Biochemical EPR imaging of skin

EPR Imaging (EPRI) of spin labels is a powerful method for investigating skin and can give information about biochemical processes which are involved in numerous skin diseases. Furthermore it enables the non invasive investigation of the liberation, penetration and distribution of spin labelled drugs. The basis of these measurements is spectral spatial EPR imaging employing modulated field gradients and simultaneous field scans (MOSS). A skin region (?=6 mm) was treated with a 10 μl spin label solution (1 mM). EPR spectra of 128 points were recorded in 128 spatial planes resulting in a 128×128 image matrix. A spatial resolution of better than 10 μm can be obtained for a spectral line width of 0.1 mT and a gradient of 4 Tm^?1.In vivo imaging on mammalian skin can be performed by employing surface coils at S-band frequencies, 3 GHz.     

Progressive EPR imaging with adaptive projection acquisition

Continuous wave electron paramagnetic resonance imaging (EPRI) of living biological systems requires rapid acquisition and visualization of free radical images. In the commonly used multiple-stage back-projection image reconstruction algorithm, the EPR image cannot be reconstructed until a complete set of projections is collected. If the data acquisition is incomplete, the previously acquired incomplete data set is no longer useful. In this work, a 3-dimensional progressive EPRI technique was implemented based on inverse Radon transform in which a 3-dimensional EPR image is acquired and reconstructed gradually from low resolution to high resolution. An adaptive data acquisition strategy is proposed to determine the significance of projections and acquire them in an order from the most significant to the least significant. The image acquisition can be terminated at any time if further collection of projections does not improve the image resolution distinctly, providing flexibility to trade image quality with imaging time. The progressive imaging technique was validated using computer simulations as well as imaging experiments. The adaptive acquisition uses 50-70% less projections as compared to the regular acquisition. In conclusion, adaptive data acquisition with progressive image reconstruction should be very useful for the accelerated acquisition and visualization of free radical distribution.     

L波段三维ESR成像系统的研制（Ⅱ）——L波段三维ESR成像系统

叙述了一个L波段（1.05 GHz）用于ESR和ESR成像的装置，用这套自制装置实现了3D ESR成像. 该装置由L波段ESR谱仪、三组梯度场线圈及控制单元和PC机数据采集系统组成. 样品腔是一个3-环2-缝再进入式谐振腔，可放入直径为20 mm、 长30 mm的H₂O样品，空谐振腔的频率是1.05 GHz. 微波振荡频率用自动频率控制（AFC）的方法自动锁在有载腔的频率上. 梯度场线圈沿X-，Y-和Z-轴产生线性梯度场，在中心40 mm球形范围内梯度场强度为2 mT/cm. 依照Lauterbur's方法进行3D ESR 图像重建. 用该系统检测了样品中TEMPO氮氧自由基的3D空间分布. 得到了TEMPO的2D、3D ESR图像、用像素灰度表示的自旋密度分布图及3D ESR-CT图像.     

EPR spectroscopy and imaging of TEMPO-labeled magnetite nanoparticles

The article presents results of a study of TEMPO-labeled polymer coated superparamagnetic iron(II,III) oxide nanoparticles using both Electron Paramagnetic Resonance (EPR) spectroscopy and Electron Paramagnetic Resonance imaging technique (EPRI). The X-band (9.4 GHz) EPR spectroscopy was used to investigate the behavior of TEMPO-labeled polymer coated magnetite nanoparticles in different conditions (temperature and orientation in magnetic field). The broad line, which comes from the core of Fe₃O₄ nanoparticles, shows anisotropy. This signal broadens with decreasing temperature, its intensity increases with increasing temperature and the g factor decreases with increasing temperature. The shape of the signal from nitroxide radical strongly depends on temperature. When temperature is higher than 200 K, a narrow triplet appears, but when it is lower than 200 K the signal consists of broad asymmetric lines. Analysis of the signal allowed characterization of the motion of the spin label attached to nanoparticles. Values of anisotropy parameter ɛ and rotational correlation time τ_c were calculated for TEMPO in the fast rotation regime.The ability of TEMPO-labeled PEG coated magnetite nanoparticles to diffuse within the hydrogel medium was also investigated. The EPR imaging of nanoparticles diffusion in hydrogel was made at room temperature using an EPR L-band (1 GHz) spectrometer. EPRI has been proved effective for evaluation of changes in the spatial distribution of nanoparticles in the sample.     

