Development of a resonator with automatic tuning and coupling capability to minimize sample motion noise for in vivo EPR spectroscopy

EPR spectroscopy has been applied to measure free radicals in vivo; however, respiratory, cardiac, and other movements of living animals are a major source of noise and spectral distortion. Sample motions result in changes in resonator frequency, Q, and coupling. These instabilities limit the applications that can be performed and the quality of data that can be obtained. Therefore, it is of great importance to develop resonators with automatic tuning and automatic coupling capability. We report the development of automatic tuning and automatic coupling provisions for a 750-MHz transversely oriented electric field reentrant resonator using two electronically tunable high Q hyperabrupt varactor diodes and feedback loops. In both moving phantoms and living mice, these automatic coupling control and automatic tuning control provisions resulted in an 8- to 10-fold increase in signal-to-noise ratio.     

A tunable reentrant resonator with transverse orientation of electric field for in vivo EPR spectroscopy

There has been a need for development of microwave resonator designs optimized to provide high sensitivity and high stability for EPR spectroscopy and imaging measurements of in vivo systems. The design and construction of a novel reentrant resonator with transversely oriented electric field (TERR) and rectangular sample opening cross section for EPR spectroscopy and imaging of in vivo biological samples, such as the whole body of mice and rats, is described. This design with its transversely oriented capacitive element enables wide and simple setting of the center frequency by trimming the dimensions of the capacitive plate over the range 100-900 MHz with unloaded Q values of approximately 1100 at 750 MHz, while the mechanical adjustment mechanism allows smooth continuous frequency tuning in the range +/-50 MHz. This orientation of the capacitive element limits the electric field based loss of resonator Q observed with large lossy samples, and it facilitates the use of capacitive coupling. Both microwave performance data and EPR measurements of aqueous samples demonstrate high sensitivity and stability of the design, which make it well suited for in vivo applications.     

Analysis of the tuning and operation of reflection resonator EPR spectrometers

This paper investigates basic characteristics of the electron paramagnetic resonance (EPR) signal obtained from spectrometers employing reflection resonators. General equations are presented which reveal the phase and amplitude dependence on instrumental parameters of both components of the continuous wave (CW) EPR signal (absorption and dispersion). New phase vector diagrams derived from these general equations are presented for the analysis of the EPR response. The dependence of the phase and absolute value of the CW EPR signal on the local oscillator (LO) phase and on resonator offset and coupling is presented and analyzed. The EPR spectrometer tuning procedures for both balanced and unbalanced heterodyne receivers are analyzed in detail using the new phase diagrams. Extraneous signals at the RF input of the microwave receiver (resulting from circulator leakage and reflections in the resonator transmission line) have been taken into account and analyzed. It is shown that a final tuning condition that corresponds to an extremum of the receiver output as a function of the resonator frequency is necessary and sufficient for the acquisition of pure absorption signal. This condition is universal: it applies to all spectrometer configurations in all frequency ranges. High Frequency EPR spectrometer (130 GHz) data are used to generate experimental phase diagrams that illustrate the theoretical concepts presented in the paper. Conditions are presented under which the absorption signal can be measured with complete suppression of the dispersion, independent of the mutual frequency offset between the microwave source and the EPR sample resonator. Equations describing the approximate relationship between changes of the resonator properties (Q-factor and frequency) and paramagnetic susceptibility are derived and analyzed.     

包含源与负载耦合的滤波器诊断与调试方法

柯西法目前仅适用于诊断不包含源与负载耦合的带通滤波器。为解决这一问题,提出了一种能够诊断包含源与负载耦合的带通、带阻谐振腔滤波器的方法。利用遗传算法优化获得源与负载耦合系数并移除滤波器输入/输出端口处传输线引起的S参数的相位加载效应;使用柯西法一步确定仿真S参数对应的特征多项式;从获得的源与负载耦合系数和特征多项式中,利用已有的技术诊断出N+2阶耦合矩阵。此方法可用于指导滤波器的调试,通过对比理想的耦合矩阵与提取的耦合矩阵之间的差异,可确定滤波器问题出自何处以及调试的方向,从而加快滤波器的设计与实现。     

Coupling of waveguide and resonator by inductive and capacitive irises for EPR spectroscopy

