o-Semiquinonato and o-iminosemiquinonato rhodium complexes. EPR study of the reactions in coordination sphere of rhodium

Chemical exchange saturation transfer (CEST) processes in aqueous systems are quantified by evaluation of z-spectra, which are obtained by acquisition of the water proton signal after selective RF presaturation at different frequencies. When saturation experiments are performed in vivo, three effects are contributing: CEST, direct water saturation (spillover), and magnetization transfer (MT) mediated by protons bound to macromolecules and bulk water molecules. To analyze the combined saturation a new analytical model is introduced which is based on the weak-saturation-pulse (WSP) approximation. The model combines three single WSP approaches to a general model function. Simulations demonstrated the benefits and constraints of the model, in particular the capability of the model to reproduce the ideal proton transfer rate (PTR) and the conventional MT rate for moderate spillover effects (up to 50% direct saturation at CEST-resonant irradiation). The method offers access to PTR from z-spectra data without further knowledge of the system, but requires precise measurements with dense saturation frequency sampling of z-spectra. PTR is related to physical parameters such as concentration, transfer rates and thereby pH or temperature of tissue, using either exogenous contrast agents (PARACEST, DIACEST) or endogenous agents such as amide protons and -OH protons of small metabolites.     

基于CEST机制的pH成像方法、原理和应用

化学交换饱和转移（Chemical Exchange Saturation Transfer,CEST）技术作为一种新型的磁共振成像（Magnetic Resonance Imaging,MRI）技术.它的原理为溶质池中被激发饱和的质子与游离水中未被饱和的质子间的化学交换,能够引起水质子磁共振信号的下降,从而获得组织内生物分子的相关信息.由于质子间的交换速率k_ex与组织微环境的pH值之间存在直接联系,因而可以通过溶质质子的CEST信号对活体组织进行pH成像.目前用于pH成像的溶质分子既包括内源性游离的蛋白质、多肽分子,还包括一系列的外源性小分子和金属螯合物.通过不同类型的比率法、内源性胺和酰胺浓度-独立检测（Amine and Amide Concentration-independent Detection,AACID）等成像方法,能够获得肾脏、中风脑组织以及肿瘤组织的pH图谱.本文详细总结了2000年以来利用CEST技术进行pH成像方面的研究进展,包括对比剂、成像方法和相关应用,展望了活体组织pH成像的发展趋势和应用前景.     

Reaction pathway and H/D kinetic isotope effects of the triple proton transfer in a 7‐hydroxyquinoline‐methanol complex in the ground state: A computational approach

Multiple proton transfer (PT) is an essential process in long‐range proton transport such as proton relay in enzymes. 7‐Hydroxyquinoline (7HQ) undergoes alcohol‐mediated PT in both the excited and ground states, and this system has been investigated as a biomimetic model. In the present study, the reaction pathway of triple PT in a 7HQ‐methanol cluster, 7HQ·(MeOH)₂, in the ground state has been investigated using density functional theory calculations to clarify the reaction mechanism and the origin of the experimentally observed kinetic isotope effect (KIE). The PT takes place in an asynchronous concerted fashion, in which the oxygen atom in 7HQ first accepts a proton from the directly hydrogen‐bonded MeOH. The rate constants and primary H/D KIEs have been estimated with canonical variational transition state theory in combination with the small curvature tunneling approximation. The tunneling effect on the PT rate is significant, and the KIE is much greater than 1 at room temperature. The rule of the geometric mean for the KIEs breaks down because of the asynchronicity in the motions of 3 protons and tunneling effect. In addition, the rate constant is smaller, the KIE is larger, and the activation energy is higher compared with the experimental values in heptane solution, suggesting that the PT dynamics in solution is governed by not only the intrinsic PT process but also thermal fluctuation of the solute and solvent molecules, which plays an important role in the configurational change of the 7HQ·(MeOH)₂ complex.     

多肽和蛋白质NMR预饱和实验中饱和转移效应的研究

通过改变预饱和照射时间研究了一些多肽和蛋白质分子在水溶液中的饱和转移效应.定量分析了在照射60s之后大分子中绝大多数酰胺质子仍不受影响的原因.结果表明:具有稳定的三维溶液结构的蛋白质(如溶菌酶)中,活泼氢的信号基本上不受饱和转移影响;对于溶液结构比较稳定的多肽和蛋白质(如胰岛素),只有少部分酰胺质子信号强度受到影响;小分子六肽因为溶液中不存在稳定的构象,饱和转移效应十分显著.因此对于溶液中多肽与蛋白质构象的NMR研究,预饱和仍不失为一种简便而有效的溶剂峰压制技术.     

