Magnetic field homogeneity: a new approach to orthogonalizing and optimizing shim gradients

A new approach to optimizing shim coil currents for magnetic resonance magnets is presented. The new approach orthogonalizes the shim coil gradients to allow a simple one-dimensional optimization for each orthogonalized "composite shim." The technique demands no specialized equipment, requiring only the acquisition of simple one-dimensional NMR spectra. Examples from two high-resolution NMR spectrometers are presented, where the shim currents found by the new algorithm provide higher resolution than was obtained by the spectrometer vendor's installation engineers using field-mapping techniques. The examples shown demonstrate the advantages of the technique for high-resolution NMR, but we expect the approach will also find application in a broad variety of areas including imaging and in vivo spectroscopy.     

Spatially encoded pulse sequences for the acquisition of high resolution NMR spectra in inhomogeneous fields

We have recently proposed a protocol for retrieving nuclear magnetic resonance (NMR) spectra based on a spatially-dependent encoding of the MR interactions. It has also been shown that the spatial selectivity with which spins are manipulated during such encoding opens up new avenues towards the removal of magnetic field inhomogeneities; not by demanding extreme Bo field uniformities, but rather by compensating for the dephasing effects introduced by the field distribution at a radiofrequency excitation and/or refocusing level. The present study discusses in further detail a number of strategies deriving from this principle, geared at acquiring both uni- as well as multi-dimensional spectroscopic data at high resolution conditions. Different variants are presented, tailored according to the relative sensitivity and chemical nature of the spin system being explored. In particular a simple multi-scan experiment is discussed capable of affording substantial improvements in the spectral resolution, at nearly no sensitivity or scaling penalties. This new compensation scheme is therefore well-suited for the collection of high-resolution data in low-field systems possessing limited signal-to-noise ratios, where magnetic field heterogeneities might present a serious obstacle. Potential areas of applications of these techniques include high-field in vivo NMR studies in regions near tissue/air interfaces, clinical low field MR spectroscopy on relatively large off-center volumes difficult to shim, and ex situ NMR. The principles of the different compensation methods are reviewed and experimentally demonstrated for one-dimensional inhomogeneities; further improvements and extensions are briefly discussed.     

Optimal experiments for maximizing coherence transfer between coupled spins

Hyperpolarized noble gases (HNGs) provide exciting possibilities for MR imaging at ultra-low magnetic field strengths (<0.15 T) due to the extremely high polarizations available from optical pumping. The fringe field of many superconductive magnets used in clinical MR imaging can provide a stable magnetic field for this purpose. In addition to offering the benefit of HNG MR imaging alongside conventional high field proton MRI, this approach offers the other useful advantage of providing different field strengths at different distances from the magnet. However, the extremely strong field gradients associated with the fringe field present a major challenge for imaging since impractically high active shim currents would be required to achieve the necessary homogeneity. In this work, a simple passive shimming method based on the placement of a small number of ferromagnetic pieces is proposed to reduce the fringe field inhomogeneities to a level that can be corrected using standard active shims. The method explicitly takes into account the strong variations of the field over the volume of the ferromagnetic pieces used to shim. The method is used to obtain spectra in the fringe field of a high-field (1.89 T) superconducting magnet from hyperpolarized 129Xe gas samples at two different ultra-low field strengths (8.5 and 17 mT). The linewidths of spectra measured from imaging phantoms (30 Hz) indicate a homogeneity sufficient for MRI of the rat lung.     

Fast Automatic Adjustment of On-Axis Shims for High-Resolution NMR

A one-dimensional approach for fast, robust, automatic adjustment of on-axis shims on high-resolution NMR spectrometers based on polynomial fitting of field inhomogeneity is described. Spherical harmonic and nonspherical harmonic terms of the field distribution of shim coils are precalibrated as polynomial coefficients by successively changing shim settings. This method greatly simplifies the shim precalibration and optimization procedures and is readily to be extended to three-dimensions to include off-axis shims.     

The NMR spectra of samples dissolved in liquid-crystalline phases: automatic analysis with the aid of multiple quantum spectra--the case of flexible molecules

Homonuclear N(S) = 0 and heteronuclear N(S) not equal 0 multiple quantum spectra, involving changes in the magnetic number m(I) by (N(I)-1), (N(I) - 2), and (N(I)-3), with N(I) and N(S) the number of interacting nuclei of magnetogyric ratio gamma(I) and gamma(S), are used for the automatic analysis of (1)H NMR spectra of flexible molecules dissolved in liquid-crystalline phases. The automatic procedure has been applied to study molecules of general formula Ph-CH(2)-X starting from a parameter set having all the spectral parameters set to zero. The results of such an analysis are then used as starting parameters for analysis of the single quantum spectrum. The method was first tested when X = Br and X = H in order to compare strategies differing for the types of parameters used and was then applied to the analysis of 3-phenylprop-1-yne.     

