Two-dimensional imaging of two types of radicals by the CW-EPR method

New EPR resonators were developed by using a ceramic material with a high dielectric constant, epsilon=160. The resonators have a high quality factor, Q=10(3), and enhance the sensitivity of an EPR spectrometer up to 170 times. Some advantages of the new ceramic resonators are: (1) cheaper synthesis and simplified fabricating technology; (2) wider temperature range; and (3) ease of use. The ceramic material is produced with a titanate of complex oxides of rare-earth and alkaline metals, and has a perovskite type structure. The resonators were tested with X-band EPR spectrometers with cylindrical (TE(011)) and rectangular (TE(102)) cavities at 300 and 77K. We discovered that EPR signal strength enhancement depends on the dielectric constant of the material, resonator geometry and the size of the sample. Also, an unusual resonant mode was found in the dielectric resonator-metallic cavity structure. In this mode, the directions of microwave magnetic fields of the coupled resonators are opposite and the resonant frequency of the structure is higher than the frequency of empty metallic cavity.     

Enhanced EPR sensitivity from a ferroelectric cavity insert.

We report the development of a simple ferroelectric cavity insert that increases the electron paramagnetic resonance (EPR) sensitivity by an order of magnitude when a sample is placed within it. The insert is a hollow cylinder (length 4.8 mm, outside diameter 1.7 mm, inside diameter 0.6 mm) made from a single crystal of KTaO(3), which has a dielectric constant of 230 at X-band (9.5 GHz). Its outside dimensions were chosen to produce a resonant frequency in the X-band range, based on electromagnetic field modeling calculations. The insert increases the microwave magnetic field (H(1)) at the center of the insert by a factor of 7.4 when placed in an X-band TM(110) cavity. This increases the EPR signal for a small (volume 0.13 microL) unsaturated nitroxide spin label sample by a factor of 64 at constant microwave power, and by a factor of 9.8 at constant H(1). The insert does not significantly affect the cavity quality factor Q, indicating that this device simply redistributes the microwave fields within the cavity, focusing H(1) onto the sample inside the insert, thus increasing the filling factor. A similar signal enhancement is obtained in the TM(110) and TE(102) cavities, and when the insert is oriented either vertically (parallel to the microwave field) or horizontally (parallel to the DC magnetic field) in the TM(110) cavity. This order-of-magnitude sensitivity enhancement allows EPR spectroscopy to be performed in conventional high-Q cavities on small EPR samples previously only measurable in loop-gap or dielectric resonators. This is of particular importance for small samples of spin-labeled biomolecules.     

Aqueous flat-cells perpendicular to the electric field for use in electron paramagnetic resonance spectroscopy, II: design

This paper builds on the work of Mett and Hyde [J. Magn. Reson. 165 (2003) 137]. Various aqueous flat-cell geometries in the perpendicular orientation have been studied using Ansoft High Frequency Structure Simulator (version 9.0, Pittsburgh, PA) and Computer Simulation Technology Microwave Studio (version 5.0, Wellesley Hills, MA). The analytic theory of Mett and Hyde has been refined to predict optimum dimensions of multiple sample cell structures including the effect of the sample holder dielectric properties and the interaction of the cells with each other on EPR signal strength. From these calculations and simulations we propose a practical multiple cell sample structure for use in commercial rectangular TE102 cavities that yields 2.0-2.3 times higher sensitivity relative to a single flat-cell in the nodal orientation. We also describe a modified TE102 resonator design with square rather than cylindrical sample-access stacks that is predicted to give a factor of 2.2-2.7 enhancement in EPR signal strength of a single flat-cell in the nodal orientation. These signal enhancements are predicted with sample holders fabricated from polytetrafluoroethylene. Additional improvement in EPR signal of up to 75% can be achieved by using sample holder materials with lower dielectric constants.     