Z-spectroscopy with Alternating-Phase Irradiation

Magnetization transfer (MT) MRI and Z-spectroscopy are tools to study both water-macromolecule interactions and pH-sensitive exchange dynamics between water and the protons of mobile chemical groups within these macromolecules. Both rely on saturation of frequencies offset from water and observation of the on-resonance water signal. In this work, an RF saturation method called Z-spectroscopy with Alternating-Phase Irradiation (ZAPI) is introduced. Based on the T(2)-selectivity of the irradiation pulse, ZAPI can be used to separate the different contributions to a Z-spectrum, as well as to study the T(2) distribution of the macromolecules contributing to the MT signal. ZAPI can be run at resonance for water and with low power, thus minimizing problems with specific absorption rate (SAR) limits in clinical applications. In this paper, physical and practical aspects of ZAPI are discussed and the sequence is applied in vitro to sample systems and in vivo to rat head to demonstrate the method.     

Magnetization transfer contrast (MTC) in FLASH MR imaging

Magnetization transfer between bound and free protons was used as a source of contrast in high speed MR imaging using the FLASH technique. Contrast in FLASH MR images was found to depend upon the reduced magnetization and the spin lattice relaxation rate of free protons in the presence of bound proton radio-frequency saturation. MTC FLASH imaging was thus used to estimate the variation with saturation frequency of free proton spin-lattice relaxation during magnetization transfer.     

Complete relaxation and conformational exchange matrix (CORCEMA) analysis of intermolecular saturation transfer effects in reversibly forming ligand-receptor complexes

A couple of recent applications of intermolecular NOE (INOE) experiments as applied to biomolecular systems involve the (i) saturation transfer difference NMR (STD-NMR) method and (ii) the intermolecular cross-saturation NMR (ICS-NMR) experiment. STD-NMR is a promising tool for rapid screening of a large library of compounds to identify bioactive ligands binding to a target protein. Additionally, it is also useful in mapping the binding epitopes presented by a bioactive ligand to its target protein. In this latter application, the STD-NMR technique is essentially similar to the ICS-NMR experiment, which is used to map protein-protein or protein-nucleic acid contact surfaces in complexes. In this work, we present a complete relaxation and conformational exchange matrix (CORCEMA) theory (H. N. B. Moseley et al., J. Magn. Reson. B 108, 243-261 (1995)) applicable for these two closely related experiments. As in our previous work, we show that when exchange is fast on the relaxation rate scale, a simplified CORCEMA theory can be formulated using a generalized average relaxation rate matrix. Its range of validity is established by comparing its predictions with those of the exact CORCEMA theory which is valid for all exchange rates. Using some ideal model systems we have analyzed the factors that influence the ligand proton intensity changes when the resonances from some protons on the receptor protein are saturated. The results show that the intensity changes in the ligand signals in an intermolecular NOE experiment are very much dependent upon: (1) the saturation time, (2) the location of the saturated receptor protons with respect to the ligand protons, (3) the conformation of the ligand-receptor interface, (4) the rotational correlation times for the molecular species, (5) the kinetics of the reversibly forming complex, and (6) the ligand/receptor ratio. As an example of a typical application of the STD-NMR experiment we have also simulated the STD effects for a hypothetical trisaccharide bound to a protein. The CORCEMA theory for INOE and the associated algorithm are useful in a quantitative interpretation of the intensity changes in the ligand in both the STD-NMR and ICS-NMR, provided the identity of the receptor protons experiencing direct RF saturation is known. The formalism presented here is likely to be useful in the design of bioactive ligands to a specific target protein and in the quantitative mapping of binding epitopes and interfaces between molecules in complexes.     

3 MeV质子辐照对AlGaN/GaN高电子迁移率晶体管的影响

研究了AlGaN/GaN 高电子迁移率晶体管(HEMT)的质子辐照效应. 在3 MeV质子辐照下, 当辐照剂量达到1× 10¹⁵ protons/cm²时, 漏极饱和电流下降了20%, 最大跨导降低了5%. 随着剂量增加, 阈值电压向正向漂移, 栅泄露电流增加. 在相同辐照剂量下, 1.8 MeV质子辐照要比3 MeV质子辐照退化严重. 从SRIM软件仿真中得到不同能量质子在AlGaN/GaN异质结中的辐射损伤区, 以及在一定深度形成的空位密度. 结合变频C-V测试结果进行分析, 表明了质子辐照引入空位缺陷可能是AlGaN/GaN HEMT器件电学特性退化的主要原因.     