An eight-coil high-frequency probehead design for high-throughput nuclear magnetic resonance spectroscopy

In order to increase the throughput of high-resolution nuclear magnetic resonance spectroscopy a multiple-coil probe, which enables the simultaneous analysis of eight different samples, was designed. The probe, consisting of eight identical solenoidal coils, was constructed for operation at 600 MHz. By using four receivers and radiofrequency switches, spectra from eight different chemical solutions were acquired in the time normally required for one. Two-dimensional COSY, gradient COSY, and TOCSY data have been acquired. Intercoil electrical isolation was between 25 and 45 dB, with signal cross-talk between approximately 1 and 5% measured by NMR. The spectral linewidths for the eight coils were between 3 and 6Hz for a single optimized shim setting.     

Beyond k-space: spectral localization using higher order gradients

Chemical shift imaging (CSI) often suffers from the inconvenient shape of its spatial response function (SRF), which affects both localization and signal-to-noise ratio. Replacing the magnetic field gradients for phase encoding by higher order magnetic fields allows a better adjustment of the SRF to the structures in the sample. We combined this principle with the SLOOP (spectral localization with optimal pointspread function) technique to simultaneously obtain spectra from several arbitrarily shaped compartments within a sample. Linear combinations of the fields of the shim coils are used to generate the pulsed fields for phase encoding. Their shapes are matched to the given sample geometry by numerical optimization. Using this method, spectra from a phantom were obtained that show a higher signal-to-noise ratio and a strongly reduced contamination compared to an equivalent CSI experiment.     

纯位移核磁共振氢谱及其应用

J耦合引起的核磁共振(NMR)信号多重裂分的数目和耦合常数反映了磁性原子核之间的化学键数目和空间位置信息,是研究分子结构的重要依据之一.但是当分子中磁性原子核数目增加时,NMR谱图特别是一维核磁共振氢谱(1D ~1H NMR)中,J耦合所致的多重裂分造成谱图重叠,严重干扰结构指认和定量分析.利用纯位移(亦称宽带同核去耦)~1H NMR谱图可以消除J耦合效应(即将相邻质子间耦合所引起的多重裂分融合成一个单峰),得到与去耦碳谱相似的、只含化学位移信息的谱图.该文首先介绍了三种最受关注的获取纯位移核磁共振氢谱技术——BIRD、ZS和PSYCHE的基本原理,随后综述了纯位移~1H NMR谱图的典型应用.     

基于边界元方法的超导核磁共振成像设备高阶轴向匀场线圈优化算法

在磁共振成像设备中,为了消除目标区域内的高阶谐波磁场分量,传统方法采用无源匀场,但该方法匀场精度较低,针对性较差,适用于全局匀场,而有源匀场则可以通过优化线圈分布来产生所需要的特定的磁场分布.但是,由于匀场线圈线型的复杂度会随着线圈阶数的增加而增加,难以满足设计需要,因此本文提出了一种用于磁共振成像超导匀场线圈系统的多变量非线性优化设计方法.该方法基于边界元方法,将匀场线圈所产生的磁场与目标磁场之间的偏差作为目标函数,线匝间距、线圈半径等作为约束条件,通过非线性优化算法,得到满足设计要求的线圈分布.通过一个中心磁场为0.5 T的开放式双平面磁共振成像超导轴向匀场线圈的设计案例,说明本方法具有计算效率高、灵活性好的特点.     

Simple mobile single-sided NMR apparatus with a relatively homogeneous B0 distribution

