宽带脉冲DC SQUID核磁共振谱仪的研制

DC SQUID NMR在研究凝聚态体系 ,尤其在研究低温下量子有序态等方面是一项非常有价值的技术。文中描述了在带有宽带电子设备的商业 DC SQUID基础上建立起宽带脉冲谱仪 ,以及马鞍形激发线圈、采集线圈和低温装置的设计 ,并测量了铂样品在 4.2 Kz温度下的 NMR信号。     

NMR at very low fields

Although nuclear magnetic resonance in low fields around or below the Earth's magnetic field is almost as old as nuclear magnetic resonance itself, the recent years have experienced a revival of this technique that is opposed to the common trend towards higher and higher fields. The background of this development is the expectation that the low-field domain may open a new window for the study of molecular structure and dynamics. Here, we will give an overview on the specific features in the low-field domain, both from the technical and from the physical point of view. In addition, we present a short passage on the option of magnetic resonance imaging in fields of the micro-Tesla range.     

低噪声HT_c rf SQUID芯片可控制备的实验研究

针对低内禀噪声要求条件下HTcrf SQUID芯片制备成品率和优质率低等问题,通过对YBCO薄膜的PLD制备工艺参数及所制作的YBCO薄膜性能与微观形貌的观测分析,提出晶界结构的非均匀和不一致性可能是影响低噪声台阶边沿型晶界结制备质量的观点,进而以淀积温度为典型控制参数设计了一组实验,对实验获取的YBCO薄膜和SQUID芯片的性能测试表明:YBCO薄膜生长的三高条件(高淀积温度、高氧分压和高激光能量密度)易造成薄膜表面平整度恶化和晶界构型的不均匀,而选择合适的淀积温度可有效提高SQUID芯片的噪声性能。     

An efficient calibration method for SQUID measurement system using three orthogonal Helmholtz coils

For a practical superconducting quantum interference device(SQUID) based measurement system,the Tesla/volt coefficient must be accurately calibrated.In this paper,we propose a highly efficient method of calibrating a SQUID magnetometer system using three orthogonal Helmholtz coils.The Tesla/volt coefficient is regarded as the magnitude of a vector pointing to the normal direction of the pickup coil.By applying magnetic fields through a three-dimensional Helmholtz coil,the Tesla/volt coefficient can be directly calculated from magnetometer responses to the three orthogonally applied magnetic fields.Calibration with alternating current(AC) field is normally used for better signal-to-noise ratio in noisy urban environments and the results are compared with the direct current(DC) calibration to avoid possible effects due to eddy current.In our experiment,a calibration relative error of about 6.89 × 10-4is obtained,and the error is mainly caused by the non-orthogonality of three axes of the Helmholtz coils.The method does not need precise alignment of the magnetometer inside the Helmholtz coil.It can be used for the multichannel magnetometer system calibration effectively and accurately.     

The transfer of the quantum correlation from two-mode nonclassical state field to the supercurrents in two distant SQUID rings

We have considered two distant mesoscopic superconducting quantum interference device (SQUID) rings A and B in the presence of two-mode nonclassical state fields and investigated the correlation of the supercurrents in the two rings using the normalized correlation function $C_{\rm AB}$. We show that when the parameter $\alpha$ is very small for the separable state with the density matrix $\hat {\rho } = (\left| {\alpha , - \alpha } \right\rangle \left\langle {\alpha , - \alpha } \right| + \left| { - \alpha ,\alpha } \right\rangle \left\langle { - \alpha ,\alpha } \right|) / 2$ and entangled coherent state (ECS) $\left| u \right\rangle = N_1 (\left| {\alpha , - \alpha } \right\rangle + \left| { - \alpha ,\alpha } \right\rangle )$ fields, the dynamic behaviours of the normalized correlation function $C_{\rm AB}$ are similar, but it is quite different for the entangled coherent state $\left| {u}' \right\rangle = N_2 (\left| {\alpha , - \alpha } \right\rangle - \left| { - \alpha ,\alpha } \right\rangle )$ field. When the parameter $\alpha $ is very large, the dynamic behaviours of $C_{\rm AB}$ are almost the same for the separable state, entangled coherent state $\left| u \right\rangle $ and $\left| {u}' \right\rangle $ fields. For the two-mode squeezed vacuum state field the maximum of $C_{\rm AB}$ increases monotonically with the squeezing parameter $r$, and as $r \to \infty $, $C_{\rm AB} \to 1$. This means that the supercurrents in the two rings A and B are quantum mechanically correlated perfectly. It is concluded that not all the quantum correlations in the two-mode nonclassical state field can be transferred to the supercurrents; and the transfer depends on the state of the two-mode nonclassical state field prepared.     