Measurement of APT using a combined CERT-AREX approach with varying duty cycles

The goal is to develop an imaging method where contrast reflects amide-water magnetization exchange, with minimal signal contributions from other sources. Conventional chemical exchange saturation transfer (CEST) imaging of amides (often called amide proton transfer, or APT, and quantified by the metric MTR_asym) is confounded by several factors unrelated to amides, such as aliphatic protons, water relaxation, and macromolecular magnetization transfer. In this work, we examined the effects of combining our previous chemical exchange rotation (CERT) approach with the non-linear AREX method while using different duty cycles (DC) for the label and reference scans. The dependencies of this approach, named AREX_double,vdc, on tissue parameters, including T₁, T₂, semi-solid component concentration (f_m), relayed nuclear Overhauser enhancement (rNOE), and nearby amines, were studied through numerical simulations and control sample experiments at 9.4 T and 1 μT irradiation. Simulations and experiments show that AREX_double,vdc is sensitive to amide-water exchange effects, but is relatively insensitive to T₁, T₂, f_m, nearby amine, and distant aliphatic protons, while the conventional metric MTR_asym, as well as several other APT imaging methods, are significantly affected by at least some of these confounding factors.     

GEANT4SPE质子屏蔽和半导体材料辐射效应模拟

利用蒙特卡罗软件GEANT4模拟太阳宇宙射线中能量为1 MeV~10 GeV质子对航天飞行器的影响,透射质子对半导体材料的损伤效应,计算外壳铝层对质子能谱的屏蔽效应.模拟结果表明,质子在介质中的线性能量转移、射程等和参考数据吻合较好;沿质子轨迹纵向能量沉积出现Bragg峰,且非弹性作用是影响能量沉积Bragg曲线的重要因素;对于半导体Si材料,反冲原子主要分布在质子轨迹线周围,并沿轨迹线横向‘扩散’,浓度降低;Al层屏蔽使入射质子能谱硬化,当Al层厚度超过10 mm时,厚度增加对屏蔽效果的改善不明显,反而次级粒子辐射增强效应变大.     

质子辐照对国产“一”字型保偏光纤损伤效应研究

航天器在空间环境中运行时,会受到质子的辐照,光纤环作为航天器上光纤陀螺的重要组成部件受辐照影响 最为严重.为了研究国产“一”字型保偏光纤因质子辐照导致辐照诱导损耗的变化规律及其辐照损伤机理, 选择质子能量为5 MeV和10 MeV,光源波长为1310 nm,原位测量了光纤传输功率变化情况,计算出辐照诱导损耗. 利用SRIM软件,模拟能量分别为5 MeV和10 MeV质子辐照在光纤中的电离和位移损伤分布.借助X 射线光电子能谱仪分析辐照前后O 1s和Si 2p解析谱,借助傅里叶变换红外光谱仪观察光纤辐照前后光谱变化情况研究发现,在波长为1310 nm处, 光纤的辐照诱导损耗随着质子注量的增加而增长,主要原因是由于光纤纤芯中Si-OH的浓度增加所导致. 而且能量为5 MeV质子辐照造成光纤的辐照诱导损耗比10 MeV严重,这是因为5 MeV质子在光纤纤芯处造成的 位移和电离损伤均比10 MeV严重,即产生的Si-OH数量多.     

Concerted versus stepwise mechanisms of cyclic proton transfer: Experiments,simulations, and current challenges

Proton transfer (PT) is a process of fundamental importance in hydrogen (H)-bonded systems. At cryogenic or moderate temperatures, pronounced quantum tunneling may happen due to the light mass of H. Single PT processes have been extensively studied. However, for PT involving multiple protons, our understanding remains in its infancy stage due to the complicated interplay between the high-dimensional nature of the process and the quantum nature of tunneling. Cyclic H-bonded systems are typical examples of this, where PT can happen separately via a "stepwise" mechanism or collectively via a "concerted" mechanism. In the first scenario, some protons hop first, typically resulting in metastable intermediate states (ISs) and the reaction pathway passes through multiple transition states. Whilst in the concerted mechanism, all protons move simultaneously, resulting in only one barrier along the path. Here, we review previous experimental and theoretical studies probing quantum tunneling in several representative systems for cyclic PT, with more focus on recent theoretical findings with path-integral based methods. For gas-phase porphyrin and porphycene, as well as porphycene on a metal surface, theoretical predictions are consistent with experimental observations, and enhance our understanding of the processes. Yet, discrepancies in the PT kinetic isotope effects between experiment and theory appear in two systems, most noticeably in water tetramer adsorbed on NaCl (001) surface, and also hinted in porphycene adsorbed on Ag (110) surface. In ice I_h, controversy surrounding concerted PT remains even between experiments. Despite of the recent progress in both theoretical methods and experimental techniques, multiple PT processes in cyclic H-bonded systems remain to be mysterious.     

