Fitting of EPR spectra: the importance of a flexible bandwidth

Utilizing a standard spin Hamiltonian for an S=32 spin system, we fit complete X-band powder EPR spectra of the Cr(oxalate)(3)(3-) anion diluted into K(3)[Co(oxalate)(3)]·3H(2)O. By using models for the bandshape and bandwidths of varying degree of flexibility, we show that the successful outcome of such a fitting endeavour very much depends on the used bandshape-bandwidth model. The best results are obtained when the bandwidth model incorporates anisotropic intrinsic bandwidths in addition to being able to account for inhomogeneous line broadening caused by distributions of the spin Hamiltonian parameters.     

Application of magnetic field over-modulation for improved EPR linewidth measurements using probes with Lorentzian lineshape

Magnetic field modulation in CW electron paramagnetic resonance (EPR) is used for signal detection. However, it can also distort signal lineshape. In experiments where the linewidth information is of particular importance, small modulation amplitude is usually used to limit the lineshape distortion. The use of small modulation amplitude, however, results in low signal-to-noise ratio and therefore affects the precision of linewidth measurements. Recently, a new spectral simulation model has been developed enabling accurate fitting of modulation-broadened EPR spectra in liquids. Since the use of large modulation amplitude (over-modulation) can significantly enhance the EPR signal, the precision of linewidth measurements is therefore greatly improved. We investigated the over-modulation technique in EPR oximetry experiments using the oxygen-sensing probe lithium octa-n-butoxy-substitued naphthalocyanine (LiNc-BuO). Modulation amplitudes 2-18 times the intrinsic linewidth of the probe were applied to increase the spectral signal-to-noise ratio. The intrinsic linewidth of the probe at different oxygen concentrations was accurately extracted through curve fitting from the enhanced spectra. Thus, we demonstrated that the over-modulation model is also applicable to particulate oxygen-sensing probes such as LiNc-BuO and that the lineshape broadening induced by oxygen is separable from that induced by over-modulation. Therefore, the over-modulation technique can be used to enhance sensitivity and improve linewidth measurements for EPR oximetry with particulate oxygen-sensing probes with Lorentzian lineshape. It should be particularly useful for in vivo oxygen measurements, in which direct linewidth measurements may not be feasible due to inadequate signal-to-noise ratio.     

Evaluation of oxygen-response times of phthalocyanine-based crystalline paramagnetic spin probes for EPR oximetry

The goal of the present study was to evaluate the temporal response of particulate-based EPR oximetry probes to changes in partial pressure of oxygen (pO(2)). In order to accurately evaluate the oxygen-response time, we developed a method for rapid modulation of pO(2) in a chamber containing the probe using an oscillator-driven speaker-diaphragm setup. The apparatus was capable of producing sinusoidal changes in pO(2) at frequencies up to 300 Hz or more. The pressure-modulation setup was used to evaluate the temporal response of some of the most commonly used phthalocyanine-based particulate probes. For validation, the time-response of the probes was compared to that of a high sensitivity pressure sensor. The results revealed that some particulate probes could respond to changes in pO(2) with a temporal response of 3.3 ms (300 Hz). The observations were interpreted in the light of their crystalline packing in favor of oxygen diffusion. The results of the present study should enable the selection of probes for oximetry applications requiring high temporal resolution.     

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.     

高时间分辨MRPC的位置灵敏读出方法

根据MRPC工作机制和高时间分辨的特性, 研制一种位置灵敏MRPC原型及读出方法. 该探测器具有10个220μm气隙, 有效探测面积为20cm×20cm. 前端电子学采用专用ASIC芯片, 具有快时间响应和输入电荷-输出信号宽度的转换功能. 采取同时读取信号传输时间差和感应信号分布的方法实现两维读出. 对该探测器性能的束流测试结果显示: 沿着读出条方向及其垂直方向的位置分辨分别为4.5mm和1.6mm, 其时间分辨达到63ps, 探测效率>95%.     

The EPR Argument in a Relational Interpretation of Quantum Mechanics

It is shown that in the Rovelli relational interpretation of quantum mechanics, in which the notion of absolute or observer independent state is rejected, the conclusion of the ordinary EPR argument turns out to be frame-dependent, provided the conditions of the original argument are suitably adapted to the new interpretation. The consequences of this result for the peaceful coexistence of quantum mechanics and special relativity are briefly discussed.     

