细胞内蛋白质磁共振

细胞内的环境异常复杂,其中生物大分子的浓度超过300 mg/mL并占据着大约30%的细胞内空间. 然而,直到目前为止大多数的蛋白质研究仍然在细胞外或是甚至非常稀的缓冲液中进行. 细胞内磁共振（In-cell NMR）提供了一个可以直接非损伤地获取细胞内原子水平信息的方法. 虽然In-cell NMR在近10年里有了较大的发展,但是这一技术尚未成熟. 在该篇综述中,作者首先总结制约这一技术发展的因素以及研究中需要注意的事项,最后讨论了未来的发展方向.     

Electrical Mobility Magnetic Resonance Spectroscopy (EMMRS)

A method to determine electrical mobility of charge carriers containing paramagnetic elements is presented. The motion-induced phase shift of the transverse magnetization component is observed by magnetic (nuclear or electron) resonance (MR). In fluid media, this method can determine the type of carriers and respective motion, lifetimes distribution, thermal and frequency dispersion of the mobility, translational relaxation rate and activation energies of these processes.

     

Nuclear Magnetic Resonance Spectroscopy Study of a Disaccharidic Crown Ether.

Abstract

The disaccharidic anhydro derivative 6-O-(5,6-anhydro-3-deoxy-1,2-O-isopropylidene α-D-glucofuranos-3-yl)-1,2-O-isopropylidene-3-O-n-dodecyl-α-D-glucofuranose (1) led to the disaccharidic crown ether 2 in 40% yield when treated at low concentration with 2.5 eq. of KOH in toluene-Me₂SO. Compound 2 structure was proved through a detailed NMR analysis (¹H, ¹³C, ¹H-¹H and ¹³C-¹H 2D correlations). This structural elucidation indicated that compound 2 resulted from the intramolecular attack of the C-5-O^?alkoxide group, generated in the basic medium, on the C-6′ carbon of the 5′,6′-anhydro group.     

An Overview of 195Pt Nuclear Magnetic Resonance Spectroscopy

Abstract

This brief, non‐exhaustive review describes some basic theoretical aspects of ¹⁹⁵Pt nuclear magnetic resonance spectroscopy and also the empirical approach used by the researchers in the field. The different factors which influence the chemical shifts are discussed. The couplings constants between ¹⁹⁵Pt and other isotopes, which have a spin of 1/2 (such as, ¹H and ¹³C) bring further important information on the structures of Pt compounds. Recently, ¹⁹⁵Pt‐NMR spectroscopy in the liquid state has been used successfully in many research fields, e.g., the determination of enantiomeric composition and absolute configuration, in the area of biosensors and biomarkers, in cluster chemistry, in cancer research and in kinetic studies. While liquid‐state ¹⁹⁵Pt‐NMR spectroscopy encompasses a wide range of areas, the parallel solid‐state technique has only been employed over the past few years, mainly in studies of heterogeneous catalysis and is more industrially oriented.     

1.5T关节超导核磁共振成像主磁体电磁机械特性分析

本文设计了用于关节成像的1.5T超导核磁共振成像(MRI)主磁体的电磁结构与机械支撑结构.首先计算了主磁体成像区域及磁体周围的电磁场分布.在此基础上,采用电磁-结构耦合方法计算了主磁体与支撑结构中的应力、应变分布情况.同时分析了不同的支撑材料对磁体应力/应变的影响.给出了1.5T超导MRI主磁体支撑结构的设计标准.     

Characterization of Copper-Modified ZSM-5 with Sorbed Pyridine Using Nuclear Magnetic Resonance Spectroscopy

Solid-state ¹H, ¹³C and ²⁹Si MAS NMR experiments were used to detect sorbed pyridine in hydrated copper-exchanged forms of synthetic zeolite ZSM-5, which is widely used in industry and green chemistry as well. The paper follows on from the previous study of sorption of organic pollutants by copper-modified forms of ZSM-5. Multinuclear MAS NMR experiments performed on hydrated and dehydrated copper-exchanged ZSM-5 samples with sorbed pyridine indicate that dissociation of water molecules in the vicinity of copper cations results in formation of new acid sites in the zeolite channels. Through their reaction with sorbed pyridine molecules, pyridinium ions are formed. ¹³C MAS NMR spectra also confirmed the presence of pyridine molecules not involved in forming pyridinium ions in the copper-modified ZSM-5 samples. From the changes in ²⁹Si NMR spectra, some slight changes in the structure of original copper-modified ZSM-5 after pyridine sorption can be also deduced.     

Wide-Line Nuclear Magnetic Resonance Spectroscopy of Sulfur-33 in Minerals

Abstract

Nuclear magnetic resonance spectra of ³³S in solid samples were obtained for the first time. Although the natural abundance of ³³S is quite low (0.74 percent), good signals were obtained for sphalerite (ZnS) and pyrrhotite (Fe_1?xS). In addition, separate signals were obtained for the first time for a binary mixture of sulfur compounds (sulfur dissolved in liquid CS₂).     