Analysis of two stacked cylindrical dielectric resonators in a TE₁₀₂ microwave cavity for magnetic resonance spectroscopy

The frequency, field distributions and filling factors of a DR/TE??? probe, consisting of two cylindrical dielectric resonators (DR1 and DR2) in a rectangular TE??? cavity, are simulated and analyzed by finite element methods. The TE(+++) mode formed by the in-phase coupling of the TE??(δ)(DR1), TE??(δ)(DR2) and TE??? basic modes, is the most appropriate mode for X-band EPR experiments. The corresponding simulated B(+++) fields of the TE(+++) mode have significant amplitudes at DR1, DR2 and the cavity's iris resulting in efficient coupling between the DR/TE??? probe and the microwave bridge. At the experimental configuration, B(+++) in the vicinity of DR2 is much larger than that around DR1 indicating that DR1 mainly acts as a frequency tuner. In contrast to a simple microwave shield, the resonant cavity is an essential component of the probe that affects its frequency. The two dielectric resonators are always coupled and this is enhanced by the cavity. When DR1 and DR2 are close to the cavity walls, the TE(+++) frequency and B(+++) distribution are very similar to that of the empty TE??? cavity. When all the experimental details are taken into account, the agreement between the experimental and simulated TE(+++) frequencies is excellent. This confirms that the resonating mode of the spectrometer's DR/TE??? probe is the TE(+++) mode. Additional proof is obtained from B?(x), which is the calculated maximum x component of B(+++). It is predominantly due to DR2 and is approximately 4.4 G. The B?(x) maximum value of the DR/TE??? probe is found to be slightly larger than that for a single resonator in a cavity because DR1 further concentrates the cavity's magnetic field along its x axis. Even though DR1 slightly enhances the performance of the DR/TE??? probe its main benefit is to act as a frequency tuner. A waveguide iris can be used to over-couple the DR/TE??? probe and lower its Q to ≈150. Under these conditions, the probe has a short dead time and a large bandwidth. The DR/TE??? probe's calculated conversion factor is approximately three times that of a regular cavity making it a good candidate for pulsed EPR experiments.     

Aqueous flat cells perpendicular to the electric field for use in electron paramagnetic resonance spectroscopy

An analytic solution of the Maxwell equations for aqueous flat cells in rectangular TE(102) cavities has led to the prediction of significant (3-6 times) X-band EPR signal improvement over the standard flat cell for a new sample configuration consisting of many flat cells oriented perpendicular to the electric field nodal plane. Analytic full wave solutions in the presence of sample and wall losses have been obtained and numerically evaluated. Observation of the predicted fields led to a classification of three distinct types of sample loss mechanisms, which, in turn inspired sample designs that minimize each loss type. The resulting EPR signal enhancement is due to the presence and centering of a tangential electric field node within each individual sample region. Samples that saturate with the available RF magnetic field and those that do not are considered. Signal enhancement appears in both types. These observations, done for the TE(102) mode, carry over to the uniform field (UF) modes, a relatively new class of microwave cavities for use in EPR spectroscopy developed in this laboratory. Rectangular UF modes have an RF magnetic field magnitude that is uniform in a plane. Based on this analysis, a practical multiple flat-cell design is proposed.     

Modes and Fields of Two Stacked Dielectric Resonators in a Cavity of an Electron Paramagnetic Resonance Probe

An electron paramagnetic resonance (EPR) probe consisting of two dielectric resonators (DRs) and a cavity (CV) is ideal for EPR experiments where both signal enhancement and tuning capabilities are required. The coupling of two DRs, resonating in their \({\text{TE}}_{01\delta }\) mode and a CV resonating in its \({\text{TE}}_{011}\) mode, is studied using energy-coupled mode theory (ECMT). The frequencies and eigenvectors of the three coupled modes are analytically derived. As predicted numerically, ECMT confirms that the \({\text{TE}}^{ + + - }\) and \({\text{TE}}^{ + - - }\) modes are indeed found to be degenerate at a specific distance between the two DRs \(d_{12}\). Additionally, the condition at which degeneracy occurs is specified. For a considerable range, the calculated frequency of the \({\text{TE}}^{ + + + }\) mode changes linearly with respect to \(d_{12}\). The \({\text{TE}}^{ + + + }\) mode showed a 500 MHz frequency change over a distance of 2 cm, when the resonance frequency is around 9.7 GHz. This enables the experimentalist to linearly tune the probe over this large frequency range. Finally the asymmetric configuration, where one of the resonators (DR2) is kept at the cavity center and the other one is allowed to move along the cavity axis, is studied. It is estimated that the frequency changes by 600 MHz over a distance of 1.5 cm. A formula for the magnitude of the magnetic field along the cavity axis, where the EPR samples are usually placed, is developed. This is crucial in determining the magnetic field in the vicinity of the sample and the probe’s filling factor.     

