Electron Spin Resonance System Research Articles

Frequency multiplexing enables parallel multi-sample EPR

Electron paramagnetic resonance (EPR) spectroscopy stands out as a powerful analytical technique with extensive applications in the fields of biology, chemistry, physics, and material sciences. It proves invaluable for investigating the molecular structure and reaction mechanisms of substances containing unpaired electrons, such as metal complexes, organic and inorganic radicals, and intermediate states in chemical reactions. However, despite their remarkable capabilities, EPR systems face significant limitations in terms of sample throughput, as current commercial systems only target the analysis of one sample at a time. Here we introduce a novel scheme for conducting ultra-high frequency continuous-wave EPR (CW EPR) targeting the EPR spectroscopy of multiple microliter volume samples in parallel. Our proof-of-principle prototype involves two decoupled detection cells equipped with high qualty factor Q=104\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$Q=104$$\\end{document} solenoidal coils tuned to 488 and 589 MHz, ensuring a significant frequency gap for effective radio frequency (RF) decoupling between the channels. To further enhance electromagnetic decoupling, an orthogonal alignment of the coils was adopted. The paper further presents an innovative radiofrequency circuit concept that utilizes a single physical RF channel to simultaneously conduct parallel EPR on up to eight cells. Parallel EPR experiments on two BDPA samples, each with a sample volume of 18.3 μL, registered signal-to-noise ratios of 255 and 252 for the two EPR measurement cells, with no observable coupling. The showcased prototype, built using cost-effective commercially available fabrication technology, is readily scalable and represents an initial step with promising potential for advancing sample screening with high-throughput parallel EPR.

Electron Paramagnetic Resonance Implemented with Multiple Harmonic Detections Successfully Maps Extracellular pH In Vivo.

Extracellular acidification indicates a metabolic shift in cancer cells and is, along with tissue hypoxia, a hallmark of tumor malignancy. Thus, non-invasive mapping of extracellular pH (pHe) is essential for researchers to understand the tumor microenvironment and to monitor tumor response to metabolism-targeting drugs. While electron paramagnetic resonance (EPR) has been successfully used to map pHe in mouse xenograft models, this method is not sensitive enough to map pHe with a moderate amount of exogenous pH-sensitive probes. Here, we show that a modified EPR system achieves twofold higher sensitivity by using the multiple harmonic detection (MHD) method and improves the robustness of pHe mapping in mouse xenograft models. Our results demonstrate that treatment of a mouse xenograft model of human-derived pancreatic ductal adenocarcinoma cells with the carbonic anhydrase IX (CAIX) inhibitor U-104 delays tumor growth with a concurrent tendency toward further extracellular acidification. We anticipate that EPR-based pHe mapping can be expanded to monitor the response of other metabolism-targeting drugs. Furthermore, pHe monitoring can also be used for the development of improved metabolism-targeting cancer treatments.

Noninvasive detection of the endogenous free radical melanin in human skin melanomas using electron paramagnetic resonance (EPR).

We explored the capability of low-frequency Electron Paramagnetic Resonance (EPR) to noninvasively detect melanin (a stable semiquinone free radical) in the human skin. As previous in vitro studies on biopsies suggested that the EPR signal from melanin was different when measured in skin melanomas or benign nevi, we conducted a prospective first-in-man clinical EPR study in patients with skin lesions suspicious of melanoma. EPR spectra were obtained using a spectrometer operating at 1GHz, with a surface coil placed over the area of interest. Two clinical studies were carried out: 1) healthy volunteers (n=45) presenting different skin phototypes; 2) patients (n=88) with skin lesions suspicious of melanoma (n=100) requiring surgical resection. EPR data obtained before surgery were compared with histopathology results. The method was not sensitive enough to measure differences in melanin content due to changes in skin pigmentation. In patients, 92% of the spectra were analyzable. The EPR signal of melanin was significantly higher (p<0.0001) in melanoma lesions (n=26) than that in benign atypical nevi (n=62). A trend toward a higher signal intensity (though not significant) was observed in high Breslow depth melanomas (a marker of skin invasion) than in low Breslow lesions. To date, no naturally occurring free radicals have been detected by low-frequency EPR systems adapted for clinical studies. Here, we demonstrated for the first time the ability of this technology to detect an endogenous free radical, opening new avenues for evaluating clinical EPR as a potential aid in the diagnosis of pigmented skin lesions.