Whole-body T2* mapping at 1.5 T

This study investigated the feasibility of an MRI protocol providing whole-body T2* maps at 1.5 T. Seven healthy volunteers (mean age=30.1+/-3.7, three women and four men) and two patients (both male, 53 and 46 years old) affected by transfusion-dependent anemias participated in the study. Coronally oriented images of five subsequent body levels were acquired using a fat-suppressed multiecho 2D gradient-echo sequence (12 echo times ranging from 4.8 to 76.3 ms were selected) and afterwards composed. Parametrical T2* maps of the whole body were reconstructed on a pixel-by-pixel basis. For both, healthy volunteers and patients, representative T2* values were computed from extended regions of interest (ROIs). Good-quality whole-body T2* maps were computed in all volunteers and patients. In healthy volunteers, T2* values were assessed in the cerebral white (58.5+/-4.2 ms) and gray (81.4+/-5.5 ms) matter, liver (34.3+/-7.0 ms), spleen (63.5+/-3.3 ms), kidneys (65.4+/-10.3 ms) and skeletal muscles (~30 ms). The liver presented faster relaxation rates in males as compared to females. One patient (serum ferritin concentration=927 microg/dl) showed shortened T2* values in liver (3.6+/-5.5 ms), spleen (3.1+/-4.8 ms), kidneys (11.1+/-7.1 ms) and muscles (25.1+/-3.4 ms). The second patient (serum ferritin concentration=346 microg/dl) presented reduced T2* values in liver (3.9+/-7.3 ms), spleen (20.1+/-9.8 ms) and kidneys (24.6+/-7.7 ms). The presented technique may find clinical application in the assessment of the iron burden in the entire body, and in monitoring of chelation therapies in patients treated with frequent blood transfusions.     

Gd-DTPA adrenal gland enhancement at 1.5 T

The change in relative signal intensity of normal adrenal glands in 31 patients was evaluated following bolus administration of 0.1 mmol/kg of gadolinium diethylenetriamine pentacetic acid (Gd-DTPA). A marked increase in relative intensity of greater than 300% was observed within 2.5 min following contrast administration upon comparison of pre- and postcontrast T1-weighted gradient-echo images (TR = 47 msec, TE = 13 msec, pulse angle 80 degrees). Significantly elevated relative intensities of 55% and 44% persisted on postcontrast T1-weighted spin-echo images obtained at further delay times averaging 8 and 20 min, respectively, when compared to the identical precontrast sequence.     

远红外激光磁共振光谱技术及对含碳自由基分子的观测

本文报道国内建成的远红外激光磁共振 (FIRLMR)光谱仪的技术特点和工作原理。该谱仪采用CO2 激光横向泵浦远红外激光 ,样品吸收池置于远红外激光谐振腔内 ,由聚丙烯薄膜与远红外激光增益池隔开以获得很高的灵敏度 ,从而对寿命很短的自由基分子进行研究。利用该光谱仪在远红外波段测量得到了多个瞬态自由基分子CCH ,CF和CH2 的光谱 ,这些自由基分子由微波放电产生的氟原子与甲烷CH4 反应生成。     

Increased Posterior Cingulate Glutamate and Choline Measured by Magnetic Resonance Spectroscopy in Hypothyroidism

Patients with hypothyroidism always suffer from neuropsychiatric symptoms such as lack of concentration, anxiety, and depression. Recent studies show that the glutamatergic system is the key part to neuropsychiatric accommodation, although the fundamental process of the dysfunction is not well understood. Therefore, our study is devoted to investigate the change of brain metabolisms by focusing on glutamate concentration in patients with hypothyroidism. Using proton magnetic resonance spectroscopy, we try to find out the possible correlation between hypothyroidism and glutamatergic system. Twenty-one untreated hypothyroidism patients and 21 age- and gender-matched controls were included in this study. Posterior cingulate cortex is the region of interest and was examined by magnetic resonance spectroscopy with a technique referred as TE-averaged PRESS at 3T field strength. The intensity of glutamate, choline, N-acetylaspartate and creatine was assessed utilizing jMRUI v4.0 software. Hypothyroid patients showed an increase of glutamate (p = 0.013) and choline (p = 0.01) in the posterior cingulate cortex compared with controls. Signal intensity of glutamate and choline increased in the region of the posterior cingulate cortex in patients with hypothyroidism. This change indicated a potential role of glutamate in the brain dysfunction in hypothyroidism, and a possible immunological mechanisms effect on Cho’s level.     