Lithium naphthalocyanine as a new molecular radical probe for electron paramagnetic resonance oximetry

A new lithium naphthalocyanine dye aggregate [Li₂Nc][LiNc] is reported as a potential electron paramagnetic resonance (EPR) oximetry probe for accurate measurement of oxygen concentration in biological systems. The Li₂Nc is diamagnetic; however, the LiNc molecule has an unpaired electron and hence is paramagnetic. The aggregate shows a strong and single line EPR signal that is non-saturating at normal EPR power levels. An oxygen-dependent peak-to-peak EPR spectral width ranging from 0.51 G (at pO₂: 0 mmHg) to 26.2 G (at pO₂: 760 mmHg) has been observed. The application of this probe has been demonstrated in the measurement of arterial and venous oxygen tensions in a rat.     

Open-type EPR spectrometer to measure electron spins of a sample located outside a resonator

An open-type electron paramagnetic resonance (EPR) spectrometer to measure a sample located outside a resonator was fabricated. As the resonator, the field modulation coils, and the main magnet were integrated on the resonator side in the sensor head, the space for a sample was opened. Thus, a large sample could be placed at the end of the resonator without much limitation on the size. For an application of this apparatus, various coal masses were placed on the resonator of the sensor head and EPR measurements were performed nondestructively. It was found that the EPR signal intensity of coals showed a good correlation with the carbon-to-hydrogen ratio, one of the parameters for classifying coal.     

Development and testing of a CW-EPR apparatus for imaging of short-lifetime nitroxyl radicals in mouse head

This article describes a method for reducing the acquisition time in three-dimensional (3D) continuous-wave electron paramagnetic resonance (CW-EPR) imaging. To visualize nitroxyl spin probes, which have a short lifetime in living organisms, the acquisition time for a data set of spectral projections should be shorter than the lifetime of the spin probes. To decrease the total time required for data acquisition, the duration of magnetic field scanning was reduced to 0.5 s. Moreover, the number of projections was decreased by using the concept of a uniform distribution. To demonstrate this faster data acquisition, two kinds of nitroxyl radicals with different decay rates were measured in mice. 3D EPR imaging of 4-hydroxy-2,2,6,6-tetramethylpiperidine-d₁₇-1-¹⁵N-1-oxyl in mouse head was successfully carried out. 3D EPR imaging of nitroxyl spin probes with a half-life of a few minutes was achieved for the first time in live animals.     

Regularized optimization (RO) reconstruction for oximetric EPR imaging

A new algorithm for EPR imaging oximetry is described and tested with experimental data for the case of one spatial and one spectral dimension. A single species with variable linewidth is assumed. Instead of creating a 2D image, two one-dimensional profiles are reconstructed: the concentration of the radical and the corresponding oxygen concentration, which reduces the dimensionality of the problem. The algorithm (i) seeks to minimize the discrepancy between experimental data and projections calculated from the profiles and (ii) uses Tikhonov regularization to constrain the smoothness of the results. This approach controllably smoothes profiles rather than the data, while preserving sharp features.     

Retrospective correction of bias in diffusion tensor imaging arising from coil combination mode