An analytic circuit model for slot coupling from a waveguide to a loop-gap resonator (LGR) in a context of electron paramagnetic resonance (EPR) spectroscopy is presented. The physical dimensions of the waveguide, iris, LGR, and aqueous sample are transformed into circuit values of inductance, capacitance, and resistance. These values are used in a solution of circuit equations that results in a prediction of the radio frequency (rf) currents, magnitude and phase, frequency, and magnetic and electric stored energies near the critical coupling. The circuit geometry reflects magnetic flux conservation between the iris and LGR as well as modification of the outer loop LGR currents by the iris. Unlike conventional models, coupling is not explicitly based on a mutual inductance between the iris and LGR. Instead, the conducting wall high-frequency rf boundary condition is used to define surface currents, regions, and circuit topology with lumped-circuit values of self-inductance, capacitance, and resistance. Match is produced by a combination of self-inductive and capacitive circuit coupling. Two conditions must be met to achieve match. First, the equivalent resistance of the LGR as seen by the iris must be transformed into the waveguide characteristic impedance. This transformation is met at a particular frequency relative to the natural LGR resonance frequency. The frequency shift magnitude is largely determined by the LGR properties, weakly dependent on the iris length and placement, and independent of other iris dimensions. The second condition for match is that the iris reactance at this frequency shift must cancel the residual reactance of the LGR. This second condition is sensitive to the iris dimensions. If both conditions are not simultaneously satisfied, overcoupling or undercoupling results. A slotted iris with a length equal to the size of the large dimension of the waveguide is found to have many properties opposite to a conventional iris with shorter length. Notably, the magnetic field near the iris tends to reinforce rather than oppose the magnetic field in the resonator. The long iris improves the LGR EPR performance by providing increased rf magnetic field homogeneity at the sample, higher signal, and reduced total frequency shift since the shifts due to sample and iris tend to cancel. Investigations reveal that the first match condition can be adjusted by LGR dimensional changes and such adjustment can eliminate the frequency shift. Results are consistent with Ansoft High Frequency Structure Simulator (Version 10.1, Ansoft Corporation, Pittsburgh, PA) simulations and can be extended to cavity resonators.     

High frequency and field EPR spectroscopy of Mn(III) complexes in frozen solutions

We have performed high-frequency and -field electron paramagnetic resonance (HFEPR) experiments on two complexes of high-spin Mn(III) (3d(4),S=2): mesotetrasulfonato-porphyrinatomanganese(III) (Mn(TSP)) and [(R,R)-(-)-N,N(')-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III)] (Mn(salen)). The main aim of this work was to qualitatively and quantitatively characterize the conditions suitable for HFEPR of high-spin transition metal complexes in frozen solutions, and compare them with experiments performed on solid samples. Mn(TSP) is a porphyrin complex soluble in water, in contrast to most metalloporphyrins. Mn(salen), often referred to as Jacobsen's catalyst, is a complex widely used in organic synthesis for alkene epoxidation, and is soluble in organic solvents. High-quality HFEPR signals were observed for solid state Mn(TSP), as has been previously shown for many Mn(III) complexes. The present study is, however, the first to report high-quality HFEPR spectra of a Mn(III) complex in frozen aqueous solution. Analysis of the data yielded the following spin Hamiltonian parameters: S=2; D=-3.16+/-0.02 cm(-1), E=0, and isotropic g=2.00(2). No X-band EPR signals were observed for Mn(TSP), which is a consequence of this being a rigorously axial spin system. Mn(salen), in contrast, did not give good quality HFEPR spectra in the solid state, but high-quality HFEPR spectra were recorded in frozen organic solutions. Analysis of the data yielded the following spin Hamiltonian parameters: S=2; D=-2.47+/-0.02 cm(-1), |E|=0.17+/-0.01 cm(-1), and isotropic g=2.00(2). These values differ from those reported using X-band parallel mode EPR [J. Am. Chem. Soc. 123 (2001) 5710], as discussed in the text. Therefore, a comparison between HFEPR and parallel-mode X-band spectroscopy is made. Finally, the concentration sensitivity aspect of HFEPR spectroscopy is also discussed.     

Advanced theory of driven birdcage resonator with losses for biomedical magnetic resonance imaging and spectroscopy