Use of a SQUID array to detect T-cells with magnetic nanoparticles in determining transplant rejection

Acute rejection in organ transplant is signaled by the proliferation of T-cells that target and kill the donor cells requiring painful biopsies to detect rejection onset. An alternative non-invasive technique is proposed using a multi-channel superconducting quantum interference device (SQUID) magnetometer to detect T-cell lymphocytes in the transplanted organ labeled with magnetic nanoparticles conjugated to antibodies specifically attached to lymphocytic ligand receptors. After a magnetic field pulse, the T-cells produce a decaying magnetic signal with a characteristic time of the order of a second. The extreme sensitivity of this technique, 10(5) cells, can provide early warning of impending transplant rejection and monitor immune-suppressive chemotherapy.     

Low-field microwave absorption in pulse laser deposited FeSi thin film

Low field microwave absorption (LFMA) measurements at 9.4 GHz (X-band), were carried out on pulse laser deposited (PLD) polycrystalline B20 cubic structure FeSi thin film grown on Si (111) substrate. The LFMA properties of the films were investigated as a function of DC field, temperature, microwave power and the orientation of DC field with respect to the film surface. The LFMA signal is very strong when the DC field is parallel to the film surface and vanishes at higher angles. The LFMA signal strength increases as the microwave power is increased. The LFMA signal disappears around 340 K, which can be attributed to the disappearance of ferromagnetic state well above room temperature in these films. We believe that domain structure evolution in low fields, which in turn modifies the low field permeability as well as the anisotropy, could be the origin of the LFMA observed in these films. The observation of LFMA opens the possibility of the FeSi films to be used as low magnetic field sensors in the microwave and rf frequency regions.     

Field sweep broadline NMR spectroscopy

A novel NMR spectrometer is described that is uniquely versatile in its ability to accurately record broad lines by sweeping the superconducting magnetic field and to perform standard high resolution solid state NMR experiments. Broadline observation is illustrated by ²⁷Al spectra from static samples. Such an instrument opens up many nuclei for serious study by NMR in the solid state for the first time.     

Resolution enhancement in in vivo NMR spectroscopy: detection of intermolecular zero-quantum coherences

Intermolecular zero-quantum coherences are insensitive to magnetic field inhomogeneities. For this reason we have applied the HOMOGENIZED sequence [Vathyam et al., Science 272 (1996) 92] to phantoms containing metabolites at low concentrations, phantoms with air inclusions, an intact grape, and the head of a rat in vivo at 750 MHz. In the 1H-spectra, the water signal is efficiently suppressed and line broadening due to susceptibility gradients is effectively removed along the indirectly detected dimension. We have obtained a 1H-spectrum of a 2.5 mM solution of gamma-aminobutyric acid in 12 min scan time. In the phantom with air inclusions a reduction of line widths from 0.48 ppm in the direct dimension to 0.07 ppm in the indirect dimension was observed, while in a deshimmed grape the reduction was from 1.4 to 0.07 ppm. In a spectrum of the grape we were able to resolve glucose resonances at 0.3 ppm from the water in 6 min scan time. J-coupling information was partly retained. In the in vivo spectra of the rat brain five major metabolites were observed.     

Low temperature probe for dynamic nuclear polarization and multiple-pulse solid-state NMR

Here, we describe the design and performance characteristics of a low temperature probe for dynamic nuclear polarization (DNP) experiments, which is compatible with demanding multiple-pulse experiments. The competing goals of a high-Q microwave cavity to achieve large DNP enhancements and a high efficiency NMR circuit for multiple-pulse control lead to inevitable engineering tradeoffs. We have designed two probes-one with a single-resonance RF circuit and a horn-mirror cavity configuration for the microwaves and a second with a double-resonance RF circuit and a double-horn cavity configuration. The advantage of the design is that the sample is in vacuum, the RF circuits are locally tuned, and the microwave resonator has a large internal volume that is compatible with the use of RF and gradient coils.     

