2 的3d轨道波函数、点电荷—偶极子模型和Ni2 -6X-(X=F,Cl,Br,I)络合物的μ-κ-α模型,建立了结构参数与光谱、EPR谱之间的定量关系,利用完全对角化方法,由光谱和电子顺磁共振(EPR)谱,确定了CsMgBr3:Ni2 晶体在77K温度时的局域结构参数,统一解释了CsMgBr3:Ni2 晶体的局域结构、光谱和EPR谱。所得理论结果与实验值符合得很好。此外,还讨论了晶体局域结构发生畸变的原因。     

Multifrequency EPR spectra of molecular oxygen in solid Air

Multifrequency EPR spectra in the 94 to 550 GHz range were performed on solid air samples condensed at 5 K in the waveguide of a single pass probe. The spectra of molecular oxygen were observed and interpreted in the frame of the spin Hamiltonian model as axial S = 1 spectra with a zero field splitting parameter D = 3.572(3) cm⁻¹. The result of this study is relevant in the field of high field–high frequency EPR application in which solid air O₂ is a common paramagnetic impurity.     

A novel approach to the simulation of nitroxide spin label EPR spectra from a single truncated dynamical trajectory

A simple effective method for calculation of EPR spectra from a single truncated dynamical trajectory of spin probe orientations is reported. It is shown that an accurate simulation can be achieved from the small initial fraction of a dynamical trajectory until the point when the autocorrelation function of re-orientational motion of spin label has relaxed. This substantially reduces the amount of time for spectra simulation compared to previous approaches, which require multiple full length trajectories (normally of several microseconds) to achieve the desired resolution of EPR spectra. Our method is applicable to trajectories generated from both Brownian dynamics and molecular dynamics (MD) calculations. Simulations of EPR spectra from Brownian dynamical trajectories under a variety of motional conditions including bi-modal dynamics with different hopping rates between the modes are compared to those performed by conventional method. Since the relatively short timescales of spin label motions are realistically accessible by modern MD computational methods, our approach, for the first time, opens the prospect of the simulation of EPR spectra entirely from MD trajectories of real proteins structures.     

Detection of energetic light charged particles by solid state nuclear track detectors

Experiments have been carried out to detect ₂ ³He particles and : rotons having energies up to 10 MeV/nucleon by using Kodak CA80-15, cellulose nitrate plastic track detector. Various etching conditions were tried in order to develop tracks for whole of the energy range considered. Detailed analysis seems to indicate that at high energies, the tracks are mainly produced by “secondaries” (elastically scattered nuclei of C, N, O and H, and other reaction products) while in the low energy region, the slowed down “primaries” play the dominant role. The prolonged etching factors of these detectors for different types of tracks have also been obtained and used to derive their average etchable ranges in the materials concerned.     

常温下YGaG:Fe3+体系的EPR谱研究

本文采用对角化三角晶场中d5组态离子的完全能量矩阵的方法,研究了YGaG:Fe3 体系的EPR谱与局域晶格畸变的关系,利用EPR谱的低对称参量D和(a-F)的实验值确定出Fe3 离子在YGaG:Fe3 体系中的键长R=0.2005 nm,键角θ=51.498°,以及晶格畸变角Δθ=0.954°。     

新型X波段多功能EPR谱仪的设计与性能

本文设计和研制了一款新型X波段多功能电子顺磁共振（electron paramagnetic resonance,EPR）谱仪,并为其开发一款新的控制和读出系统（control and readout system,CRS）来操控微波脉冲的产生和信号的采集,提高了系统的集成度和可扩展性. 该谱仪可实现常规的连续波EPR（continuous-wave EPR,cw-EPR）、脉冲EPR（pulsed EPR）和瞬态EPR（transient EPR,trEPR）实验,并装配了6~300 K的无液氦变温装置,以及兼具平行模式与垂直模式的新型双模连续波谐振腔和用于脉冲EPR及trEPR的介质腔. 针对新型EPR谱仪和新谐振腔,本文利用双模连续波、脉冲和瞬态三个不同方式的EPR实验,对其功能进行了验证.     

Variable temperature EPR spectra of Copper (II) ions in kainite crystals

X-band electron paramagnetic resonance (EPR) studies on divalent copper ions embedded in KMgClSO₄·3H₂O single crystals have been performed at low temperature (123 K). The angular variation of the EPR spectra reveals the presence of two Cu²⁺ sites, which have different orientations. The spin-Hamiltonian parameters of this six-coordinated cupric ion have been evaluated from the EPR spectra at 123 K. The forbidden lines due to Δm_I=±1 transitions are observed in between allowed transitions. The temperature variation EPR studies have also been performed both for a single crystal and a polycrystalline sample. The ground state wavefunction of Cu²⁺ ions has been estimated and is found to be an admixture of d_3z²−r² and d_x²−y². The temperature variation of the EPR spectra reveals that Cu²⁺ ions exhibit dynamic Jahn-Teller effect. From the polycrystalline EPR data, the temperature dependent magnetic susceptibilities are evaluated and discussed.     