A complete time-dependent physics theory of symmetric unperturbed driven hybrid birdcage resonator was developed for general application. In particular, the theory can be applied for radiofrequency (RF) coil engineering, computer simulations of coil-sample interaction, etc. Explicit time dependence is evaluated for different forms of driving voltage. The major steps of the solution development are shown and appropriate explanations are given. Green's functions and spectral density formula were developed for any form of periodic driving voltage. The concept of distributed power losses based on transmission line theory is developed for evaluation of local losses of a coil. Three major types of power losses are estimated as equivalent series resistances in the circuit of the birdcage resonator. Values of generated resistances in legs and end-rings are estimated. An application of the theory is shown for many practical cases. Experimental curve of B₁ field polarization dependence is measured for eight-sections birdcage coil. It was shown that the steady-state driven resonance frequencies do not depend on damping factor unlike the free oscillation (transient) frequencies. An equivalent active resistance is generated due to interaction of RF electromagnetic field with a sample. Resistance of the conductor (enhanced by skin effect), Eddy currents and dielectric losses are the major types of losses which contribute to the values of generated resistances. A biomedical sample for magnetic resonance imaging and spectroscopy is the source of the both Eddy current and dielectric losses of a coil. As demonstrated by the theory, Eddy current loss is the major effect of coil shielding.     

Analysis and optimisation of the tuning of the twelfths for a clarinet resonator

Even if the tuning between the first and second register of a clarinet has been optimized by instrument makers, the lowest twelfths remain slightly too large (inharmonicity). In this article, we study the problem from two different points of view. First, we systematically review various physical reasons why this inharmonicity may take place, and the effect of different bore perturbations inserted in cylindrical instruments such as bore flare, open and closed holes, taper, temperature gradients, visco-thermal effects, etc. Applications to a real clarinet resonator and comparisons with impedance measurements are then presented. A commonly accepted idea is that the register hole is the dominant cause for this inharmonicity: it is natural to expect that opening this hole will shift the position of the resonances of the instrument to higher frequencies, except of course for the note for which the hole is exactly at the pressure node. We show that the real situation is actually more complicated because other effects, such as open holes or bore taper and bell, introduce resonance shifts that are comparable but with opposite sign, so that a relatively good overall compensation takes place. This is checked by experimental and theoretical studies of the acoustical impedance curves of a clarinet. The origin of the observed inharmonicity in playing frequencies is therefore different, maybe related to the reed or the vocal tract. In a second part, we use an elementary model of the clarinet in order to isolate the effect of the register hole: a perfect cylindrical tube without closed holes. Optimization techniques are then used to calculate an optimum location for the register hole (without taking into account the use of the register hole as a B flat tone hole); the result turns out to be close to the location chosen by clarinet makers. Finally, attempts are made numerically to improve the situation by introducing small perturbations in the higher part of the cylindrical resonator, but no satisfactory improvement is obtained.     

Probeheads and instrumentation for pulse EPR and ENDOR spectroscopy with chirped radio frequency pulses and magnetic field steps

Probeheads and instrumentation for modern X-band pulse EPR and ENDOR experiments with chirped radio-frequency pulses and rapidB ₀-field pulses are described. The resonant frequency, the quality factor and, for the first time, the response of a pulse ENDOR resonator structure to a microwave pulse in the subnanosecond time scale have been calculated. The performance of the probeheads for time-domain chirp ENDOR and electron Zeeman-resolved EPR is demonstrated.     

凸面光栅成像光谱仪全视场自动化光谱定标系统设计

为了确定凸面光栅成像光谱仪的光谱特性,需要对凸面光栅成像光谱仪进行光谱定标。基于单色准直光法设计了一套全视场光谱定标系统,引入球面镜提供准直光,采用一块可以自由滑动和转动的折转镜改变定标光线的入射角,实现了全谱段自动化光谱定标。运用光学设计软件CODEV对光谱定标系统进行了部分光学模拟,证明了整个系统的可靠性。结合光谱定标系统的结构和特点,对整个光谱定标系统进行了精度分析。理论分析结果表明,该系统的光谱定标精度优于1%。该定标系统具有体积小、通用性强等特点,可为其他成像光谱仪的光谱定标提供参考。     

Optical fiber sensor for the measurement of electric field intensity and voltage (OPSEF)

An optical fiber sensor for measuring high electric field intensity and voltage, which utilizes the electro-optic effect of bismuth silicone oxide single crystal, has been developed successfully, and the fundamental characteristics have been evaluated. The electric field intensity distribution inside the coaxial electrodes has been measured with this sensor. The measured results are in agreement with the theoretical values.     

Dielectric half-disk resonator with whispering-gallery modes for measurements of the electric properties of water

We study experimentally the possibility of measuring the dielectric properties of water in the millimeter wavelength range using dielectric resonators excited at the whispering-gallery modes. The influence of various conditions for excitation of such resonators by a local source on the sensitivity and resolution of the performed measurements is shown. Electrodynamic characteristics of the dielectric resonator as a cell for measurements of the electric properties of water are studied. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 51, No. 9, pp. 769–776, September 2008.     