PurposeTo quantify and retrospectively correct for systematic differences in diffusion tensor imaging (DTI) measurements due to differences in coil combination mode.BackgroundMulti-channel coils are now standard among MRI systems. There are several options for combining signal from multiple coils during image reconstruction, including sum-of-squares (SOS) and adaptive combine (AC). This contribution examines the bias between SOS- and AC-derived measures of tissue microstructure and a strategy for limiting that bias.MethodsFive healthy subjects were scanned under an institutional review board-approved protocol. Each set of raw image data was reconstructed twice—once with SOS and once with AC. The diffusion tensor was calculated from SOS- and AC-derived data by two algorithms—standard log-linear least squares and an approach that accounts for the impact of coil combination on signal statistics. Systematic differences between SOS and AC in terms of tissue microstructure (axial diffusivity, radial diffusivity, mean diffusivity and fractional anisotropy) were evaluated on a voxel-by-voxel basis.ResultsSOS-based tissue microstructure values are systematically lower than AC-based measures throughout the brain in each subject when using the standard tensor calculation method. The difference between SOS and AC can be virtually eliminated by taking into account the signal statistics associated with coil combination.ConclusionsThe impact of coil combination mode on diffusion tensor-based measures of tissue microstructure is statistically significant but can be corrected retrospectively. The ability to do so is expected to facilitate pooling of data among imaging protocols.     

Atomic structure and diffusion properties of superanisotropic diffusive systems

The diffusion of oxygen tracer atoms has is, and a diffusion-structural analysis is made of the oxygen subsystem of the Sr_2.4Ca_1.6Bi₂O_8.8 oxide representing a copper-free precursor of bismuth high-T _c superconductors. The diffusion in this compound has been shown to be superanisotropic. It has been established that superanisotropic diffusion in the oxygen subsystem of oxide systems, rather than being connected with the high-temperature superconductivity and the existence of CuO₂ planes, is accounted for by the general features of their crystal structure.     

在体电子自旋共振(EPR)波谱和成像技术在生物医学中的应用

活性氧和氮自由基(ROS/RNS)在一系列的人类疾病中扮演着双重角色. 它们可以是氧化剂, 诱导氧化状态, 导致组织损伤. 它们又可以是信号传导因子, 诱发保护性反应, 使得被调节的组织器官经受得起更强的损伤. 鉴于它们在生物医学中的重要作用, 检测它们产生和分布的技术的研究因而变得必要和紧迫. 在体电子自旋共振(EPR)波谱和成像技术渐已被应用于活体生物体系中用以表针和显像ROS/RNS. EPR 波谱特性(包括线宽、强度和寿命)以及空间分布信息已为动物甚至人体病理模型中氧化还原状态和氧分布的检测提供不可缺少的依据. 该文将简单描述和讨论一系列在体EPR 波谱和成像技术在器官和组织中的应用, 其中包括活体组织氧化还原状态, 活体组织氧分布和时间演化, 自由基空间以及谱-空间成像等.     

Sequential CW-EPR image acquisition with 760-MHz surface coil array

This paper describes the development of a surface coil array that consists of two inductively coupled surface-coil resonators, for use in continuous-wave electron paramagnetic resonance (CW-EPR) imaging at 760 MHz. To make sequential EPR image acquisition possible, we decoupled the surface coils using PIN-diode switches, to enable the shifting of the resonators resonance frequency by more than 200 MHz. To assess the effectiveness of the surface coil array in CW-EPR imaging, two-dimensional images of a solution of nitroxyl radicals were measured with the developed coil array. Compared to equivalent single coil acquired images, we found the visualized area to be extended approximately 2-fold when using the surface coil array. The ability to visualize larger regions of interest through the use of a surface coil array, may offer great potential in future EPR imaging studies.     

Systematic approach to cutoff frequency selection in continuous-wave electron paramagnetic resonance imaging

This article describes a systematic method for determining the cutoff frequency of the low-pass window function that is used for deconvolution in two-dimensional continuous-wave electron paramagnetic resonance (EPR) imaging. An evaluation function for the criterion used to select the cutoff frequency is proposed, and is the product of the effective width of the point spread function for a localized point signal and the noise amplitude of a resultant EPR image. The present method was applied to EPR imaging for a phantom, and the result of cutoff frequency selection was compared with that based on a previously reported method for the same projection data set. The evaluation function has a global minimum point that gives the appropriate cutoff frequency. Images with reasonably good resolution and noise suppression can be obtained from projections with an automatically selected cutoff frequency based on the present method.     