Radiation effects of 50-MeV protons on PNP bipolar junction transistors

The effects of radiation on 3CG110 PNP bipolar junction transistors (BJTs) are characterized using 50-MeV protons, 40-MeV Si ions, and 1-MeV electrons. In this paper, electrical characteristics and deep level transient spectroscopy (DLTS) are utilized to analyze radiation defects induced by ionization and displacement damage. The experimental results show a degradation of the current gain and an increase in the types of radiation defect with increasing fluences of 50-MeV protons. Moreover, by comparing the types of damage caused by different radiation sources, the characteristics of the radiation defects induced by irradiation show that 50-MeV proton irradiation can produce both ionization and displacement defects in the 3CG110 PNP BJTs, in contrast to 40-MeV Si ions, which mainly generate displacement defects, and 1-MeV electrons, which mainly produce ionization defects. This work provides direct evidence of a synergistic effect between the ionization and displacement defects caused in PNP BJTs by 50-MeV protons.     

Simultaneous determination of labile proton concentration and exchange rate utilizing optimal RF power: Radio frequency power (RFP) dependence of chemical exchange saturation transfer (CEST) MRI

Chemical exchange saturation transfer (CEST) MRI is increasingly used to probe mobile proteins and microenvironment properties, and shows great promise for tumor and stroke diagnosis. However, CEST MRI contrast mechanism is complex, depending not only on the CEST agent concentration, exchange and relaxation properties, but also varying with experimental conditions such as magnetic field strength and RF power. Hence, it remains somewhat difficult to quantify apparent CEST MRI contrast for properties such as pH, temperature and protein content. In particular, CEST MRI is susceptible to RF spillover effects in that RF irradiation may directly saturate the bulk water MR signal, leading to an optimal RF power at which the CEST contrast is maximal. Whereas RF spillover is generally considered an adverse effect, it is noted here that the optimal RF power strongly varies with exchange rate, although with negligible dependence on labile proton concentration. An empirical solution suggested that optimal RF power may serve as a sensitive parameter for simultaneously determining the labile proton content and exchange rate, hence, allowing improved characterization of the CEST system. The empirical solution was confirmed by numerical simulation, and experimental validation is needed to further evaluate the proposed technique.     

The effect of interaction time and saturation of rock on specific energy in ND:YAG laser perforating

Laser perforating in oil and gas wells is a new scientific approach to the generation of uniform holes at a selected pitch to increasing the permeability of rocks. The influence of laser irradiation time and rock saturation by water and heavy oil on the specific energy, the energy required to remove the unit weight of rock, used during Nd:YAG laser perforating. The results show that an increase in the laser irradiation time increases the depth of the rock hole as well as the specific energy used, with a nonlinear relationship. Here, the estimated equation of rate of penetration as a function of the specific energy (SE) is free from saturation effects. The type of saturation influences the specific energy; the amount of SE required for water saturated samples is more than that required for the heavy oil saturated samples, and heavy oil saturated samples needed more SE than the dry samples.     

纳米静态随机存储器低能质子单粒子翻转敏感性研究

针对65, 90, 250 nm三种不同特征尺寸的静态随机存储器基于国内和国外质子加速器试验平台, 获取了从低能到高能完整的质子单粒子翻转截面曲线. 试验结果表明, 对于纳米器件1 MeV以下低能质子所引起的单粒子翻转截面比高能质子单粒子翻转饱和截面最高可达3个数量级. 采用基于试验数据和器件信息相结合的方法, 构建了较为精确的复合灵敏体积几何结构模型, 在此基础上采用蒙特卡罗方法揭示了低能质子穿过多层金属布线层, 由于能量岐离使展宽能谱处于布拉格峰值的附近, 通过直接电离方式将能量集中沉积在灵敏体积内, 是导致单粒子翻转截面峰值的根本原因. 并针对某一轨道环境预估了低能质子对空间质子单粒子翻转率的贡献.     