X射线光电子能谱与13C核磁共振在生物质碳表征中的应用

近年来,生物质碳(biochar)作为新型吸附剂被广泛研究。但由于制备biochar的生物质原料和热解温度的不同,使biochar的结构和组成存在差异,从而影响其对污染物的吸附。目前关于biochar的结构和组成的研究还不够全面。因此,结合了能谱与光谱分析的手段,对biochar的结构和组成进行了深入的分析。选取木质类(柳树枝条)和草类(水稻秸秆)作为原料,分别在不同热解温度(300,450和600℃)下制得biochars,并对biochars样品进行元素分析、X射线光电子能谱分析(XPS)和固态13 C核磁共振(13 C NMR)研究,以阐明不同热解温度和生物质来源的biochars的结构和组成。结果显示:biochar的H/C,O/C和(O+N)/C的比值随着热解温度的升高而降低;草类biochar比木质类biochar具有更高的灰分含量和表面极性;木质类biochar的矿物主要分布在样品颗粒内部,其表面被有机质覆盖,而草类biochar部分矿物暴露在样品颗粒表面;13 C NMR显示低温制得的biochar主要由芳香碳、脂肪碳、羧基和羰基碳组成,高温制得的biochar主要由芳香碳组成,且低温制得biochars中,木质类biochars比草类biochars含有更高的木质素的残留碳结构,这是由于木质类biochars原材料中含有更高的木质素。     

Radiation-damping effects in a birdcage resonator with hyperpolarised 3He gas NMR at 1.5 T

The presence and diagnosis of radiation damping could have major implications in NMR experiments with hyperpolarised gases, where accurate knowledge of the flip angle is imperative. In this work radiation damping was observed and investigated in a low-pass birdcage resonator (Q=250) with samples of hyperpolarised 3He at 1.5 T. With an initially highly polarised (P=38%) sample of 3He in a spherical cell, the observed FID had a distorted line shape with a spectral line width that was three times that of the same sample in a virtually depolarised state (1 Hz line width for P<1%). Moreover a linear relation between the sample's magnetisation (M0) and the line width of the spectrum was observed which is indicative of radiation damping. With highly polarised samples, significant radiation damping was observed and the effect was a lower than expected rate of depletion of M0 in RF flip angle calibration experiments, which led to significant underestimate of the RF flip angle. To our knowledge this is the first report of radiation damping in a birdcage resonator with samples hyperpolarised or otherwise. Experimental observation of radiation damping could be used as means of measuring coil efficiency as an alternative to the geometrical filling factor (eta) the definition of which is open to question for a birdcage resonator. Estimates of the birdcage filling factor from the measured damping time constants (eta(RD)=0.4%) are compared to those derived from electromagnetic energy ratios (eta(E)=1.6%) and metallic sphere frequency shift methods (eta(fs)=1.4%). These figures are much lower than the simple volume geometrical upper limit of eta(v)=3.7% derived from the ratio of cell volume to total coil volume (shield included). The physical explanation for this shortfall is that the bulk of the magnetic energy stored in the birdcage is spatially distributed predominantly between the rungs and the shield, and not in the coil centre where the sample is placed and where the B1+ field has its highest spatial homogeneity.     

Chemical Applications of Nuclear Magnetic Resonance at High Fields

Abstract

A review confined to nuclear magnetic resonance measurements in a particular field-strength range needs some justification. Although the advent of the superconducting magnet in NMR presents quite novel problems for the spectrometer designer, and involves the user in some new operating techniques, the jump from 100 MHz (for proton resonances) to 220 MHz does not involve any new form of spectroscopy, any more than did the earlier advances from 40 MHz to 60 MHz, and thence to 100 MHz. The advantages in spectrometer performance which result from using a superconducting magnet are of degree, not of kind, and one is not called upon to learn anything new about NMR in order to interpret the spectra; indeed, the effect in many cases is to simplify the interpretation, so that a sophisticated quantum-mechanical approach is less often needed.     

Raman磁共振谱中强单量子信号的压抑

通常单量子信号的强度在Raman磁共振谱中要比其它多量子信号的强度大得多,因而易引起接收机饱和,使信号发生变形,不利于多量子信号的检测,因此压抑强的单量子峰是必要的.积算符理论分析表明,异核体系Raman磁共振谱的单,多量子峰的共振频率及其信号强度关于频偏满足对称关系:当频偏由正变为负时,单量子信号的强度亦随之改变了符号.因此,对正负频偏(数值相等)的两次Raman磁共振实验的FID信号进行累加,就可压抑强的单量子峰,而对于多量子峰则在大的频偏条件下不会相互抵消.因此,这样的实验累加可以保持多量子信号的强度而压抑掉强的单量子峰.作为实验验证,我们给出了异核AX_n体系(CHCl₃,CH₂Cl₂,CH₃OH)的按上述正负频偏循环累加采样方法得到Raman磁共振¹³C实验谱.实验结果同理论预言完全一致.     

Selected States Magnetic Resonance Spectroscopy (SSMRS): Detection of Paramagnetic Element Dynamics

Abstract

Magnetic resonance (MR) response obtained in a strongly heterogeneous magnetic field with a linear gradient is analysed. It is shown that the employment of strong magnetic field gradients enables the MR spectroscopy to be accomplished in a system with selectively populated energy states (SSMRS). The method can be applied for measuring such physical quantities as the spin diffusion coefficient, D, spin-lattice, T_1m and spin-spin, T_2m, relaxation times and mobility, p_m, of paramagnetic elements in individual Zeeman energy states.