Semi-automated EPR system for direct monitoring the photocatalytic activity of TiO2 suspension using TEMPOL model compound.

The photocatalytic activity of TiO2 nanoparticles in aqueous solutions is commonly evaluated by monitoring the rate of methylene blue bleaching and phenols degradation, but both substrates suffer from many drawbacks, e.g., the high capacity of dark adsorption, self-degradation, and photosensitization. Besides, filtration is always required to separate the particulate photocatalyst before the analysis. Herein, we investigated the potential use of electron paramagnetic resonance(EPR) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL) to directly monitor the photocatalytic activity of TiO2 suspensions without the need for filtration. The results showed that TEMPOL aqueous solution is in the dark and under UV-A illumination, does not absorb UV-A and visible light, and has negligible dark adsorption. The influence of TEMPOL concentration, light intensity, and TiO2 loading on the photocatalytic deactivation rate has been investigated. The mechanisms of TEMPOL deactivation in the presence and absence of oxygen as well as in the presence of methanol •OH radicals' scavenger have been discussed. The photocatalytic deactivation products have been analyzed using EPR, 1H-NMR, and 13C-NMR spectroscopies. It is found that the deactivation of TEMPOL is initiated by •OH radicals and α-H abstraction from the 4-piperidine position followed by the formation of TEMPONE (4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl) and 4-oxo-2,2,6,6-tetramethylpiperidine). In the presence of methanol, the formed α-hydroxyl radicals (•CH2OH) attack the nitroxide side of TEMPOL and produce 4-hydroxy-tetramethylpiperidine. Same activity trends have been observed for the photocatalytic methanol oxidation and TEMPOL deactivation over different types of TiO2 photocatalysts evincing that the proposed method has a potential for direct monitoring of the activities of photocatalyst suspensions.

Development of Electron Paramagnetic Resonance Magnet System for In Vivo Tooth Dosimetry

As part of a homebuilt continuous wave electron paramagnetic resonance (EPR) spectrometer operating at 1.2 GHz, a magnet system for in vivo tooth dosimetry was developed. The magnet was designed by adopting NdFeB permanent magnet (PM) for the main magnetic field generation. For each pole of the magnet, 32 cylindrical PMs were arranged in 2 axially aligned ring arrays. The pole gap was 18 cm, which was wide enough for a human head breadth. The measured magnetic field was compared with the magnetic field distribution calculated in a finite element method (FEM) simulation. EPR spectra of intact human teeth irradiated 5 and 30 Gy were measured for the performance test with the developed magnet system and spectrometer. The measured mean magnetic flux density was estimated to be 44.45 mT with homogeneity of 1,600 ppm in a 2 cm diameter of the spherical volume of the XY plane, which was comparable to the FEM simulation results. The sweep coefficient of the magnetic field sweep coil was 0.35 mT per Ampere in both the measurement and FEM simulation. With ±9 A current, the sweep range was 5.7 mT, which was sufficiently wide to measure the tooth radiation-induced signal (RIS) and reference material. The peak-to-peak amplitude of the measured modulation field was 0.38 mT at the center of the magnet. With the developed magnet fully integrated into an EPR system, the EPR spectra of 5 and 30 Gy irradiated teeth were successfully acquired. The developed magnet system showed sufficiently acceptable performance in terms of magnetic flux density and homogeneity. The EPR spectrum of tooth RIS could be measured ex vivo. The RIS of 5 and 30 Gy irradiated teeth was clearly distinguishable from intact human teeth.

Three-dimensional electron paramagnetic resonance imaging of mice using ascorbic acid sensitive nitroxide imaging probes