Grain Boundary Diffusion in C<Subscript>60</Subscript> Thin Films

This paper focuses on the effect of grain boundaries on the diffusion processes in polycrystalline C₆₀ thin films. Electrically induced diffusion of Au was investigated by in situ measurements of the film conductivity. Electron Paramagnetic Resonance (EPR) spectroscopy was used to study diffusion of oxygen. Increase in grain sizes in polycrystalline C₆₀ thin films was found to result in the acceleration of gold and oxygen diffusion. The results are interpreted assuming that these impurities diffuse in C₆₀ films dominantly along grain boundaries.     

A new method for the determination of oxygen solubilities by EPR

Free radicals dissolved in oxygen-containing solutions give rise to EPR spectra characterized by very broad lines due to Heisenberg spin exchange. In the method herein proposed oxygen is consumed at a constant rate, within the cavity of an EPR spectrometer, by alkyl radicals generatedin situ by thermal decomposition of an aliphatic azo compound in the presence of a nitroxide probe. The effect of decreasing the oxygen concentration is to reduce the width, and therefore to increase the height of the spectral lines of the nitroxide, which reach a maximum when oxygen has been completely consumed. From the knowledge of the rate of generation of the alkyl radicals, the oxygen solubility in a given solvent can be easily determined.     

Design and Demonstration of Four-Channel Received Coil Arrays for Vertical-Field MRI

The layout of radio-frequency received coils is related to signal-to-noise ratio (SNR) in magnetic resonance imaging (MRI). In this paper, different structures of four-channel received coil arrays for vertical-field MRI are constructed and optimized by establishing the relationship between coil geometry and SNR to achieve a high SNR and a uniform SNR distribution in the region of interest (ROI). Then, the SNR distributions of three optimized configurations, including rectangular loops, non-definite shape surface coils, and solenoid loops as the main unit, are simulated and compared. The four-channel coil of solenoid loops as the main unit has been found to have the best performance with the highest mean SNR in the ROI when imaging without acceleration. In addition, g-factor and 2D SENSE SNR in yoz-plane are simply analyzed, which show a sharp decrease in SNR for all the coils. Finally, all the coils are manufactured and operated at a 0.5 T permanent magnet MRI system with phantom and joint imaging experiments. Using pixel-by-pixel manner to evaluate SNR map, the experimental results are consistent with the simulation results, while parallel imaging experiment results show that the major consideration in low field MRI is the improvement of SNR value and uniformity rather than that of the imaging speed. As different constructions of four-channel received coils are investigated, we have found the most effective configuration with high and uniform SNR for vertical-field MRI.     

Brain Imaging with Slotted Hybridized Magnetic Metamaterial Hat at 7-T MRI

Study of human pathologies and acquisition of anatomical images without any surgical intervention inside human body is possible because of magnetic resonance imaging (MRI), which is the keystone technique to characterize the psychology and neurochemistry of human body. However, for clinical trials, the study and cure of human diseases are followed by medical investigations of different animal anatomies. By employing different imaging techniques to animal anatomical models during their clinical trials yielded in exceptional image acquisition without any surgical invasion in the model, which resulted in noninvasive technique as compared to surgical invasion and opened the possibility to study human pathologies more precisely. This work exploits the notable properties of unique combination of multi-circular hybridized surface coils which can be used as hybridized magnetic metamaterial hat (HMMH). HMMH not only strengthens the uniformity of radio frequency (RF) rotational symmetry around its axis but also improves the signal-to-noise ratio (SNR) for rat’s brain imaging at 7-T MRI. We analyzed a periodic array of strongly coupled circular copper coils attached on circular coil shaped printed circuit board (PCB) substrate. In the design, some copper coils were inspired by the slot cavity loaded with parametric elements (capacitor and inductor). In addition, coils in the form of HMMH exploited the advantages of the hybrid modes which exhibited better and deeper RF sensitivity into the region of interest (ROI) as compared to single loop RF coil by exciting two Eigen modes simultaneously which resulted in homogenized magnetic field (B-field) and enhanced SNR at ROI. At resonance, the value of relative negative permeability, μ _r  = ?7 + j11 was achieved at 300 MHz for 7-T MRI. Furthermore, image quality at ROI was optimized by varying rat’s head position under magnetic resonance (MR) coil of MRI apparatus and in the presence or absence of HMMH. Design configuration and circuit model analysis were also done.     