The virtual NMR spectrometer: a computer program for efficient simulation of NMR experiments involving pulsed field gradients

This paper presents a software program, the Virtual NMR Spectrometer, for computer simulation of multichannel, multidimensional NMR experiments on user-defined spin systems. The program is capable of reproducing most features of the modern NMR experiment, including homo- and heteronuclear pulse sequences, phase cycling, pulsed field gradients, and shaped pulses. Two different approaches are implemented to simulate the effect of pulsed field gradients on coherence selection, an explicit calculation of all coherence transfer pathways, and an effective approximate method using integration over multiple positions in the sample. The applications of the Virtual NMR Spectrometer are illustrated using homonuclear COSY and DQF COSY experiments with gradient selection, heteronuclear HSQC, and TROSY. The program uses an intuitive graphical user interface, which resembles the appearance and operation of a real spectrometer. A translator is used to allow the user to design pulse sequences with the same programming language used in the actual experiment on a real spectrometer. The Virtual NMR Spectrometer is designed as a useful tool for developing new NMR experiments and for tuning and adjusting the experimental setup for existing ones prior to running costly NMR experiments, in order to reduce the setup time on a real spectrometer. It will also be a useful aid for learning the general principles of magnetic resonance and contemporary innovations in NMR pulse sequence design.     

Variable temperature system using vortex tube cooling and fiber optic temperature measurement for low temperature magic angle spinning NMR

We describe the construction and operation of a variable temperature (VT) system for a high field fast magic angle spinning (MAS) probe. The probe is used in NMR investigations of biological macromolecules, where stable setting and continuous measurement of the temperature over periods of several days are required in order to prevent sample overheating and degradation. The VT system described is used at and below room temperature. A vortex tube is used to provide cooling in the temperature range of -20 to 20 degrees C, while a liquid nitrogen-cooled heat exchanger is used below -20 degrees C. Using this arrangement, the lowest temperature that is practically achievable is -140 degrees C. Measurement of the air temperature near the spinning rotor is accomplished using a fiber optic thermometer that utilizes the temperature dependence of the absorption edge of GaAs. The absorption edge of GaAs also has a magnetic field dependence that we have measured and corrected for. This dependence was calibrated at several field strengths using the well-known temperature dependence of the (1)H chemical shift difference of the protons in methanol.     

Four complementary theoretical approaches for the analysis of NMR paramagnetic relaxation

Four theoretical and computational approaches used at the University of Michigan to analyze NMR paramagnetic relaxation enhancement (NMR-PRE) are described. The primary objective of the theory is to describe the relationship of the NMR-PRE phenomenon to the electron spin hamiltonian and the spin energy level structure when zero field splitting interactions are significant. Four formulations of theory are discussed: (1) spin dynamics simulation; (2) the laboratory frame "constant H(S)" formulation; (3) the Molecular Frame "constant H(S)" formulation; and (4) the zfs-limit "constant H(S)" formulation. No single theoretical approach describes all important aspects of the relaxation mechanism in a fully satisfactory way. We use the four formulations in a complementary manner to provide as complete a picture of the relaxation mechanism as possible. We also discuss the integration of NMR-PRE theory and recently developed theory of electron spin relaxation which accounts for effects of the permanent zfs hamiltonian.     

DOUBLESLICING: a non-iterative single profile multi-exponential curve resolution procedure. Application to time-domain NMR transverse relaxation data

A new non-iterative curve resolution technique for resolving single decay profiles is proposed. The new technique, called DoubleSlicing, is based on the Decra (Direct Exponential Curve Resolution Algorithm) principle. While the original Decra was designed to resolve several decay curves simultaneously and thus fitting common pure exponentials, DoubleSlicing can resolve single decay profiles by a simple double data transformation followed by an analytical and unique three-way decomposition. The new approach is successfully demonstrated on experimental NMR CPMG relaxation data, measured on combinations of unmixed paramagnetic CuSO(4) solutions. Decay signals of the water component were acquired following an innovative experimental design that ensured no interaction between the components present in each sample under observation. DoubleSlicing proved to be accurate in estimating relaxation times differing in one order of magnitude (range: 19.6-159.4ms). Its performance was comparable to discrete exponential fitting with the advantage of being much faster - in terms of computation time, DoubleSlicing outperformed exponential fitting by a factor of four.     