Nitroxide compounds have been used as redox-sensitive imaging probes by electron paramagnetic resonance (EPR) for assessing oxidative stress in vivo. Fast redox reactions of nitroxide radicals are favorable for assessment of higher redox sensitivity; however, a variety of nitroxides have not been trialed for use as imaging probes due to their very rapid in vivo reduction, which cannot be captured at the slow operation speed of existing EPR imagers. To overcome this limitation, we improved our EPR system to provide a stable and highly sensitive imaging operation. We challenged the improved EPR imager to perform three-dimensional (3D) EPR imaging of mouse brain using two useful nitroxide imaging probes, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol) and 2,6-dispiro-4′,4ʺ-dipyrane-piperidine-4-one-N-oxyl (DiPy). The second-order rate constant of DiPy with ascorbic acid is 10 times larger than that of Tempol. The improved EPR imager obtained clear 3D EPR images of mouse brain and demonstrated that Tempol could exist with an unpaired electron. The imager also successfully obtained 3D EPR images of mouse head after administration of DiPy. As 126 projections can be acquired in a period of 6 s, 3D EPR imaging can visualize the sequential process of DiPy entering the brain, being distributed within the brain, and being reduced within the brain. These improvements to the EPR imager will enable useful nitroxide imaging probes that were previously unsuitable as imaging probes due to their rapid reduction to be considered for use for sensitive redox assessment in an in vivo system.

Development of an L-band resonator optimized for fast scan EPR imaging of the mouse head.

To develop a novel resonator for high-quality fast scan electron paramagnetic resonance (EPR) and EPR/NMR co-imaging of the head and brain of mice at 1.25 GHz. Resonator dimensions were scaled to fit the mouse head with maximum filling factor. A single-loop 6-gap resonator of 20 mm diameter and 20 mm length was constructed. High resonator stability was achieved utilizing a fixed position double coupling loop. Symmetrical mutually inverted connections rendered it insensitive to field modulation and fast scan. Coupling adjustment was provided by a parallel-connected variable capacitor located at the feeding line at λ/4 distance. To minimize radiation loss, the shield around the resonator was supplemented with a planar conductive disc that focuses return magnetic flux. Coupling of the resonator loaded with the mouse head was efficient and easy. This resonator enabled high-quality in vivo 3D EPR imaging of the mouse head following intravenous infusion of nitroxide probes. With this resonator and rapid scan EPR system, 4 ms scans were acquired in forward and reverse directions so that images with 2-scan 3,136 projections were acquired in 25 s. Head images were achieved with resolutions of 0.4 mm, enabling visualization of probe localization and uptake across the blood-brain barrier. This resonator design provides good sensitivity, high stability, and B1 field homogeneity for in vivo fast scan EPR of the mouse head and brain, enabling faster measurements and higher resolution imaging of probe uptake, localization, and metabolism than previously possible.

Compact electron spin resonance skin oximeter: Properties and initial clinical results

Skin oxygen level is of significance for the diagnosis and treatment of many clinical problems, such as chronic wounds and diabetic foot ulcers. Furthermore, skin oxygen levels can be correlated to arterial oxygen partial pressure, thereby revealing potentially dangerous conditions such as hyperoxia (too much oxygen), which may occur in ventilated neonates. Traditionally, skin oxygen levels are measured using electrochemical methods and, more recently, also by fluorescence lifetime techniques. These approaches suffer from several drawbacks, rendering them suboptimal. The purpose of this work is to develop an electron spin resonance (ESR) -based method for monitoring oxygen partial pressure (pO2 ) in skin tissue. A compact sensor for pulsed ESR is designed and constructed. Our ESR-based method makes use of a unique exogenous paramagnetic spin probe that is placed on the skin in a special partially sealed sticker, and subsequently measuring its signal with the compact pulsed ESR sensor that includes a miniature magnet and a small S-band (~2.3 GHz) microwave resonator. The inverse of the spin-spin relaxation time (1/T2 ) measured by ESR is shown to be linearly correlated with pO2 levels. The sensor and its matching sticker were tested both in vitro and in vivo (with human subjects). Measured skin pO2 levels reached equilibrium after ~2-3 h and were found to be comparable to those measured by continuous-wave (CW) ESR using a large electromagnet. A compact pulsed ESR sensor with a matching paramagnetic sticker can be used for pO2 monitoring of the skin tissue, similar to large bulky CW ESR systems.

Ferromagnetic resonance imbalance at high microwave power: Effect on the Gilbert damping parameter

Nowadays, electron spin resonance (ESR) systems are routinely used to measure the ferromagnetic resonance (FMR) in a wide range of experiments. However, the number of spins in ferromagnets far exceeds the small number of spins in paramagnetic systems that ESR systems were originally designed for. In this study, we show that high spin concentration and microwave input power—conditions routinely met in various FMR experiments—lead to the strong distortion of the FMR shape due to the sublinear operating regime of the microwave detector. We introduce the additional imbalance term in the FMR Lorentzian fitting function that allows extracting correct values of the Gilbert damping parameter under such conditions. Our results are crucial for the quantitative estimation of the Gilbert damping—the key parameter in many magnetic and spintronics measurements.