高分辨率间断有限元方法

间断有限元方法是集高分辨率有限差分方法和有限体积方法的优点发展起来的一种数值方法,在计算流体动力学问题上显示了优良的效能.利用守恒问题给出间断有限元方法的基本概念和过程,利用简单算例给出该方法的精度分析和限制器对精度的影响,并给出浅水波问题、交通流问题和波传播问题的数值模拟结果,进一步,综合评介该方法在椭圆、抛物、对流扩散、Hamilton-Jacobi方程、Navier-Stokes方程等的实际应用进展.     

The chaotic ball: An intuitive analogy for EPR experiments

Actual realisations of EPR experiments donot demonstrate non-locality. A model is presented that should enable non-specialists as well as specialists to understand how easy it is to find realistic explanations for the observations. The model also suggests new areas where realistic (hidden-variable) models can give valid predictions whilst quantum mechanics fails. It offers straightforward explanations for some anomalies that Aspect was unable to account for, providing perhaps the first experimental evidence that a hidden-variable theory can besuperior to quantum mechanics. The apparent success of quantum mechanics in predicting results is shown to be largely due to the use of unjustifiable and biased analysis of the data. Data that has been discarded because it did not lead to a valid Bell's test may give further evidence that hidden variables exist.     

Use of electron irradiation in studying thermal donors in silicon by the EPR method

The bistable thermal donors in Czochralski-grown silicon crystals were investigated by EPR spectroscopy and IR-absorption techniques. It is shown that using heat treatment at a temperature ≤400°C and appropriate conductivity compensation by irradiation with 3.5 MeV electrons, one can select from the total signal the EPR-signal associated with only one type, namely TDD2, of the thermal donors. Based on the model of a two-center core structure of the given complexes, an explanation of the EPR-spectroscopy data on the oxygen thermal donors in silicon is suggested. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 188–191, March–April, 2000.     

Separation and Enrichment of the Active Component of Carbon Based Paramagnetic Materials for Use in EPR Oximetry

Carbon based paramagnetic materials are frequently used for EPR oximetry, especiallyin vivo,but the EPR spectra of these materials often have more than one paramagnetic center and/or relatively low signal intensity. To determine whether the multi-components of carbon based materials could be separated and enriched in the active component, we used density gradient centrifugation to separate the materials into several fractions. We studied two types of coals, gloxy and Pocahontas, and found these materials to have large density distribution. The separated density fractions had very different EPR spectra and intensities. The active component from the coal material had a more homogeneous EPR signal and significantly increased EPR signal intensity, whereas for India ink, only slight changes were observed. This result can be very useful in the development of better probes for EPR oximetry.     

CCD对高空间分辨率波前干涉检测的影响

推导并用实验验证了光强与入射波前在单位像元面积里成近似线性关系,从而得到入射波前经CCD采样后的功率谱密度（PSD）公式.根据该公式,模拟分析了影响CCD采集系统的系统传递函数的各个因素：入射波前、CCD的填充因子及CCD的曝光时间,得出了他们与系统传递函数的定性关系,并且通过实验明确CCD曝光时间对高空间分辨率波前检测不确定度的影响,为高空间分辨率干涉设计提供了理论依据.     

The Limits of Common Cause Approach to EPR Correlation

It is often argued that no local common cause models of EPR correlation exist. However, Szabó and Rédei pointed out that such arguments have the tacit assumption that plural correlations have the same common causes. Furthermore, Szabó showed that for EPR correlation a local common cause model in his sense exists. One of his requirements is that common cause events are statistically independent of apparatus settings on each side. However, as Szabó knows, to meet this requirement does not entail that different combinations of common cause events (e.g. meet and join in lattice-theoretic terminology) are statistically independent of measurement settings. This further condition is formulated in two ways. First, the apparatus settings are completely independent of such combinations. Second, the apparatus settings on each side are independent of such combinations. Does a common cause model which meets the former and the latter respectively exist? This problem is considered. In particular, the latter version is Szabó’s and Rédei’s open problem. Negative answers are given to both versions.     

Estimation of mean and median pO2 values for a composite EPR spectrum

Electron paramagnetic resonance (EPR)-based oximetry is capable of quantifying oxygen content in samples. However, for a heterogeneous environment with multiple pO2 values, peak-to-peak linewidth of the composite EPR lineshape does not provide a reliable estimate of the overall pO2 in the sample. The estimate, depending on the heterogeneity, can be severely biased towards narrow components. To address this issue, we suggest a postprocessing method to recover the linewidth histogram which can be used in estimating meaningful parameters, such as the mean and median pO2 values. This information, although not as comprehensive as obtained by EPR spectral-spatial imaging, goes beyond what can be generally achieved with conventional EPR spectroscopy. Substantially shorter acquisition times, in comparison to EPR imaging, may prompt its use in clinically relevant models. For validation, simulation and EPR experiment data are presented.     