垂直入射条件下金属环的谐振特性

本文研究垂直入射条件下水平极化和垂直极化时金属开口谐振环(split ring resonator, SRR)的电磁响应行为. 通过分析这两种情况下的透射系数、介电常数和磁导率, 发现垂直极化时, SRR可以产生电谐振实现负介电常数, 其频段远高于磁谐振频段; 水平极化时, SRR只能产生磁谐振实现负磁导率, 其频段与水平入射时的SRR的磁谐振频段相对应. 通过仿真对此进行了证明, 并对产生电谐振和磁谐振的原因进行了分析.     

用于速调管功率合成输出结构的转向波导设计

 为X波段高峰值功率速调管功率合成输出结构设计了一个工作在9 GHz的转向波导，用于连接功率合成器和速调管输出腔。转向波导结构由中心矩形谐振腔、两个矩形耦合孔和两边的输入输出波导组成；输入和输出波导由速调管输出腔和功率合成器确定，分别工作在TE₁₀和TE₀₁模式，它们相互垂直并偏离矩形谐振腔的中心；中间的矩形谐振腔工作在TM₁₁₀，TE₁₀₁和TE₀₁₁混合模式。这种转向波导结构的3个反射零点构成了较宽的传输通带。将连接转向波导结构的功率合成器加载到速调管输出腔,计算了功率合成器加载后速调管输出腔的间隙阻抗。计算结果表明：功率合成器的加载对输出腔间隙阻抗影响不大。设计的转向波导结构很好地应用到了速调管功率合成输出结构中。     

High-field ESR on aligned membranes: a simple method to record spectra from different membrane orientations in the magnetic field

A combination of isopotential spin-dry ultracentrifugation (ISDU) and microtome techniques was used to facilitate the collection of high field/high frequency (170 GHz) ESR spectra corresponding to different orientations of the membrane normal relative to the magnetic field. This technique is particularly valuable for aligned biological samples in vitro. At 170 GHz, conventional sample preparation techniques based solely on ISDU constrained the sample to be oriented so that the membrane normal was parallel to the applied magnetic field due to the geometry and the millimeter wave field distribution of the Fabry-Pérot resonator used in these experiments. This orientational constraint limited the information that could be obtained from aligned membranes at high field. The combined ISDU/microtome technique overcame this limitation. Spectra from spin-labeled Gramicidin A and the spin label cholestane in aligned DPPC membranes provide a demonstration of the technique. We also discuss some virtues of high field/high frequency ESR on aligned membranes compared to X-band.     

Nanoparticle kinetic effects experimentally observed in a magnetic fluid under a quasi-homogeneous magnetic field

The effect of a quasi-homogeneous external magnetic field on a created and decaying space nanoparticle structure and its distribution in a sample of a magnetic fluid was studied. This space structure was created as a grating by applying an interference field of two crossed Ar laser beams. The magnetic field was formed using two electromagnets and was applied in three main directions of the created nanoparticle grating. The magnetic field oriented parallel to the strips of the grating or perpendicular to the grating plain does not significantly change the shape of it. The magnetic field oriented in the perpendicular direction to the grating plain causes redistribution of the nanoparticles and as a consequence a perpendicular nanoparticle “quasi-grating” arises.     

