High-Bandwidth Q-Band EPR Resonators

The emerging technology of ultra-wide-band spectrometers in electron paramagnetic resonance—enabled by recent technological advances—provides the means for new experimental schemes, a broader range of samples, and huge gains in measurement time. Broadband detection does, however, require that the resonator provides sufficient bandwidth and, despite resonator compensation schemes, excitation bandwidth is ultimately limited by resonator bandwidth. Here, we present the design of three resonators for Q-band frequencies (33–36 GHz) with a larger bandwidth than what was reported so far. The new resonators are of a loop-gap type with 4–6 loops and were designed for 1.6 mm sample tubes to achieve higher field homogeneity than in existing resonators for 3 mm samples, a feature that is beneficial for precise spin control. The loop-gap design provides good separation of the B ₁ and E field, enabling robust modes with powder samples as well as with frozen water samples as the resonant behavior is largely independent of the dielectric properties of the samples. Experiments confirm the trends in bandwidth and field strength and the increased B ₁ field homogeneity predicted by the simulations. Variation of the position of the coupling rod allows the adjustment of the quality factor Q and thus the bandwidth over a broad range. The increased bandwidth of the loop-gap resonators was exploited in double electron–electron resonance measurements of a Cu(II)-PyMTA ruler to yield significantly higher modulation depth and thus higher sensitivity.     

Coarse and Fine Control of the EPR Frequency of a Loop-Gap Resonator Using a Single-Turn Coil with a Varactor Diode Attached

Coarse control and fine control of the resonant frequency of a loop-gap resonator (LGR) operating at an electron paramagnetic resonance (EPR) frequency of ca. 650 MHz were achieved using a single-turn coil with a varactor diode attached (a frequency shift coil). When the distance between the LGR and the frequency shift coil was changed from 15 to 10 mm under the condition of constant voltage to the varactor diode (0 V), a shift of the resonant frequency of the LGR of ca. 20 MHz was observed (coarse frequency control). When the voltage applied to the varactor diode was changed from 0 to 15 V at the same distance between the LGR and the frequency shift coil (10 mm), a shift of the resonant frequency of the LGR of ca. 200 kHz was observed (fine frequency control). There were no significant changes in sensitivity of EPR measurements of a phantom (comprised of agar with a nitroxide radical and physiological saline solution) without and with the frequency shift coil. The EPR sensitivity did not change discernibly when the resonant frequency was shifted by the frequency shift coil. Furthermore, radio-frequency phase adjustment for homodyne detection could be performed by using the frequency shift coil without applying frequency modulation to the carrier wave.     

A New Q-Band EPR Probe for Quantitative Studies of Even Electron Metalloproteins

Existing Q-band (35 GHz) EPR spectrometers employ cylindrical cavities for more intense microwave magnetic fields B₁, but are so constructed that only one orientation between the external field B and B₁is allowed, namely the B B₁orientation, thus limiting the use of the spectrometer to measurements on Kramers spin systems (odd electron systems). We have designed and built a Q-band microwave probe to detect EPR signals in even electron systems, which operates in the range 2 K ≤ T ≤ 300 K for studies of metalloprotein samples. The cylindrical microwave cavity operates in the TE₀₁₁mode with cylindrical wall coupling to the waveguide, thus allowing all orientations of the external magnetic field B relative to the microwave field B₁. Such orientations allow observation of EPR transitions in non-Kramers ions (even electron) which are either forbidden or significantly weaker for B B₁. Rotation of the external magnetic field also permits easy differentiation between spin systems from even and odd electron oxidation states. The cavity consists of a metallic helix and thin metallic end walls mounted on epoxy supports, which allows efficient penetration of the modulation field. The first quantitative EPR measurements from a metalloprotein (Hemerythrin) at 35 GHz with B₁ B are presented.     

An X-Band Crossed-Loop EPR Resonator

A copper X-band (9.22 GHz) cross-loop resonator has been constructed for use with 4 mm sample tubes. The Q for the two resonators is 380 and 350, respectively. The resonator efficiency is about 1 G per square root of watt. Operation has been demonstrated with measurement of T ₁ by saturation recovery for samples of coal and an immobilized nitroxide.     

Twin LC Resonator System for EPR Measurements Operating at Radio-Frequency

Two LC resonant circuits resonating at the same frequency (245 MHz) faced each other with reverse polarity (twin electron paramagnetic resonance (EPR) resonator). For the inductor of the LC circuit, a square single-turn one-loop coil (width, 38 mm) was fabricated. Each LC circuit was independently tuned using mechanical variable capacitors. A cylindrical phantom (diameter, 25 mm) including a 1 mM nitroxide radical physiological saline solution was located at the center of two coils (distance between these coils, 50 mm). Two resonant frequencies (the lower and the higher ones) were observed at each LC circuit of the twin EPR resonator with termination of the other LC circuit. The lower resonant frequency alone was observed when the powers from two LC circuits of the twin EPR resonator were combined by a 180° combiner. On the other hand, the higher frequency alone was observed when they were combined by a 0° combiner. EPR signals could be obtained using the 180° combiner (lower frequency) but not the 0° combiner (higher frequency).     