High Resolution MRI of Small Joints: Impact of Spatial Resolution on Diagnostic Performance and SNR

This study focuses on the spatial resolution required for cartilage imaging. The purposes of this study were (I) to analyze the diagnostic performance in diagnosing artificially produced cartilage lesions in a small joint model using an optimized fat saturated three-dimensional gradient-echo sequence, (II) to relate the lesion size and depth as diagnosed in the magnetic resonance images with the corresponding pathologic findings and (III) to assess signal-to-noise (SNR) ratios for each of the protocols. Twenty-five artificial cartilage lesions were created in the knee joints of 10 rabbits. These specimens and seven specimens without lesions were imaged at 1.5 T using a three-dimensional gradient-echo sequence with varying slice thickness, field of view and matrix. A total of 404 corresponding images were selected, 50% with and 50% without cartilage lesions. Six radiologists scored all images according to five levels of confidence and receiver operating characteristic (ROC) analysis was performed. Lesion size and depth were compared to the corresponding pathological specimen sections. Additionally SNR ratios were calculated. ROC analysis of pooled data from all readers showed the highest area under the ROC curve for the sequence with the highest spatial resolution, while the diagnostic performance was significantly lower in the other sequences (p <0.01). Assessment of the lesion size and depth was correct in 45% and 40% respectively with the highest resolution and in 29% and 23% with the lowest resolution. SNR ratios decreased with increasing spatial resolution. In conclusion this study shows that increasing spatial resolution improves diagnostic performance in cartilage lesions, though SNR decreases substantially. Assessment of correct lesion size and depth still is limited.     

A Method to Model the EPR Spectra of Paramagnetic Particles Exhibiting Anisotropy of the g Factor

A simple method for calculating the EPR spectra of paramagnetic particles with a triple anisotropy of the g factor, which precludes computation of elliptical integrals, is described. The possibilities of the method have been checked by comparing the spectra of the SO₂ ^– ion-radicals obtained in the process of thermolysis of dithionates of barium, strontium, and calcium sulfate whose spectra were calculated. The comparison shows a satisfactory agreement between the experimental and calculated spectra.     

提高布里渊光时域反射应变仪测量空间分辨力的等效脉冲光拟合法

由于探测光脉冲宽度受到限制,布里渊光时域反射仪(BOTDR)在对光纤上的应变进行分布式测量时,空间分辨力只能达到1 m。针对布里渊光时域反射仪单次采样接收背向布里渊散射信号(BBS)需要一定的时间,提出了基于等效脉冲光的多洛仑兹拟合法以提高其应变测量的空间分辨力。该方法将探测光脉冲在布里渊光时域反射仪完成单次采样所需的时间上进行积分,将积分函数作为等效脉冲光的表达式,再根据等效脉冲光的形状将布里渊光时域反射仪接收到的背向布里渊散射谱(BBS)细分,并对它进行多洛仑兹迭代拟合,准确求得每个细分布里渊散射谱的中心频率,进而利用光纤中布里渊频移与应变的对应关系,得到光纤中与细分布里渊散射谱对应的细分光纤单元上的应变情况。实验结果表明,利用这种方法,可使布里渊光时域反射仪应变测量的空间分辨力提高至0.05 m。     

高分辨分子吸收光谱中的波长校准方法

本文提出高分辨分子吸收光谱中，以碘分子谱作为参考标准的波长校准方法，编制了以人机交互方式自动完成波长校准的软件，并应用于16 422-17 896cm^-1可见光波段范围内的N2^ 分子离子的高分辨吸收谱线的波长校准，结果表明其绝对准确度可达0.006cm^-1。     

一种新型功能化双自由基的合成及EPR表征

新开发的双自由基(TN3)由全取代三苯甲基自由基(trityl)和氮氧自由基两部分组成.TN3的室温EPR谱图由4条不对称的宽谱线组成,具有典型的双自由基特征.以抗坏血酸作为模型化合物发现该双自由基能用来同时检测体系的氧化还原态和氧气浓度.