A portable EPR system for the absolute polarimetry of noble gases

A simple and portable electron paramagnetic resonance (EPR) system has been developed for the absolute polarimetry of noble gases polarized by spin-exchange optical pumping. By using modern digital technology together with software implementation of phase-sensitive detection and feedback control, the new system has become much more compact than the conventional EPR apparatus and can be easily transported anywhere. The main components of the new EPR system are a computer and a PC-based oscilloscope with a built-in function generator. The raw signal data is processed in real time by a computer, which offers great flexibility to the new system. By modifying the data-processing algorithm, it can be customized and applied to other scientific and engineering measurements that utilize phase-sensitive detection.

Development of High-Field and High-Pressure ESR System and Application to Triangular Antiferromagnet $$\hbox {CsCuCl}_{3}$$

We have developed a new hybrid-type pressure cell for the high-pressure and high-field electron spin resonance (ESR) measurement using a widely used Oxford 15 T superconducting magnet with the variable temperature insert (VTI). The size of the pressure cell was optimized and a probe was also specially designed so as to be fitted to the VTI. We confirmed that the new pressure cell can generate the pressure up to at least 2.0 GPa repeatedly. Using this new ESR system, high-pressure and high-field ESR measurement was performed on the triangular antiferromagnet $$\hbox {CsCuCl}_{3}$$ for $$H \parallel c$$ at 4.2 K in the frequency region 60 GHz–420 GHz. We succeeded in observing the significant pressure effect of this compound. Moreover, a new ESR mode which is expected to correspond to the 1/3 magnetization plateau was observed at 0.80 GPa.

Advanced surface resonators for electron spin resonance of single microcrystals.

Electron spin resonance (ESR) spectroscopy of paramagnetic species in single crystals is a powerful tool for characterizing the latter's magnetic interaction parameters in detail. Conventional ESR systems are optimized for millimeter-size samples and make use of cavities and resonators that accommodate tubes and capillaries in the range 1-5 mm. Unfortunately, in the case of many interesting materials such as enzymes and inorganic catalytic materials (e.g., zeolites), single crystals can only be obtained in micron-scale sizes (1-200 µm). To boost ESR sensitivity and to enable experiments on microcrystals, the ESR resonator needs to be adapted to the size and shape of these specific samples. Here, we present a unique family of miniature surface resonators, known as "ParPar" resonators, whose mode volume and shape are optimized for such micron-scale single crystals. This approach significantly improves upon the samples' filling factor and thus enables the measurement of much smaller crystals than was previously possible. We present here the design of such resonators with a typical mode dimension of 20-50 µm, as well as details about their fabrication and testing methods. The devices' resonant mode(s) are characterized by ESR microimaging and compared to the theoretical calculations. Moreover, experimental ESR spectra of single microcrystals with typical sizes of ∼25-50 µm are presented. The measured spin sensitivity for the 50-µm resonator at cryogenic temperatures of 50 K is found to be ∼1.8 × 106 spins/G √Hz for a Cu-doped single crystal sample that is representative of many biological samples of relevance.

Surface loop-gap resonators for electron spin resonance at W-band.

Electron spin resonance (ESR) is a spectroscopic method used to detect paramagnetic materials, reveal their structure, and also image their position in a sample. ESR makes use of a large static magnetic field to split the energy levels of the electron magnetic moment of the paramagnetic species. A strong microwave magnetic field is applied to excite the spins, and subsequently the ESR system detects their faint microwave signal response. The sensitivity of an ESR system is greatly influenced by the magnitude of the static field and the properties of the microwave resonator used to detect the spin signal. In general terms, the higher the static field (microwave frequency) and the smaller the resonator, the more sensitive the system will be. Previous work aimed at high-sensitivity ESR was focused on the development and testing of very small resonators operating at moderate magnetic fields in the range of ∼0.1-1.2 T (maximum frequency of ∼35 GHz). Here, we describe the design, construction, and testing of recently developed miniature surface loop-gap resonators used in ESR and operating at a much higher frequency of ∼95 GHz (W-band, corresponding to a field of ∼3.4 T). Such resonators can greatly enhance the sensitivity of ESR and also improve the resulting spectral resolution due to the higher static field employed. A detailed description of the resonator's design and coupling mechanism, as well as the supporting probe head, is provided. We also discuss the production method of the resonators and probe head and, in the end, provide preliminary experimental results that show the setup's high spin sensitivity and compare it to theoretical predictions.

