Comparison of Continuous Wave, Spin Echo, and Rapid Scan EPR of Irradiated Fused Quartz

The E' defect in irradiated fused quartz has spin lattice relaxation times (T(1)) about 100 to 300 μs and spin-spin relaxation times (T(2)) up to about 200 μs, depending on the concentration of defects and other species in the sample. These long relaxation times make it difficult to record an unsaturated continuous wave (CW) electron paramagnetic resonance (EPR) signal that is free of passage effects. Signals measured at X-band (~9.5 GHz) by three EPR methods: conventional slow-scan field modulated EPR, rapid scan EPR, and pulsed EPR, were compared. To acquire spectra with comparable signal-to-noise, both pulsed and rapid scan EPR require less time than conventional CW EPR. Rapid scan spectroscopy does not require the high power amplifiers that are needed for pulsed EPR. The pulsed spectra, and rapid scan spectra obtained by deconvolution of the experimental data, are free of passage effects.     

Use of the Frank sequence in pulsed EPR

The Frank polyphase sequence has been applied to pulsed EPR of triarylmethyl radicals at 25 6 MHz (9.1 mT magnetic field), using 256 phase pulses. In EPR, as in NMR, use of a Frank sequence of phase steps permits pulsed FID signal acquisition with very low power microwave/RF pulses (ca. 1.5 mW in the application reported here) relative to standard pulsed EPR. A 0.2 mM aqueous solution of a triarylmethyl radical was studied using a 16 mm diameter cross-loop resonator to isolate the EPR signal detection system from the incident pulses.     

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.     

EPR and ENDOR Studies of Shallow Donors in SiC

Recent progress in the investigation of the electronic structure of the shallow nitrogen (N) and phosphorus (P) donors in 3C–, 4H– and 6H–SiC is reviewed with focus on the applications of magnetic resonance including electron paramagnetic resonance (EPR) and other pulsed methods such as electron spin echo, pulsed electron nuclear double resonance (ENDOR), electron spin-echo envelope modulation and two-dimensional EPR. EPR and ENDOR studies of the ²⁹Si and ¹³C hyperfine interactions of the shallow N donors and their spin localization in the lattice are discussed. The use of high-frequency EPR in combination with other pulsed magnetic resonance techniques for identification of low-temperature P-related centers in P-doped 3C–, 4H– and 6H–SiC and for determination of the valley–orbit splitting of the shallow N and P donors are presented and discussed.     

Pulsed Electron-Nuclear Double Resonance (ENDOR) at 140 GHz

We describe a spectrometer for pulsed ENDOR at 140 GHz, which is based on microwave IMPATT diode amplifiers and a probe consisting of a TE011 cavity with a high-quality resonance circuit for variable radiofrequency irradiation. For pulsed EPR we obtain an absolute sensitivity of 3x10(9) spins/Gauss at 20 K. The performance of the spectrometer is demonstrated with pulsed ENDOR spectra of a standard bis-diphenylene-phenyl-allyl (BDPA) doped into polystyrene and of the tyrosyl radical from E. coli ribonucleotide reductase (RNR). The EPR spectrum of the RNR tyrosyl radical displays substantial g-anisotropy at 5 T and is used to demonstrate orientation-selective Davies-ENDOR.     

Pulsed 95 GHz high-field EPR heterodyne spectrometer with high spectral and time resolution

Various time resolved EPR methods are applied to different test samples to demonstrate the abilities of pulsed high-field EPR spectroscopy. Two-pulse-echo field swept EPR spectroscopy on a nitroxide radical shows the increased spectral resolution by separating different spin systems by their relaxation properties. Additionally N¹⁴ electron-spin-echo-envelope-modulation (ESEEM) is observed for these systems at fields as high as 3.5 T. Thus, the N¹⁴ hyperfine interaction couplings can be probed by ESEEM and pulsed ENDOR (electron-nuclear-double-resonance) experiments. The sensitivity of pulsed ENDOR experiments is compared with cw-ENDOR. The different linewidths and amplitudes of the two methods are discussed. Transient nutation experiments on light induced triplet states demonstrate the high sensitivity and time resolution of high-field pulsed EPR. The sensitivity and time resolution of our 95 GHz spectrometer are determined and compared with pulsed X-band EPR spectrometer performances.     

A design of resonant cavity with an improved coupling-adjusting mechanism for the W-band EPR spectrometer

We report a new design of resonant cavity for a W-band electron paramagnetic resonance (EPR) spectrometer. An improved coupling-adjusting mechanism, which is robust, compact, and suits with both solenoid-type and split-pair magnets, is utilized on the cavity, and thus enables both continuous-wave (CW) and pulsed EPR experiments. It is achieved by a tiny metal cylinder in the iris. The coupling coefficient can be varied from 0.2 to 17.9. Furthermore, two pistons at each end of the cavity allow for adjustment of the resonant frequency. A horizontal TE₀₁₁ geometry also makes the cavity compatible with the two frequently used types of magnets. The coupling-varying ability has been demonstrated by reflection coefficient (S₁₁) measurement. CW and pulsed EPR experiments have been conducted. The performance data indicates a prospect of wide applications of the cavity in fields of physics, chemistry and biology.     

