自主研制核磁共振波谱仪的性能评估

主要介绍自主研制500 MHz核磁共振谱仪的性能评估情况,旨在建立一台功能完整的核磁共振波谱仪. 首先利用系统调试使控制台各个硬件单元在用户软件控制下实现NMR实验中的基本功能,然后通过性能测试保障功率线性度、信号稳定性和场频联锁的可靠性,实验验证了谱仪溶剂峰压制的效果,并获得良好的探头线形指标（0.43/5.46/10.73 Hz）和¹H灵敏度指标（信噪比为728∶1）,表明自主研制500 MHz核磁共振波谱仪系统能够满足常规核磁共振实验需求.     

核磁共振高信噪比弱信号检测的理论与实验研究

基于小型射频线圈的核磁共振检测探头在波谱分析和成像研究中具有广泛的应用,如化学位移波谱分析、磁共振成像和勘探测井等技术领域。但是,由于外加静磁场作用下,自旋体系发生塞曼能级分裂后,高低能态之间的核自旋数量之差很小,普遍存在检测信噪比很低的问题,而且初级磁共振接收信号的质量受所用探头线圈电气参数的影响较大。研究结果表明,在特定的被测样品和接收线圈占空比以及静磁场等条件不变的情况下,检测信噪比与单位电流产生的射频磁场成正比,而与线圈高频电阻的平方根成反比。在永磁0.39Tesla主磁场条件下,研究了趋肤效应影响下小型螺线管线圈几何参数的优化设计方法。理论仿真和实际的测量结果表明,几何参数为线径0.5 mm、直径5.5 mm的10匝微螺线管线圈,在16.9 MHz谐振频率上,相对信噪比取得一个极大值点,对应的Q值约为199.8,与阻抗分析仪测得结果有较好的吻合,验证了该核磁共振检测线圈设计新方法是合理的。本文提出的基于线圈电磁特性的高信噪比检测探头设计方法,可推广到目前的质子密度成像、岩心弛豫谱分析等应用中。     

基于FPGA的低场核磁共振谱仪脉冲编程器设计与实现

脉冲编程器在核磁共振(NMR) 谱仪中非常重要,具有产生脉冲序列所需的射频脉冲,控制回波信号的同步接收等功能. 基于FPGA的同步性能和时序控制功能,设计了低场NMR谱仪的脉冲编程器,可产生任意脉冲序列,实现脉冲频率、相位、幅度的灵活调节. 利用设计的脉冲编程器在0.540 Tesla均匀磁场下进行了CuSO₄溶液的T₁和T₂测量,得到高信噪比的NMR回波串.     

微波顺磁共振实验的若干改进

微波顺磁共振实验是近代物理实验中的基本实验之一。近年来我们吸取了兄弟院校开设这个实验的宝贵经验,经过反复试验,对这个实验作了以下几个方面的改进。(1)关于微波源一些实用的电子顺磁共振波谱仪有比较复杂的稳频装置,以及较高的灵敏度。北京大学董太乾的调频调场式电子顺磁共振波谱仪作了一项很大的革新,用调频方法省去了稳频装置,直接接收代替了外差接收,灵敏度也比较高,而且比前面提到的那类波谱仪简单。华中师院龙传安等的“电子顺磁共振”实     

场效应管核电四极共振谱仪

本文描述了一台场效应管超再生核四极共振谱仪的工作原理和性能;谱仪的振荡检波级是作者研制的一个频率覆盖范围较宽、灵敏度较高的场效应管(FET)超再生振荡检波器。文中还给出用本谱仪显示、记录的部分化学样品中的³⁵Cl核和³⁷Cl核的核四极共振(NQR)谱,并对使用场效应管的超再生振荡检波器的灵敏度作初步探讨。     

基于压缩感知/重采样的NMR噪声抑制新方法

发展高灵敏检测方法是分析化学的永恒主题之一,提高信号强度和降低噪声水平是增强灵敏度的根本途径.在核磁共振波谱(NMR)分析中,通常采用高磁场强度的谱仪或复杂的脉冲实验方法来提高信号强度,或通过使用超低温探头来降低噪声水平,但这无疑会提高实验成本或增加实验难度.相较而言,利用数据后处理方法辨识和抑制噪声,是更为经济的提高信噪比(SNR)的途径.因此,该文在前期研究中发展的基于统计学中重采样原理的数据后处理方法(NASR)的基础上,通过引入压缩感知(CS)技术,对重采样方法进行了优化改进,所发展的NMR数据处理新方法(CS_NASR)可有效排除主观因素影响,提高处理结果的鲁棒性.     