Accelerated electron paramagnetic resonance imaging using partial Fourier compressed sensing reconstruction

PurposeElectron paramagnetic resonance (EPR) imaging has evolved as a promising tool to provide non-invasive assessment of tissue oxygenation levels. Due to the extremely short T₂ relaxation time of electrons, single point imaging (SPI) is used in EPRI, limiting achievable spatial and temporal resolution. This presents a problem when attempting to measure changes in hypoxic state. In order to capture oxygen variation in hypoxic tissues and localize cycling hypoxia regions, an accelerated EPRI imaging method with minimal loss of information is needed.MethodsWe present an image acceleration technique, partial Fourier compressed sensing (PFCS), that combines compressed sensing (CS) and partial Fourier reconstruction. PFCS augments the original CS equation using conjugate symmetry information for missing measurements. To further improve image quality in order to reconstruct low-resolution EPRI images, a projection onto convex sets (POCS)-based phase map and a spherical-sampling mask are used in the reconstruction process. The PFCS technique was used in phantoms and in vivo SCC7 tumor mice to evaluate image quality and accuracy in estimating O₂ concentration.ResultsIn both phantom and in vivo experiments, PFCS demonstrated the ability to reconstruct images more accurately with at least a 4-fold acceleration compared to traditional CS. Meanwhile, PFCS is able to better preserve the distinct spatial pattern in a phantom with a spatial resolution of 0.6 mm. On phantoms containing Oxo63 solution with different oxygen concentrations, PFCS reconstructed linewidth maps that were discriminative of different O₂ concentrations. Moreover, PFCS reconstruction of partially sampled data provided a better discrimination of hypoxic and oxygenated regions in a leg tumor compared to traditional CS reconstructed images.ConclusionsEPR images with an acceleration factor of four are feasible using PFCS with reasonable assessment of tissue oxygenation. The technique can greatly enhance EPR applications and improve our understanding cycling hypoxia. Moreover this technique can be easily extended to various MRI applications.     

Paramagnetic defects in gamma-irradiated Na/K-silicate glasses

Gamma-irradiated alkali silicate glasses of the variable composition 22xNa₂O · 22(1 ? x)K₂O · 3CaO · 75SiO₂ have been studied using the electron paramagnetic resonance (EPR) method. It has been established that, upon the successive replacement Na ?? K in the two-alkali silicate glass, the EPR spectrum of hole centers on nonbridging oxygen atoms can be represented as a superposition of signals from the oxygen centers HC ₁(Na), HC ₂(Na), HC ₁(K), and HC ₂(K), which are characteristic of single-alkali silicate systems. The concentration dependences of hole and electron paramagnetic centers do not exhibit specific features that can be interpreted as a manifestation of the ??mixed-alkali effect.?? The results obtained have been discussed taking into account the extended model of centers on nonbridging oxygen atoms.     

An optimized solenoidal head radiofrequency coil for low-field magnetic resonance imaging

Applications of low-field magnetic resonance imaging (MRI) systems (<0.3 T) are limited due to the signal-to-noise ratio (SNR) being lower than that provided by systems based on superconductive magnets (≥1.5 T). Therefore, the design of radiofrequency (RF) coils for low-field MRI requires careful consideration as significant gains in SNR can be achieved with the proper design of the RF coil. This article describes an analytical method for the optimization of solenoidal coils. Coil and sample losses are analyzed to provide maximum SNR and optimum B₁ field homogeneity. The calculations are performed for solenoidal coils optimized for the human head at 0.2 T, but the method could also be applied to any solenoidal coil for imaging other anatomical regions at low field. Several coils were constructed to compare experimental and theoretical results. A head magnetic resonance image obtained at 0.2 T with the optimum design is presented.