This work presents a simple design for a mobile single-sided nuclear magnetic resonance (NMR) apparatus with a relatively homogeneous static magnetic field (B₀) distribution. In the proposed design, the B₀ magnetic field of the apparatus is synthesized using only two permanent magnet blocks, i.e., a cube (main) magnet and a small shim magnet placed above the main magnet. The magnetic flux of the shim magnet partially cancels out that of the main magnet, subsequently creating a smooth B₀ profile above the shim magnet where low-resolution NMR experiments are performed. Compared with many previously published designs, this straightforward design simplifies the construction of the apparatus and simultaneously generates a B₀ field parallel to the apparatus surface, allowing the use of a simple loop-type radiofrequency (RF) coil. Additionally, an apparatus prototype is constructed according to the proposed design. Weighing only 1.8 kg, the constructed apparatus has a compact structure and can be held in the palm of a hand. The apparatus generates a B₀ strength of about 0.0746 T. Within a B₀ field deviation of 3 mT, the region with a relatively homogeneous B₀ distribution extends to about 11 mm above the shim magnet. The proposed apparatus can detect a clear Hahn echo or Carr-Purcell-Meiboom-Gill (CPMG) echoes of a pencil eraser block or a bottle of oil placed on the apparatus in 5 s with signal averaging using an RF transmitter power of only 19 W; the detection range of the apparatus exceeds 6 mm. The strength of the residual static magnetic field gradient of the apparatus is roughly estimated at 0.58 T/m. Applying different CPMG echo spacings in this residual static gradient leads to various transverse relaxation time (T₂) contrasts for liquids with distinct viscosities such as water and oil. Two nondestructive inspection applications of the apparatus, including correlating the concentrations of magnetic nanoparticle solutions with their measured transverse relaxation rates (R₂) and monitoring the outgassing from an opened bottle of oxygen-supersaturated water by measuring its longitudinal relaxation rate (R₁), are also demonstrated.     

Combined passive and active shimming for in vivo MR spectroscopy at high magnetic fields

The use of high magnetic fields increases the sensitivity and spectral dispersion in magnetic resonance spectroscopy (MRS) of brain metabolites. Practical limitations arise, however, from susceptibility-induced field distortions, which are increased at higher magnetic field strengths. Solutions to this problem include optimized shimming, provided that active, i.e., electronic, shimming can operate over a sufficient range. To meet our shim requirements, which were an order of magnitude greater than the active shim capacity of our 7T MR system, we developed a combined passive and active shim approach. Simple geometries of ferromagnetic shim elements were derived and numerically optimized to generate a complete set of second-order spherical harmonic shim functions in a modular manner. The major goals of the shim design were maximization of shim field accuracy and ease of practical implementation. The theoretically optimized ferro-shim geometries were mounted on a cylindrical surface and placed inside the magnet bore, surrounding the subject's head and the RF coil. Passive shimming generated very strong shim fields and eliminated the worst of the field distortions, after which the field was further optimized by flexible and highly accurate active shimming. Here, the passive-shimming procedure was first evaluated theoretically, then applied in phantom studies and subsequently validated for in vivo 1H MRS in the macaque visual cortex. No artifacts due to the passive shim setup were observed; adjustments were reproducible between sessions. The modularity and the reduction to two pieces per shim term in this study is an important simplification that makes the method applicable also for passive shimming within single sessions. The feasibility of very strong, flexible and high-quality shimming via a combined approach of passive and active shimming is of great practical relevance for MR imaging and spectroscopy at high field strengths where shim power is limited or where shimming of specific anatomical regions inherently requires strong shim fields.     

Identification of organic molecules from a structure database using proton and carbon NMR analysis results

A compound is identified by matching its proton and/or carbon NMR spectra to NIH PubChem molecular structures. The matching process involves analyzing 1D proton, 1D carbon, DEPT, and/or HSQC spectra, and comparing the number of NMR resonances, detected proton and carbon shifts, likely number of methyl- and methoxy-groups, and an optionally specified molecular formula to predicted proton and carbon shifts of PubChem structures. A structure verification module rates the consistency between experimental spectral analysis results and a proposed structure (not limited to PubChem structures) and assigns observed shifts to the proposed structure. The spectral analysis, structure identification, and structure verification are largely automated in a software package and can be performed in minutes.     

High resolution NMR spectroscopy of rat brain in vivo through indirect zero-quantum-coherence detection

The time evolution of zero-quantum-coherences (ZQCs) is insensitive to magnetic field inhomogeneity. Using a 2D indirect ZQC detection method it is shown that high-resolution (1)H NMR spectra can be obtained from rat brain in vivo at 11.74T that are immune to magnetic field inhomogeneity. Simulations based on the density matrix formalism, as well as in vitro measurements are used to demonstrate the features of 2D ZQC NMR spectra. Unique spectral information which is normally not directly available from regular (1)H NMR spectra can be extracted and used for compound identification or improved prior knowledge during spectral fitting.     