AlxGa1-xAs俄歇灵敏度因子的测定

利用PHI610俄歇谱仪测定了Al,Ga和As的俄歇灵敏度因子。对6种不同x值的Al_xGa_1-xAs样品进行俄歇定量分析。结果与X射线双晶衍射测量值非常一致。结果表明,利用自身谱仪测定的俄歇灵敏度因子进行的定量分析结果,与目前通常使用的手册或内标法提供的元素相对灵敏度因子的定量分析结果相比,测量精度得到大大提高。 关键词：     

利用高温超导直流量子干涉器件进行10$lt;sup$gt;-6$lt;/sup$gt; T量级磁场下核磁共振的研究

研究了水样品在10^-6 T量级磁场下的核磁共振谱.核磁共振信号由一个工作在液氮温度的高温超导直流量子干涉仪记录,测量在一个简易磁屏蔽室中进行.在7—70 μT的磁场范围内都观察到了15 ml水样品的核磁共振信号.相应的^1H的核磁共振频率为300—3000 Hz.在实验中获取的单次测量信噪比约为4,通过对信号的100次平均,信噪比可达到约40.进一步讨论了剩余磁场、预极化时间和采样时间对结果的影响.最后用数字滤波之后平均的方法初步得到了时域的自由感应衰减信号. 关键词： 超导量子干涉仪 核磁共振     

一种精密的边限振荡器型NQR谱仪及其应用

本文介绍一种精密的场效应管边限振荡器型核四极矩共振(NQR)谱仪。工作频率范围14MHz~35MHz,分段连续可调。这种谱仪的灵敏度高、波形失真小。在室温下,多晶粉未状氯酸钾样品中³⁵Cl的NQR频率测量精度大约3×10^-6。重结晶样品中³⁵Cl的NQR谱一次微分信号信噪比S/N ≥ 150。用该谱仪对KClO3、NaClO3、NaCl样品进行测试,得到氯的同位素³⁵Cl和37Cl的四极耦合常数比(eQq₃5Cl/(eQq₃7Cl的实测值分别为1.2687363、1.2687306、1.2687361。在77K到393K温度区间测量了氯酸钾多晶粉未状样品中³⁵Cl的NQR共振频率和温度的关系,在冰水混合温度附近,温度每变化0.1K,NQR频率的变化是478Hz。     

Bi系高温超导磁共振成像射频接收线圈的成像研究

射频接收线圈是磁共振成像系统输入通道的第一级,提高接收线圈的信噪比可以提高系统的图像质量.对于低场磁共振成像系统,如果能够降低常规铜接收线圈的等效串联电阻,就能够提高其信噪比.由于高温超导材料的直流电阻为零,交流传输损耗也远小于铜,采用高温超导材料制作磁共振接收线圈能够提高信噪比.本文采用Bi2223带材,设计、制作了超导接收线圈,并在0.23 T的磁共振成像系统中进行了成像实验.结果表明,超导接收线圈的图像信噪比比常规铜线圈提高约76%.     

High homogeneity B(1) 30.2 MHz Nuclear Magnetic Resonance Probe for off-resonance relaxation times measurements

This paper reports on design and construction of a double coil high-homogeneity ensuring Nuclear Magnetic Resonance Probe for off-resonance relaxation time measurements. NMR off-resonance experiments pose unique technical problems. Long irradiation can overheat the sample, dephase the spins because of B(1) field inhomogeneity and degrade the signal received by requiring the receiver bandwidth to be broader than that needed for normal experiment. The probe proposed solves these problems by introducing a separate off-resonance irradiation coil which is larger than the receiver coil and is wound up on the dewar tube that separates it from the receiver coil thus also thermally protects the sample from overheating. Large size of the irradiation coil also improves the field homogeneity because as a ratio of the sample diameter to the magnet (coil) diameter increases, the field inhomogeneity also increases (Blümich et al., 2008) [1]. The small receiver coil offers maximization of the filling factor and a high signal to the noise ratio.     