Real-time liver uptake and biodistribution of magnetic nanoparticles determined by AC biosusceptometry

We describe the development of a joint in vivo/ex vivo protocol to monitor magnetic nanoparticles in animal models. Alternating current biosusceptometry (ACB) enables the assessment of magnetic nanoparticle accumulation, followed by quantitative analysis of concentrations in organs of interest. We present a study of real-time liver accumulation, followed by the assessment of sequential biodistribution using the same technique. For quantification, we validated our results by comparing all of the data with electron spin resonance (ESR). The ACB had viable temporal resolution and accuracy to differentiate temporal parameters of liver accumulation, caused by vasculature extravasation and macrophages action. The biodistribution experiment showed different uptake profiles for different doses and injection protocols. Comparisons with the ESR system indicated a correlation index of 0.993. We present the ACB system as an accessible and versatile tool to monitor magnetic nanoparticles, allowing in vivo and real-time evaluations of distribution and quantitative assessments of particle concentrations.

Overview of physical dosimetry methods for triage application integrated in the new European network RENEB

Purpose: In the EC-funded project RENEB (Realizing the European Network in Biodosimetry), physical methods applied to fortuitous dosimetric materials are used to complement biological dosimetry, to increase dose assessment capacity for large-scale radiation/nuclear accidents. This paper describes the work performed to implement Optically Stimulated Luminescence (OSL) and Electron Paramagnetic Resonance (EPR) dosimetry techniques.Materials and methods: OSL is applied to electronic components and EPR to touch-screen glass from mobile phones. To implement these new approaches, several blind tests and inter-laboratory comparisons (ILC) were organized for each assay.Results: OSL systems have shown good performances. EPR systems also show good performance in controlled conditions, but ILC have also demonstrated that post-irradiation exposure to sunlight increases the complexity of the EPR signal analysis.Conclusions: Physically-based dosimetry techniques present high capacity, new possibilities for accident dosimetry, especially in the case of large-scale events. Some of the techniques applied can be considered as operational (e.g. OSL on Surface Mounting Devices [SMD]) and provide a large increase of measurement capacity for existing networks. Other techniques and devices currently undergoing validation or development in Europe could lead to considerable increases in the capacity of the RENEB accident dosimetry network.

Development of multi-frequency ESR system for high-pressure measurements up to 2.5 GPa

A new piston-cylinder pressure cell for electron spin resonance (ESR) has been developed. The pressure cell consists of a double-layer hybrid-type cylinder with internal components made of the ZrO2-based ceramics. It can generate a pressure of 2GPa repeatedly and reaches a maximum pressure of around 2.5GPa. A high-pressure ESR system using a cryogen-free superconducting magnet up 10T has also been developed for this hybrid-type pressure cell. The frequency region is from 50GHz to 400GHz. This is the first time a pressure above 2GPa has been achieved in multi-frequency ESR system using a piston-cylinder pressure cell. We demonstrate its potential by showing the results of the high-pressure ESR of the S=1 system with the single ion anisotropy NiSnCl6·6H2O and the S=1/2 quantum spin system CsCuCl3. We performed ESR measurements of these systems above 2GPa successfully.

Toward 2D and 3D imaging of magnetic nanoparticles using EPR measurements.