Combining a Magnetic Field Modulation Coil with a Surface-Coil-Type EPR Resonator

It is thought that the design of magnetic field modulation coils is one of the factors limiting enlargement of the sample size in electron paramagnetic resonance (EPR) measurements. In this study, we miniaturized the magnetic field modulation coil and combined it with a surface-coil-type resonator (SCR). The inductor of the SCR was a circular single-turn one-loop coil (diameter, 1 mm), and the magnetic field modulation coil was a twin-loop coil consisting of two solenoid coils each made of 15 turns of copper wire on a cylindrical bobbin with an axial length of 3 mm and an elliptical cross section (major axis, 7 mm; minor axis, 3 mm). The former was located on the latter via a spacer (thickness, 3 mm) in such a way that the directions of their axes coincided. Their combined size was about 10 mm wide, 10 mm deep, and 6 mm high. The transmission lines of the SCR were set on resonance at about 700 MHz. EPR measurements of a phantom (comprising agar that included a nitroxide radical and physiological saline solution), made with a miniaturized modulation coil combined with the SCR, exhibited a sensitivity similar to that for the conventional method. Authors' address: Hidekatsu Yokoyama, Department of Pharmaceutical Sciences, International University of Health and Welfare, 2600-1 Kitakanemaru, Ohtawara 324-8501, Japan     

Feasibility of Q-Band EPR Dosimetry in Biopsy Samples of Dental Enamel, Dentine and Bone

Electron paramagnetic resonance (EPR) dosimetry of tooth enamel in X-band has been established as a suitable method for individual reconstruction of doses 0.1 Gy and higher. The objective was to demonstrate the feasibility of using Q-band EPR in small biopsy tooth enamel samples to provide accurate measurements of radiation doses. Q-band spectra of small (<10 mg) irradiated samples of dentine and bone were studied to investigate the possibility of using Q-band EPR for dose measurements in those materials if there are limited amounts of enamel available, and there is no time for the chemical sample preparation required for accurate X-band measurements in dental enamel. Our results have shown that Q-band provides accurate measurements of radiation doses higher than 0.5 Gy in tooth enamel biopsy samples as small as 2 mg. Q-band EPR spectra in powdered dentine and bone demonstrated significantly higher resolution and sensitivity than in conventional X-band measurements.     

Three-Dimensional Diffraction-Free Airy Pulses in a Carbon Nanotube Medium under Conditions of an Optical Resonator

Russian Physics Journal - The propagation of three-dimensional extremely short optical pulses with the longitudinal Airy profile is theoretically investigated in a semiconductor carbon nanotube...     

1064nm纳秒激光脉冲激发的外腔式PbWO4拉曼激光器

研究了外腔式PbWO4拉曼激光器在纳秒脉冲抽运下的输出特性。利用主动调Q的Nd:YAG激光器产生的脉冲宽度为31.4ns,最大输出能量为200mJ的1064nm激光作为抽运源。拉曼激光谐振腔采用的是平凹腔设计。测量了输出的拉曼光脉宽与抽运能量的关系,分析了输出的拉曼光脉冲波形图和光谱图,测量了输出的拉曼光脉冲能量与抽运能量的关系,计算了转换效率与抽运能量的关系。当注入抽运光能量达到42mJ时,得到了一阶斯托克斯光脉冲的最大能量和转换效率分别为10mJ和24%,获得外腔式PbWO4拉曼激光器的一阶斯托克斯光脉冲波长为1177.6nm,典型的一阶斯托克斯光脉冲脉宽为20ns。     

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.     