Crystal field parameters for Yb ions at orthorhombic centers in garnets—Revisited

The major purpose of this paper is to clarify the deficiencies identified in the recent paper by Liu et al. (J. Lumin. 130 (2010) 103) as well as to reanalyze the available data and provide corrected results for the orthorhombic crystal field parameters (CFPs) for selected rare-earth ions in garnets. It appears that Liu et al., when utilizing the computer package for standardization of CFPs, have inadvertently confused the properties of CFPs expressed in the Wybourne notation with those in the extended Stevens operator notation. This confusion has led to misinterpretations concerning the orthorhombic standardization transformations and incorrect labeling of the CFP sets as supposedly ‘standardized’ for Yb³⁺, Pr³⁺, Nd³⁺, and Er³⁺ ions in various garnets. These deficiencies have prompted us to reconsider the CFP sets determined earlier by matching the experimental data, i.e. the orthorhombic spin Hamiltonian parameters (g factors, g_i, and hyperfine structure constants, A_i; i=x, y, z) and available optical spectral band positions, with the theoretical data calculated using the complete diagonalization method. To further verify the correctness of the present results the CFPs for orthorhombic Yb³⁺ centers in Yb₃Al₅O₁₂ and Yb₃Ga₅O₁₂ garnets are calculated using the superposition model (SPM), which requires adoption of a well-defined symmetry-adapted axis system (SAAS). Hence, the SPM calculations enable reanalysis of available CFP sets based on the correct standardization procedure and establishing the correspondence between the SAAS and the ‘nominal’ axis systems assigned to fitted CFP sets. Using the proper SAAS and general transformations of the axis systems, the relations between the calculated g_i and/or A_i values and the respective principal values determined by EPR experiments can be established. The consistent methodology utilized here may be helpful for proper reanalysis of spectroscopic data for rare-earth and transition-metal ions at orthorhombic symmetry sites in various crystals.     

Single crystal EPR studies of Mn(II) doped into zinc ammonium phosphate hexahydrate (ZnNH4PO4·6H2O): A case of interstitial site for bio-mineral analogue

Single crystal EPR studies of Mn(II)-doped zinc ammonium phosphate hexahydrate (ZnNH₄PC₄·6H₂O) have been reinvestigated at room temperature. Single crystal rotations along the three orthogonal axes indicate that the spin Hamiltonian parameters for the interstitial site are:g _xx = 1.966,g _yy = 1.972,g _zz = 1.976;D _xx = -12.28 mT,D _yy = -2.09 mT andD _zz = 14.37 mT;A _xx = 9.06 mT,A _yy = 9.06 mT andA _zz = 11.09 mT;a = -0.11 mT. These parameters differ considerably from the previous report of Chand and Agarwal and indicate the orthorhombic nature of the paramagnetic impurity. The impurity is found to enter the lattice interstitially, in contrast to earlier prediction of substitutional position. The percentage covalency of the Mn-0 bond has been estimated.     

晶体CsMgCl3:Ni2+的局部结构、光谱和EPR谱的理论研究

本文采用半自洽场(semi-SCF) 自由Ni2+的3d轨道波函数、点电荷-偶极子模型和Ni2+-6X-(X=F,Cl,Br,I)络合物的μ-κ-α模型,建立了结构参数与光谱、EPR谱之间的定量关系,利用完全对角化方法,由光谱和电子顺磁共振(EPR)谱,确定了CsMgCl3:Ni2+晶体的局部结构参数,统一解释了CsMgCl3:Ni2+晶体的吸收光谱和EPR 谱.此外,还讨论了高阶微扰方法、参量拟合方法等问题.理论计算结果与实验值符合得很好.     

EPR and optical absorption spectra of VO2+ ions in calcium oxalate monohydrate single crystals

Abstract

Electron paramagnetic resonance (EPR) and Optical absorption spectra of vanadyl ions in calcium oxalate monohydrate single crystals have been studied. EPR spectrum at room temperature exhibits an isotropic octet spectrum. The detailed EPR analysis indicates that vanadyl ions exhibit liquid like behaviour. EPR spectrum has been studied at different temperatures. It is found that at 255 K, the EPR spectrum completely disappears. The optical absorption spectrum exhibits three absorption bands characteristic of vanadyl ions in tetragonal symmetry. From the optical data, the crystal field and tetragonal parameters have been evaluated.     

Absorption and EPR spectra of Cr3+ ions in a LaBeAl11O19 crystal

Electron spectra of optical absorption and EPR of Cr³⁺ ions in a LaBeAl₁₁O₁₉ crystal are investigated. It is shown that the Cr³⁺ ions occupy, three different octahedral positions of Al³⁺ in the LaBeAl₁₁O₁₉ structure, namely, 12k, 2a, and 4f₂; the ratio of their intensitites is 1∶2∶30, respectively. Parameters of the Cr³⁺ centers are determined and its is shown that the optical absorption spectra in the visible region are practically determined by the Cr³⁺ (III) occupying the 4f₂-positions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 275–277, March–April, 1999.     

三角晶场中4A2(3d3)态离子全组态EPR理论研究

在中间场耦合图像中,建立了＾４Ａ２（３ｄ＾３）态离子全组态ＥＰＲ理论;研究了ＥＰＲ参量随三角晶参量Ｖ、Ｖ＇及立方晶场参量Ｄｑ变化关系;用完全对角化方法验证了Ｍａｃｆａ５ｌａｎｅ ＥＰＲ的三阶微扰公式,结果表明,在较大的晶场范围内微扰公式的收敛性很好;研究了ＥＰＲ参量的微观起源及自放二重态对ＥＰＲ参量的贡献,指出自旋二重 对零场分裂参量的贡献不可忽略,二重态对ｇ因子的贡献甚微。