Magnetic nanoparticles (MNPs) are an important asset in many biomedical applications. An effective working of these applications requires an accurate knowledge of the spatial MNP distribution. A promising, noninvasive, and sensitive technique to visualize MNP distributions in vivo is electron paramagnetic resonance (EPR). Currently only 1D MNP distributions can be reconstructed. In this paper, the authors propose extending 1D EPR toward 2D and 3D using computer simulations to allow accurate imaging of MNP distributions. To find the MNP distribution belonging to EPR measurements, an inverse problem needs to be solved. The solution of this inverse problem highly depends on the stability of the inverse problem. The authors adapt 1D EPR imaging to realize the imaging of multidimensional MNP distributions. Furthermore, the authors introduce partial volume excitation in which only parts of the volume are imaged to increase stability of the inverse solution and to speed up the measurements. The authors simulate EPR measurements of different 2D and 3D MNP distributions and solve the inverse problem. The stability is evaluated by calculating the condition measure and by comparing the actual MNP distribution to the reconstructed MNP distribution. Based on these simulations, the authors define requirements for the EPR system to cope with the added dimensions. Moreover, the authors investigate how EPR measurements should be conducted to improve the stability of the associated inverse problem and to increase reconstruction quality. The approach used in 1D EPR can only be employed for the reconstruction of small volumes in 2D and 3D EPRs due to numerical instability of the inverse solution. The authors performed EPR measurements of increasing cylindrical volumes and evaluated the condition measure. This showed that a reduction of the inherent symmetry in the EPR methodology is necessary. By reducing the symmetry of the EPR setup, quantitative images of larger volumes can be obtained. The authors found that, by selectively exciting parts of the volume, the authors could increase the reconstruction quality even further while reducing the amount of measurements. Additionally, the inverse solution of this activation method degrades slower for increasing volumes. Finally, the methodology was applied to noisy EPR measurements: using the reduced EPR setup's symmetry and the partial activation method, an increase in reconstruction quality of ≈ 80% can be seen with a speedup of the measurements with 10%. Applying the aforementioned requirements to the EPR setup and stabilizing the EPR measurements showed a tremendous increase in noise robustness, thereby making EPR a valuable method for quantitative imaging of multidimensional MNP distributions.

Quantitative Spin-trapping ESR Investigation of Alkoxyl Radical Derived from AAPH: Development of a Flow-injection Spin-trapping ESR System for the Oxygen Radical Absorbance Capacity Assay

A flow-injection electron spin resonance (ESR) system was developed for the quantitative detection of an alkoxyl radical (RO·, R = C(CH3)2–C(+NH2Cl−)NH2) derived from AAPH (2,2′-azobis(2,4-amidinopropane) dihydrochloride) by thermal decomposition. Optimal measurement conditions for the system were examined, and it was found that the control of the radical formation by quenching in an ice-water vessel should be effective to obtain the stable and accurate results. The system was applied for the estimation of the alkoxyl radical-elimination ability and the oxygen radical absorbance capacity values of selected biosubstances, such as Trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid), caffeic acid, 4-hydroxycinnamic acid, epinephrine, rutin, (+)-catechin, l-tryptophane, and d-mannitol. As the rate constant for the reaction between alkoxyl radical and substrate, k S, could not be unequivocally determined, the defined value, γ 50 = k S/k 1, (k 1, the rate constant for the reaction between alkoxyl radical and spin trap) was used as a reaction parameter of substrate for alkoxyl radical. The flow-injection electron spin resonance system using alkoxyl radical elimination gave valid γ 50 values for biosubstances, and the system should be a valuable method for the evaluation of the antioxidant ability.

Development of High-Pressure and Multi-Frequency ESR System and Its Application to Quantum Spin System

We have developed a high-pressure and multi-frequency electron spin resonance (ESR) system in the submillimeter wave region. The pressure is generated by the piston–cylinder pressure cell whose inner parts are all made of ceramics. The requirements for the inner parts of the pressure cell are toughness and transmission in the submillimeter wave region and they enable us to observe the transmitted light through a sample subjected to high pressure. It was found that both properties can be achieved by the combination of the inner parts made of the ZrO2-based ceramic and the Al2O3 ceramic. For the Shastry-Sutherland compound SrCu2(BO3)2, we observed the direct ESR transition from the singlet ground state to the first excited triplet sates at 1.5 GPa successfully in the frequency region from 300 to 700 GHz.

Development of High-Pressure ESR System Using Micro-coil

We have developed the high-pressure electron spin resonance (ESR) system using a micro-coil in the frequency region up to around 2 GHz and potentially 10 GHz. The hybrid-type piston-cylinder pressure cell whose maximum pressure reaches 4 GPa was used. In this study, we obtained ESR spectra at 2.3 GPa successfully, which can never be obtained by the single-layer piston-cylinder pressure cell. The minimum detectable spin number was estimated to be the order of 1012 spins/G. Moreover, it is shown that the sensitivity can be improved by two orders of magnitude using the field modulation technique. This high-pressure ESR technique is a promising one to achieve the sensitivity and the high pressure simultaneously.