Dielectric resonator-based resonant structure for sensitive ESR measurements at high-hydrostatic pressures

We present a newly developed microwave probe head that accommodates a gasketed sapphire anvil cell (SAC) for performing sensitive electron spin resonance (ESR) measurements under high-hydrostatic pressures. The system was designed around commercially available dielectric resonators (DRs) having the dielectric permittivity of approximately 30. The microwave resonant structure operates in a wide-stretched double-stacked geometry and resonates in the lowest cylindrical quasi TE(011) mode around 9.2 GHz. The most vital parts of the probe's microwave heart were made of plastic materials, thus making the resonant structure transparent to magnetic field modulation at 100 kHz. The overall ESR sensitivity of the probe was demonstrated for a small speck of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) positioned in the gasket of the SAC, using water as the pressure-transmitting medium. The system was also used for studying pressure-induced changes in spin-relaxation mechanisms of a quasi-1D-conducting polymer, K(1)C(60). For small samples located in the sample hole of the gasket the probe reveals sensitivity that is only approximately 3 times less than that yielded by regular ESR cavities.     

TE011腔使用扁平样品管提高水溶液样品ESR波谱灵敏度的研究

实验表明,在TE₀₁₁模式园柱形腔中,不但可以使用扁平样品管测量水溶液样品的ESR波谱,而且获得好的腔品质因子Q和高品质的ESR信号。所观察到的信号高度,是使用最佳尺寸毛细管样品时最大信号高度的3.2倍;又是在具有波导尺寸的TE₁₀₂腔中使用扁平样品管时所获得信号高度的3倍。本文对此作了定性的理论分析。     

Magnetic structure of FeI2 by neutron diffraction experiments

Phase transitions study of FeI₂ in high magnetic field parallel to the anisotropy axis has proved that FeI₂ has an antiferromagnetic structure (below T_N = 9.3 K) more complex than the two sublattices structure characteristic of FeCl₂ and FeBr₂.We performed neutron diffraction experiments, at room temperature and at 4.2 K using a powder sample. The results show that FeI₂ has an antiferromagnetic structure similar to the structure proposed by Keohler for MnBr₂, but with spins oriented along the crystal anisotropy axis perpendicular to the Fe⁺⁺ layers. This spin orientation is in accordance with the results of parallel and perpendicular susceptibilities study.     

磁流体粘度的实验研究

采用毛细法粘度计测量了水基Fe磁流体的粘度,分析了磁性粒子份额、表面活性剂含量以及外加磁场强度和方向对粘度的影响。实验结果表明,磁流体粘度随着磁性粒子和表面活性剂浓度的增加而增加;随着外加磁场强度的增大而增大,对于相同的磁流体,在外加磁场方向垂直于流动方向时的粘度大于外加磁场方向平行于流动方向时的粘度;表面活性剂含量的增大将减弱外加磁场对磁流体粘度的影响。     

A X-band ESR apparatus using a Whispering Gallery Mode dielectric resonator

The behaviour of a disc-shaped dielectric resonator (DR) working in the Whispering-Gallery Modes (WGM) when used for X-band ESR experiments has been tested. It has been verified that the WGM in the resonator can be excited by using the microwave bridge of a Bruker spectrometer. The microwave field is well confined in the DR also in the absence of metal shieldings as demonstrated by the high Q values of the detected resonances. A large number of such resonances has been detected from eight up to twelve gigahertz making the DR a very broadband device. ESR spectra of various powder and aqueous samples have been obtained and compared with those of the same samples recorded by using a metal cavity. The relative amplitude of the spectra demonstrated that for aqueous samples the sensitivity of DR is similar to that of the metallic cavity. Further investigations are in progress to enhance the overall performance.     

Aqueous sample in an EPR cavity: sensitivity considerations

The radial mode matching (RMM) method has been used to calculate accurately the microwave field distribution of the TE(011) mode in a spherical EPR cavity containing a linear aqueous sample, in order to understand in detail the factors affecting sensitivity in EPR measurements at X band. Specific details of the experiment were included in the calculations, such as the cavity geometry, the presence of a quartz dewar, the size of the aqueous sample, and the sample's dielectric properties. From the field distribution, several key physical parameters were calculated, including cavity Q, filling factor, mean microwave magnetic field at the sample, and cavity efficiency parameter Lambda. The dependence of EPR signal intensity on sample diameter for a cylindrical aqueous sample was calculated and measured experimentally for non-saturated and half-saturated samples. The optimal aqueous sample diameter was determined for both cases. The impact of sample temperature, conductivity, and cavity Q on sensitivity of EPR is discussed.     