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.     

Pulsed EPR in 2-mm band

A pulsed 2-mm band EPR spectrometer is described. The perspectives of 2-mm band EPR are comprehensively discussed.     

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.     

Low Field (10 mT) Pulsed Dynamic Nuclear Polarization

EPR irradiation by a train of inverting pulses has potential advantages over continuous-wave EPR irradiation in DNP applications; however, it has previously been used only at high field (5 T). This paper presents the design and testing of an apparatus for performing pulsed DNP experiments at 10 mT with large samples (17 ml). Experimental results using pulsed DNP with an aqueous solution of a narrow-linewidth paramagnetic probe are presented. A maximum DNP enhancement of about -36 with a train of inverting pulses (width 500 ns, repetition time 4 micros) was measured. A preliminary comparison showed that, when the same enhancement value is considered, the pulsed DNP technique requires an average power that is about three times higher than that required with the CW irradiation. However, for in vivo DNP applications it is very important to minimize the average power deposited in the sample. From the experimental results reported in this work, when considering the maximum enhancement, the pulsed technique requires only 2% of the average power necessary with the CW DNP technique. We believe that this reduction in the average power can be important for future DNP studies with large biological samples.     

中国电子顺磁共振(EPR)发展50年回顾

自从1945年前苏联科学家Zavoisky在固体中观察到电子顺磁共振（EPR）这一奇妙的物理现象以来,电子顺磁共振波谱学已经经历了60多年漫长的发展历程. 在世界上,20世纪50、60年代是EPR的基本理论、实验技术和实验方法迅速发展的时期,同时对我国产生了很大的影响. 从60年代开始至今,EPR波谱学在我国已有50多年的发展,其间大约可以分为3个阶段： (一) 20世纪60~80年代初是EPR波谱设备研制和技术发展的初始阶段;(二) 20世纪80年代到21世纪初主要是EPR实验技术进一步发展和实验方法及其在化学、物理学、生物学、医学等学科中的应用研究阶段;(三) 21世纪以来,开始了新的实验技术和开展更加广泛深入的应用研究,特别是开始脉冲EPR波谱学的应用和相关设备的研制.     

Some applications of pulse techniques in EPR

Overview of application of pulsed EPR is given.     

X波段脉冲电子顺磁共振谱仪的矩形腔与微型平面腔的设计

为了满足脉冲式电子顺磁共振谱仪的需要,设计并制作了连续波谐振腔和脉冲谐振腔. 连续波谐振腔采用矩形谐振腔的设计,而脉冲谐振腔采用了微型平面腔的设计. 在设计阶段,使用Ansoft-HFSS三维电磁仿真软件对2种谐振腔进行模拟计算. 微型平面腔的加工采用了微纳加工技术. 制作完成的谐振腔的参数指标由网络分析仪测定. 实验测得2种谐振腔的参数指标符合理论模拟值,并满足脉冲式电子顺磁共振谱仪的要求.     

Detection of anisotropic hyperfine transitions in zero magnetic field using field-cycling techniques

For the first time, we describe the detection of hyperfine transitions in zero magnetic field using field-cycling techniques and pulsed EPR spectroscopy. The sample investigated was coal, which shows an anisotropic electron spin-(13)C hyperfine interaction.     

Electron paramagnetic resonance of globin proteins – a successful match between spectroscopic development and protein research

At the start of the twenty-first century, the research into the haem-containing globins got a considerable impetus with the discovery of three new mammalian globins: neuroglobin, cytoglobin and androglobin. Globins are by now found in all kingdoms of life and, in many cases, their functions are still under debate. This revival in globin research increased the demand for adequate physico-chemical research tools to determine the structure-function relationships of these proteins. From early days onwards, electron paramagnetic resonance (EPR) has been used in globin research. In recent decades, the field of EPR has been revolutionised with the introduction of many new pulsed and high-field EPR techniques. In this review, we highlight how EPR has become an essential tool in globin research, and how globins equally provide ideal model systems to push technical developments in EPR.     

Electron paramagnetic and muon spin resonance studies in fullerenes

This article reviews the various EPR (CW, pulsed and time-resolved) and μSR studies reported in C₆₀/C₇₀/C₈₂ fullerenes. Different techniques for preparing paramagnetic C₆₀/C₇₀ species giving an EPR signal have been included. This literature survey is complete from the beginning of fullerene research (1985) up to middle 1994.     

Concepts for the measurement of hyperfine structure in EPR spectroscopy

Continuous wave and pulsed EPR methods for the measurement of hyperfine interactions are reviewed.