Fast acquisition of multi-dimensional spectra in solid-state NMR enabled by ultra-fast MAS

The advantages offered by ultra-fast (>60 kHz) magic angle spinning (MAS) rotation for the study of biological samples, notably containing paramagnetic centers are explored.It is shown that optimal conditions for performing solid-state ¹³C NMR under 60 kHz MAS are obtained with low-power CW ¹H decoupling, as well as after a low-power ¹H,¹³C cross-polarization step at a double-quantum matching condition. Acquisition with low-power decoupling highlights the existence of rotational decoupling sidebands. The sideband intensities and the existence of first and second rotary conditions are explained in the framework of the Floquet–van Vleck theory.As a result, optimal ¹³C spectra of the oxidized, paramagnetic form of human copper zinc superoxide dismutase (SOD) can be obtained employing rf-fields which do not exceed 40 kHz during the whole experiment. This enables the removal of unwanted heating which can lead to deterioration of the sample. Furthermore, combined with the short ¹H T₁s, this allows the repetition rate of the experiments to be shortened from 3 s to 500 ms, thus compensating for the sensitivity loss due to the smaller sample volume in a 1.3 mm rotor. The result is that 2D ¹³C–¹³C correlation could be acquired in about 24 h on less than 1 mg of SOD sample.     

Sensitivity quantification of remote detection NMR and MRI

A sensitivity analysis is presented of the remote detection NMR technique, which facilitates the spatial separation of encoding and detection of spin magnetization. Three different cases are considered: remote detection of a transient signal that must be encoded point-by-point like a free induction decay, remote detection of an experiment where the transient dimension is reduced to one data point like phase encoding in an imaging experiment, and time-of-flight (TOF) flow visualization. For all cases, the sensitivity enhancement is proportional to the relative sensitivity between the remote detector and the circuit that is used for encoding. It is shown for the case of an encoded transient signal that the sensitivity does not scale unfavorably with the number of encoded points compared to direct detection. Remote enhancement scales as the square root of the ratio of corresponding relaxation times in the two detection environments. Thus, remote detection especially increases the sensitivity of imaging experiments of porous materials with large susceptibility gradients, which cause a rapid dephasing of transverse spin magnetization. Finally, TOF remote detection, in which the detection volume is smaller than the encoded fluid volume, allows partial images corresponding to different time intervals between encoding and detection to be recorded. These partial images, which contain information about the fluid displacement, can be recorded, in an ideal case, with the same sensitivity as the full image detected in a single step with a larger coil.     

Diffusion and relaxation effects in general stray field NMR experiments

We analyze the evolution of magnetization following any series of radiofrequency pulses in strongly inhomogeneous fields, with particular attention to diffusion and relaxation effects. When the inhomogeneity of the static magnetic field approaches or exceeds the strength of the RF field, the magnetization has contributions from different coherence pathways. The diffusion or relaxation induced decay of the signal amplitude is in general nonexponential, even if the sample has single relaxation times T(1), T(2) and a single diffusion coefficient D. In addition, the shape of the echo depends on diffusion and relaxation. It is possible to separate contributions from different coherence pathways by phase cycling of the RF pulses. The general analysis is tested on stray field measurements using two different pulse sequences. We find excellent agreement between measurements and calculations. The inversion recovery sequence is used to study the relaxation effects. We demonstrate two different approaches of data analysis to extract the relaxation time T(1). Finite pulse width effects on the timing of the echo formation are also studied. Diffusion effects are analyzed using the Carr--Purcell--Meiboom--Gill sequence. In a stray field of a constant gradient g, we find that unrestricted diffusion leads to nonexponential signal decay versus echo number N, but within experimental error the diffusion attenuation is still only a function of g(2)Dt(3)(E)N, where t(E) is the echo spacing.     

低密度聚乙烯光引发交联机理Ⅴ.光引发剂二苯甲酮光解产物的NMR研究

用NMR技术对光引发剂二苯甲酮(BP)引发低密度聚乙烯模型化合物正二十四烷、正十二烷、鲨烷(异三十烷)、异辛烷和乙烯-1紫外光交联过程中的光解产物进行了检测和研究.井首次确定了BP在光引发交联体系中光解的主要产物为苯并哪醇(1,1,2,2-四苯基-1,2-乙二醇),为BP光引发聚乙烯交联的机理提供了直接的实验证据.     

超强磁场中核磁共振信号与屏蔽效应的理论研究

研究了超强磁场对于核磁共振样品中双原子分子中电子系统的哈密顿量的影响,并且给出了磁共振信号中由于外磁场与氢原子电子系统相互作用所产生的含有B02的修正项.基于核磁共振原理,获得了利用氢的NMR谱对超强磁场进行精确测量的理论依据,推导出了一种基于核磁共振技术的超强磁场测量公式,从而在理论上证明了对超强磁场进行精确测量是可行的.