基于小型化结构的各向同性负磁导率材料与左手材料

提出了一种双面环各向同性结构单元模型, 理论与实验研究了其微波电磁谐振行为. 结果表明: 在电磁波平行入射和垂直入射条件下, 该结构可在同一频段实现磁谐振, 且在谐振频段磁导率为负; 当电磁波以不同角度斜入射时, 其产生负磁导率频段也保持不变, 即该结构的电磁特性不依赖于入射角度, 双面环结构具有各向同性的特点. 将双面环结构与金属线结构组合, 该组合结构具有负折射率. 另外,双面环结构还具有小型化的优点, 在不增加结构单元几何尺寸的情况下, 通过在结构单元中引入金属化过孔的方法, 增加结构单元的电长度, 可使谐振频率大幅度地向低频方向移动, 使其在低频工作时 仍保持小型化的优点. 在双面环结构中引入金属化过孔技术可使谐振单元的几何尺寸减小50%, 在微波器件、滤波器、天线等领域有广阔的应用前景.     

High frequency single-mode resonators for EPR spectroscopy enabling rotations of the sample about two orthogonal axes

A novel single-mode resonant structure which enables the rotation of the sample about two orthogonal axes is investigated in view of electron paramagnetic resonance applications. The proposed solution is based on cylindrical non-radiative resonators laterally loaded by the sample holder. The resulting structure can still operate in non-radiative regime, although no longer rotationally invariant. These theoretical predictions, based on symmetry considerations, are confirmed by means of a finite element numerical modelling. Theoretical and computational results are then substantiated by experimental investigations at millimeter wavelengths. As a result, a single-mode resonator which enables all the relevant rotations of the sample is demonstrated at millimeter wavelengths for the first time. In this resonator the intensity of the microwave field on the sample and its orientation with respect to the static magnetic field can be kept constant during the rotations. Therefore, a complete characterization of anisotropic systems is possible at the highest sensitivity, without the need of split-coil magnets. Possible applications at very high frequencies are discussed.     

回旋管光子带隙谐振腔冷腔电磁模式分析

利用二维三角格子金属光子带隙谐振腔代替回旋管的传统柱形谐振腔,并对腔体进行了TE波模式的计算与分析.综合考虑腔体内外的结构特征,给出了光子带隙谐振腔冷腔模式理论的研究方法,发现腔内存在单模工作的可能与条件以及非角对称情况下的电磁模式分布特征.研究结果表明,利用光子带隙谐振腔代替回旋管的传统腔体,可使回旋管在不受腔体横向尺度限制的条件下实现单模工作.这对于提高回旋管的功率容量、有效实现高次单模与高次回旋谐波耦合条件下的注-波互作用、降低工作磁场并从物理上根本改变回旋管的工作状态提供了理论依据. 关键词： 回旋管 金属光子带隙 谐振腔     

Nitroxide Side-Chain Dynamics in a Spin-Labeled Helix-Forming Peptide Revealed by High-Frequency (139.5-GHz) EPR Spectroscopy

High-frequency electron paramagnetic resonance (EPR) spectroscopy has been performed on a nitroxide spin-labeled peptide in fluid aqueous solution. The peptide, which follows the single letter sequence, was reacted with the methanethiosulfonate spin label at the cysteine sulfur. The spin sensitivity of high-frequency EPR is excellent with less than 20 pmol of sample required to obtain spectra with good signal-to-noise ratios. Simulation of the temperature-dependent spectral lineshapes reveals the existence of local anisotropic motion about the nitroxide N-O bond with a motional anisotropy tau( perpendicular)/tau( parallel) ( identical with N) approaching 2.6 at 306 K. Comparison with previous work on rigidly labeled peptides suggests that the spin label is reorienting about its side-chain tether. This study demonstrates the feasibility of performing 140-GHz EPR on biological samples in fluid aqueous solution.