Investigating magnetically aligned phospholipid bilayers with EPR spectroscopy at Q-band (35 GHz): optimization and comparison with X-band (9 GHz)

This paper presents the improvement and advantages of investigating magnetically aligned phospholipid bilayers (bicelles) utilizing electron paramagnetic resonance (EPR) spectroscopy at a microwave frequency of 35 GHz (Q-band) and at a high magnetic field strength of 1.25 T when compared to weaker magnetic fields for X-band EPR studies. The nitroxide spin label 3beta-doxyl-5alpha-cholestane (cholestane or CLS) was inserted into the bicelles and utilized to demonstrate the effects of macroscopic bilayer alignment through the measurement of orientational dependent hyperfine splittings. The effects of different lanthanide ions with varying degree of magnetic susceptibility anisotropy were examined. The requirement of minimal amounts of the Tm3+ and Dy3+ lanthanide ions for well-aligned bicelles were examined for Q-band and compared with amounts required for X-band bicelle alignment studies. At a magnetic field of 1.25 T (when compared to 0.63 T at X-band), the perpendicular and parallel orientation were aligned with lower concentrations of Dy3+ and Tm3+, respectively, and thereby eliminating/minimizing the unwanted effects associated with lanthanide-protein interactions. Thus, it is much easier to magnetically align phospholipid bilayers at Q-band when compared to X-band.     

液晶在电场和剪切耦合作用下的流变学行为

本文通过理论和实验对液晶 5CB在剪切和电场耦合作用下流变行为进行了研究. 采用液晶连续理论, 建立了包括界面锚定能, 弹性自由能, 介电自由能和流动能在内的系统 Gibbs自由能公式, 通过最小化系统自由能的方法求解液晶在剪切和电场耦合作用下的取向分布及其黏度变化, 从分子基础模型上揭示了液晶在耦合作用下的流变行为、微观机理及其影响规律, 并通过流变测试对此进行验证. 对比分析了理论和试验结果的误差和原因, 发现界面锚定效应对于液晶分子的取向和黏度具有重要影响. 理论和试验结果均表明, 液晶在电场作用下具有明显的电黏效应, 表现出非牛顿流变行为, 其黏度值由剪切和电场的竞争和耦合作用共同决定. 在外电场作用下液晶的黏度可以增加到初始值的 4倍左右, 液晶这种其自身黏度可随着外场 (例如运动速度) 改变的特性在一定的条件下可以自适应地满足不同工况对黏度的要求, 这对实现智能摩擦润滑具有重要的意义. 关键词： 液晶 流变行为 电黏效应 耦合作用     

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.     

Pressure and temperature dependence of the electric field gradient (EFG) in CdS

Using the time differential perturbed angular correlation technique (TDPAC), the electric hyperfine interaction of¹¹¹Cd in the II-VI-semiconductor CdS was investigated. The results of the temperature and pressure dependence of the electric field gradient (EFG) are discussed. The binding energyE _b for¹¹¹In at a Cd lattice site and a Cd vacancy (¹¹¹In_Cd–V_Cd–pair) could be estimated to 340 meV±80 meV by means of an Arrhenius-Plot. The disappearance of the 79 MHz and 73 MHz frequencies under a pressure of about 30 kbar could be due to their vacancy character or to the beginning of the phase transition to rocksalt structure.     

金纳米环双体尺寸和耦合效应对表面等离子体共振特性的影响

采用离散偶极子近似方法系统地研究了金纳米环双体的消光光谱及其电场分布. 计算结果表明, 金纳米环双体在耦合作用下的共振消光峰对应着不同振动模式, 改变金纳米环双体的排列方式、 间距和尺寸大小, 其表面等离子体共振消光峰发生红移或蓝移. 因此可以通过对金纳米环双体结构参数和排列方式的设定, 调节其表面等离子体共振消光峰的位置. 电场分布表明, 水平排列的金纳米环双体较单个金纳米环产生更强的局部表面增强电场. 适当的小间距, 较大的内外半径的金纳米环水平阵列更适合做表面增强拉曼散射的衬底, 在生物分子检测等领域具有潜在的应用.     

Determination of the magnetic cubic anisotropy field in (111) oriented films by FMR

The angular characteristics of the resonant field in films oriented in the (111) plane is analyzed using a resonance relation and a condition for equilibrium orientation of the magnetization. A method for determining a cubic anisotropy field from the azimuthal dependence of the FMR field, which eliminates the need to first find the crystallographic directions in the film by other methods, is proposed on the basis of the results obtained. Zh. Tekh. Fiz. 67, 35–40 (February 1997)