Concepts in high-frequency EPR — Applications to bio-inorganic systems

In this contribution we describe a high-frequency high-field EPR facility which has been developed at the University of Nijmegen. We present the design of a heterodyne quasi-optical bridge based on a millimeter-wave vector network analyzer as source and detection system. The mm-waves are transported in free-space through Gaussian beam optic elements and through a corrugated guide inside the resonator insert. The Fabri-Pérot (TEM_00n) resonator is coupled through a metallic mesh and because of its bimodal property it can be operated using orthogonal detection leading to substantial improvement in sensitivity. In the first stage of the project, a multifrequency CW-facility is realized covering the 100–500 GHz range. In our initial explorative experiments we demonstrate the advantages of HF-EPR of high-spin systems: Due to the large microwave quantum, transitions which would be undetectable at X-band due to the large zerofield splitting can now be observed in good sensitivity. As a model for biological high-spin systems a sample of metmyoglobin was measured at D-band (130 GHz). Theg = 5.9 perpendicular line from theS = 5/2 ferric heme was detected and its line-width was compared to data previously obtained at Q-, X-, S- and L-band. As a model for biological integer spin systems theS = 1 signal of Ni(II) in nickel Tutton salt (Ni(NH₄)₂(SO₄)₂) was studied at 35 and 130 GHz.     

飞秒泵浦-探测实验数据分析

陈述了几种获取飞秒泵浦 探测实验数据中的光解动力学信息的解析物理模型 .其中单分量和双分量模型用来解释母体分子的单通道和双通道解离过程 ,另一个单分量模型用来解释碎片分子的解离或去激发过程 .所有模型都结合泵浦 探测实验数据予以解释     

飞秒超短脉冲的双光子干涉

利用钛宝石飞秒激光超短脉冲抽运BBO晶体,产生Ⅰ型自发光参量下转移的双光子对,在实验上得到双光子对的四阶干涉现象,证明了双光子纠缠态的关联特性。     

Quantum-mechanical predictions for EPR experiments with retardation plates

The quantum-mechanical detection probabilities for optical photon pairs are calculated for an EPR experimental arrangement with two plates (one per observer), with arbitrary wave retardations and fast-axis orientations, and two polarizers (one per observer) with arbitrary trasmission-axis orientations. Possible experimental tests of these predictions are suggested.1. It is important to observe that Clauser in his work [19] claimed that the experimental result _exp = –0.015 ± 0.025 was in agreement within errors, with the quantum theoretical prediction _QM = 0.002 of the Freedman's form of the strong Bell's inequality 0. The latter is however incompatible with the quoted values of retardations reported by Clauser that, on the contrary, give the following quantum mechanical prediction: _QM = 0.024, which is hardly compatible with the above experimental result.2. The fast-axes orientations of any inserted quarter-wave plates must remain the same during all the experimental meausrements.     

Impact of the Characteristic Impedance of Coaxial Lines on the Sensitivity of a 750-MHz Electronically Tunable EPR Resonator

A 750-MHz electronically tunable resonator was investigated in terms of the sensitivity of electron paramagnetic resonance (EPR) signal detection. The conversion efficiency of the radio-frequency magnetic field was calculated for resonators with 50- and 100-Ω coaxial coupling lines using three-dimensional (3D) microwave field and microwave circuit simulators. Based on the simulation results, two tunable resonators were physically constructed and compared in terms of EPR signal sensitivity using a nitroxyl radical solution. While the resonator with 100-Ω coaxial lines provided 14% greater signal intensity, its signal-to-noise ratio was lower than that of the resonator with 50-Ω lines. To demonstrate the capability of the constructed tunable resonator for EPR imaging experiments, a solution of nitroxyl radical and the leg of a tumor-bearing mouse were visualized.     

A Piezoceramic Resonator for Sonoluminescence Analysis

Acoustical Physics - The results of the numerical simulation and experimental study of an entirely piezoceramic cylindrical resonator to generate sonoluminescence are presented. The data on the...     

用于纳米粒子检测的双环谐振器

设计了一种可以探测单个纳米粒子的光学传感器结构,该结构由双环、双环间耦合区的通孔和直波导构成,并引入了Fano效应,进一步增强了粒子在光场中出现时的光耦合场变化.当纳米粒子穿过两个微环间的通孔时,其耦合系数和输出端的光强均发生变化,提出了一种基于双环谐振器结构的高精度耦合系数传感方法,通过检测双环谐振器耦合系数和输出端光强的变化对单体纳米粒子进行精确检测和计数.理论计算结果表明,在损耗为1 dB/cm的情况下,与单环结构相比,双环结构的灵敏度提升了两个数量级.该双环结构在减小波导损耗的同时有效提升了检测灵敏度.     

Dual-Compensating Composite Inversion Pulses for NMR

Dual-compensating composite inversion pulses described as Wigner rotation matrix has been proposed for NMR optimization. The main FORTRAN program was modified to carry out optimization of the composite pulses, and the subroutine DULSJ and DSLEQ were programed instead of “IMSL” library DBCLSJ to calculate Jacobian and Levenberg-Marquardt iteration equations. Pulse and phase angles with respect to positive and negative resonance off-set were optimized on the multidimensional surface in search for the optimal parameters. It was found that the results obtained by the proposed method are better than other exsisting pulse sequences.