In vivo magnetic resonance study of the histochemistry of coconut (Cocos nucifera)

Magnetic resonance imaging (MRI) and localized proton MR spectroscopy (MRS) techniques have been applied for studying different maturation processes in the histochemistry of coconut (Cocos nucifera). Images of the tender and mature coconut are characterized by protons of the aqueous solution present in the cavity and from the surrounding pulp, whereas the image of the dry coconut is from the protons of the fat present in the pulp. Localized proton MR spectra of the water present in the cavity from the tender and the mature coconut show several resonances due to different chemical constituents of coconut water, whereas typical spectra of the pulp from dry coconut reveal a profile of the hydrogens present in the saturated and unsaturated fatty acid chains. In addition, images obtained from a rancid coconut show the extent of internal damage and degradation due to fungal growth; the corresponding localized MR spectra of the coconut water reveal that several proton resonances are absent.     

CMOS图像传感器在质子辐照下热像素的产生和变化规律

应用于空间的图像传感器在辐射影响下产生的热像素严重影响空间光电探测性能,本文通过质子辐照试验研究了热像素的产生和变化规律。首先,使用3 MeV和10 MeV两种能量的质子对图像传感器进行辐照,分析不同能量、不同注量的质子辐照产生热像素的性质;其次,再对辐照后的器件进行退火试验,分析热像素的退火规律。对于相同注量辐照,3 MeV质子辐照下热像素产生率大约是10 MeV质子辐照下的2.3倍,但是10 MeV质子辐照产生热像素的灰度值高于3 MeV质子;辐照过程中热像素的数量都是随着注量的增加线性增加。退火过程中,热像素数量都不断减少,而3 MeV质子辐照产生的热像素相比于10 MeV质子,退火更为显著。结果表明,质子辐照下每个质子与器件之间的作用过程及产生缺陷的机制是相对独立的,不同质子的作用过程之间没有相关性。不同能量的质子辐照产生缺陷的类型不同,导致热像素具有不同特性。     

用于激光加速质子参数表征的带电粒子活化测谱技术

基于传统带电粒子活化分析技术,发展了一种用于激光加速质子参数表征的带电粒子活化测谱方法.激光加速质子轰击不同厚度铜薄膜组成的诊断滤片堆栈,使铜片活化,通过测量各铜片活度及活性区的大小,获得加速质子的空间积分能谱、角分布等参数.详细讨论了活化测谱的滤片堆栈诊断排布、符合测量及解谱方法,并对该方法的可靠性进行了自洽检验;在XG-III皮秒激光装置上开展了带电粒子活化测谱实验,利用该诊断方法,得到了加速质子的角分布、空间积分能谱等参数,实验获得的质子最高截止能量18 MeV,激光能量到质子(4 MeV)的转换效率为1.07%.     

170keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响

碳纳米管具有优异的导电性, 是未来电子元器件的理想候选材料, 应用前景广阔. 针对碳纳米管在空间电子元器件的应用需求, 本文研究了170 keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响. 采用扫描电子显微镜(SEM)、拉曼光谱仪(Raman)、X射线光电子能谱仪(XPS)及电子顺磁共振谱仪(EPR)对辐照前后碳纳米管试样的表面形貌和微观结构进行分析; 利用四探针测试仪对碳纳米管薄膜进行导电性能分析. SEM分析表明, 170 keV质子辐照条件下, 当辐照注量高于5×10¹⁵ p/cm² (protons/cm²)时, 碳纳米管薄膜表面变得粗糙疏松, 纳米管发生明显弯曲、收缩及相互缠结现象. 目前, 质子辐照纳米管发生的收缩现象被首次发现. 基于Raman和XPS分析表明, 170 keV质子辐照后碳纳米管的有序结构得到改善, 且随辐照注量增加, 碳纳米管的有序结构改善明显. 结构的改善主要是由于170 keV质子辐照碳纳米管所产生的位移效应导致缺陷重组. EPR分析表明, 随着辐照注量的增加, 碳纳米管薄膜内的非局域化电子减少. 利用四探针测试分析表明, 碳纳米管薄膜的导电性能变差, 这是由于170 keV质子辐照导致碳纳米管薄膜中的电子特性及形态发生改变. 本文研究结果有助于利用质子辐照对碳纳米管膜结构和性能进行调整, 从而制备出抗辐射的纳米电子器件.