Radiation damping in microcoil NMR probes

Radiation damping arises from the field induced in the receiver coil by large bulk magnetization and tends to selectively drive this magnetization back to equilibrium much faster than relaxation processes. The demand for increased sensitivity in mass-limited samples has led to the development of microcoil NMR probes that are capable of obtaining high quality NMR spectra with small sample volumes (nL-microL). Microcoil probes are optimized to increase sensitivity by increasing either the sample-to-coil ratio (filling factor) of the probe or quality factor of the detection coil. Though radiation damping effects have been studied in standard NMR probes, these effects have not been measured in the microcoil probes. Here a systematic evaluation of radiation damping effects in a microcoil NMR probe is presented and the results are compared with similar measurements in conventional large volume samples. These results show that radiation-damping effects in microcoil probe is much more pronounced than in 5 mm probes, and that it is critically important to optimize NMR experiments to minimize these effects. As microcoil probes provide better control of the bulk magnetization, with good RF and B0 inhomogeneity, in addition to negligible dipolar field effects due to nearly spherical sample volumes, these probes can be used exclusively to study the complex behavior of radiation damping.     

Performance of cryogenic probes as a function of ionic strength and sample tube geometry

The pursuit for more sensitive NMR probes culminated with development of the cryogenic cooled NMR probe. A key factor for the sensitivity is the overall resistance of RF circuitry and sample. Lowering the coil temperature to approximately 25 K and the use of superconducting coil material has greatly reduced the resistance contribution of the hardware. However, the resistance of a salty sample remains the same and evolves as the major factor determining the signal-to-noise ratio. Several approaches have been proposed to reduce the resistance contribution of the sample. These range from encapsulating proteins in a water cavity formed by reverse micelles in low viscosity fluids to the optimal selection of low mobility, low conductivity buffer ions. Here we demonstrate that changing the sample diameter has a pronounced effect on the sample resistance and this results in dramatic improvements of the signal-to-noise ratio and shorter pi/2 pulses. We determined these parameters for common 5 mm NMR tubes under different experimental conditions and compared them to the 2, 3 and 4 mm tubes, in addition, 5mm Shigemi tubes were included since these are widely used. We demonstrate benefits and applicability of studying NMR samples with up to 4M salt concentrations in cryogenic probes. Under high salt conditions, best results in terms of short pi/2 pulses and high signal-to-noise ratios are obtained using 2 or 3mm NMR tubes, especially when limited sample is available. The 4 mm tube is preferred when sample amounts are abundant at intermediate salt conditions.     

Small crystals and small coils in variable-temperature single-crystal NMR

Time savings by a factor of between 20 and 30 in the acquisition of multinuclear single-crystal (SC) NMR spectra have been obtained for submillimeter-size (0.01 to 0.03 mm(3)) single crystals when compared to recent results for (31)P and (87)Rb SC NMR. This gain in sensitivity is achieved by optimizing the filling factor using the smallest possible rf coil (2.0 mm inner diameter) for the specific SC probe design. Furthermore, this small coil is particularly useful for variable-temperature SC NMR studies. A probe design for such studies is presented and demonstrated experimentally.     

Planar microcoil-based microfluidic NMR probes

Microfabricated small-volume NMR probes consisting of electroplated planar microcoils integrated on a glass substrate with etched microfluidic channels are fabricated and tested. 1H NMR spectra are acquired at 300 MHz with three different probes having observed sample volumes of respectively 30, 120, and 470 nL. The achieved sensitivity enables acquisition of an 1H spectrum of 160 microg sucrose in D2O, corresponding to a proof-of-concept for on-chip NMR spectroscopy. Increase of mass-sensitivity with coil diameter reduction is demonstrated experimentally for planar microcoils. Models that enable quantitative prediction of the signal-to-noise ratio and of the influence of microfluidic channel geometry on spectral resolution are presented and successfully compared to the experimental data. The main factor presently limiting sensitivity for high-resolution applications is identified as being probe-induced static magnetic field distortions. Finally, based on the presented model and measured data, future performance of planar microcoil-based microfluidic NMR probes is extrapolated and discussed.     

Optimization of NMR receiver bandwidth by inductive coupling.

We show, by theory and experiment, that inductive coupling can be used in overcoupled mode to widen the bandwidth of a high-Q NMR coil with only a negligible degradation of signal-to-noise ratio over the bandwidth of interest. The receiver bandwidth depends on the coupling coefficient between the NMR coil and the coupling coil rather than on the quality factor of the NMR coil alone. The overall bandwidth can be optimized by a judicious choice of the coupling coefficient. Moreover, this method permits wireless reception without the need for retuning and rematching despite changes of NMR coils or samples. This technique has been incorporated in a 0.1-T imager for clinical routine. It achieves a typical bandwidth five times greater than that using a classic 50-omega matching method.     

Development of a dual cell, flow-injection sample holder, and NMR probe for comparative ligand-binding studies

NMR based ligand screening is becoming increasingly important for the very early stages of drug discovery. We have proposed a method that makes highly efficient use of a single sample of a scarce target, or one with poor or limited solubility, to screen an entire compound library. This comparative method is based on immobilizing the target for the screening procedure. In order to support the method, a dual cell, flow injection probe with a single receiver coil has been constructed. The flow injection probe has been mated to a single high performance pump and sample handling system to enable the automated analysis of large numbers of compound mixes for binding to the target. The probe, having an 8 mm 1H/2H dual tuned coil and triple axis gradients, is easily shimmed and yields NMR spectra of comparable quality to a standard 5 mm high-resolution probe. The lineshape in the presence of a solid support is identical to that in glass NMR tubes in a 5 mm probe. Control spectra of each cell are identical and well separated, while ligand binding in a complex mixture can be readily detected in 20-30 min, thus paving the way for use of the probe for actual drug discovery efforts.     

低温NMR探头的应用

在过去10年中研发新核磁共振探头一直是制造者争夺的活跃领域. 最近，因其灵敏度的巨大提高，低温冷却探头得到人们格外的关注. 利用这一技术可大量节省谱仪机时. 对于低γ核可直接测定天然丰度样品而不必标记，这远比节省机时更为重要. 本文评述了针对5～10 Hz优化2 mg天然丰度噁唑烷酮抗菌素eperezolid的 CIGAR-HMBC-¹H-¹⁵N谱的比较，一个是采自美国瓦里安公司的5 mm低温探头，另一个是采自瓦里安公司传统室温3 mm 梯度三共振探头. 利用低温探头大约10 min就可记录到大部份¹H-¹⁵N远 程相关，26 min可观察到几乎所有的远程共振. 而在同样条件下使用3 mm传统梯度反式三共振探头无法得到有用的谱图，要想取得相同的结果须累加约18 h.     

轴线起爆式螺线管型爆磁压缩发生器理论模型

 对轴线起爆式螺线管型爆磁压缩发生器进行了理论模型研究，建立了爆炸管的一维爆轰驱动模型、螺线管内空间磁场强度分布模型、爆炸管外表面磁压力模型和发生器系统的等效电路模型等，对此类发生器的物理过程进行系统描述。在此基础上，编制了相应的零维数值模拟程序CEMG 1.0，利用该程序分别对四种不同模型参数的发生器进行了理论计算和参数优化，并对其中一模型发生器爆炸管外表面的磁压力及其引起的剩余电感进行了计算，给出了剩余电感与初始输入条件及负载电感的关系，从而得到该模型的输出性能极限。对理论模型的正确性进行了实例验算证明。     

An active resonator system for CW-ESR measurement operating at 700 MHz

An active resonator system operating at 700 MHz, which can attain a high Q for CW-ESR measurements of a high loss sample, was developed. This system consisted of a loop-gap resonator (LGR), a receiver coil, an excitation coil, and a phase tunable amplifier. A part of the RF power at the LGR was picked up by the receiver coil, amplified, and irradiated to the LGR again by the excitation coil, which made up a feedback circuit. Because the feedback circuit provided the energy that canceled the loss in the resonator, the Q of the active resonator system increased. When a sample tube (inner diameter, 20 mm; axial length, 31 mm) containing a nitroxide radical and physiological saline solution was placed in the resonator, the Q could be varied from 55 to 4000. It was possible to obtain a Q of the active resonator system with sample that was higher than that of the value of the LGR without a sample in a no-feedback condition. The ESR signal intensity increased up to 7 times with the increase in Q. The sensitivity increased up to 50%, which was a much smaller advance than that of the Q, because the noise level also increased with the increase in signal intensity.