基于核岭回归方法的恒星大气物理参数的自动测量

我国大科学工程项目LAMOST巡天计划每观测夜能获取多达数万条天体光谱数据,天文学家通过对天体光谱的分析观察可以获取有效的天文信息用于天文学或天体物理学的研究。而针对海量数据,寻找自动方法分析天体光谱并进行天体各种物理参数的测量就具有重要研究意义和价值。这一课题也吸引了许多学者进行研究,但目前所尝试的算法和相应结果仍然需要进一步改进,针对这一需求深入研究了核岭回归(KRR)方法在恒星大气物理参数(包括有效温度、表面重力和金属丰度)自动测量方面的应用,特别是在我国大科学工程项目LAMOST所释放光谱数据上的应用。核岭回归是岭回归算法的进一步发展,而岭回归是最小二乘方法的一种变形,其具有解决高维多重共线性问题的能力。所以KRR方法适合于处理高维的天体光谱信息,从LAMOST的第五期释放数据中随机选择了2万条被识别为恒星的光谱数据用于实验测试,该数据既包含低信噪比数据,也包含高信噪比数据(g,r,i波段平均信噪比最低至6.7,最高到793)。首先,本文对光谱进行预处理,包括三个步骤:(1)利用小波变换对光谱数据进行去噪处理;(2)因为LAMOST采用的是后期修正的流量定标设计,所以还通过流量归一化来避免部分光谱流量值不准确的问题;(3)由于每条光谱维数高达数千维,利用主成分分析方法(PCA)对光谱进行了降维。然后,利用KRR方法建立了光谱数据和标准化后的三大参数值之间的回归模型。最后,通过设计进行不同的组合实验对KRR算法模型进行了测试分析,并与经典算法支持向量回归(SVR)进行了对比。综合所有实验结果显示KRR方法对应的有效温度、表面重力和金属丰度的测试平均绝对误差分别为82.9897 K,0.1858 dex和0.1211 dex,优于SVR的144.2308 K,0.1886 dex和0.1246 dex。特别是KRR在温度测试结果上有较大优势,由此表明KRR方法能够有效地应用于天体光谱特别是恒星光谱参数的自动测量处理中。     

Developments for the direct determination of the g-factor of a single proton in a Penning trap

The measurement and comparison of the magnetic moment (or g-factor) of the proton and antiproton provide a stringent experimental test of the CPT-theorem in the baryonic sector (Quint et al., Nucl Instrum Methods Phys Res, B 214:207, 2004). We present an experimental setup for the first direct high-precision measurement of the g-factor of a single isolated proton in a double cylindrical Penning trap. The application of the continuous Stern-Gerlach effect to detect quantum jumps between the two spin states of the particle, together with a novel trap design specially developed for this purpose, offers the possibility of measuring the magnetic moment not only of a single proton but also of a single antiproton. It is aimed to achieve a relative uncertainty of 10^???9 or better. Preliminary results including mass spectra of particle clouds as well as single proton preparation and detection are shown.     

Anisotropy of hyperfine interactions as a tool for interpretation of NMR spectra in magnetic materials

Approach for interpretation of nuclear magnetic resonance (NMR) spectra in magnetic materials is presented, consisting in employing the anisotropy of hyperfine interaction. The anisotropic parts of hyperfine magnetic fields on ⁵⁷Fe nuclei are calculated ab initio for a model example of lithium ferrite and utilized to assign the experimental NMR spectral lines to iron sites in the crystal structure.     

Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

Bulk magnetization and ¹H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe₂O₃ nano- or micro-particles have been studied. In LAP+Fe₂O₃, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe₂O₃, due to the higher proton concentration in polystyrene and stronger proton–proton dipolar coupling, an additional broadening is observed, i.e. ¹H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton–magnetic particles and proton–proton dipolar couplings. An increase of the volume magnetization by ～1 emu/cm³ affects the ¹H NMR signal width in a way that is similar to an increase of the proton concentration by ～2×10²²/cm³. ¹H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.     

Demixing of severely overlapped H NMR resonances and interpretation of anomalous intensity pattern of dipolar coupled A3 spins in a weakly aligning medium

The increasing scientific and industrial interest towards metabonomics takes advantage from the high qualitative and quantitative information level of nuclear magnetic resonance (NMR) spectroscopy. However, several chemical and physical factors can affect the absolute and the relative position of an NMR signal and it is not always possible or desirable to eliminate these effects a priori. To remove misalignment of NMR signals a posteriori, several algorithms have been proposed in the literature. The icoshift program presented here is an open source and highly efficient program designed for solving signal alignment problems in metabonomic NMR data analysis. The icoshift algorithm is based on correlation shifting of spectral intervals and employs an FFT engine that aligns all spectra simultaneously. The algorithm is demonstrated to be faster than similar methods found in the literature making full-resolution alignment of large datasets feasible and thus avoiding down-sampling steps such as binning. The algorithm uses missing values as a filling alternative in order to avoid spectral artifacts at the segment boundaries. The algorithm is made open source and the Matlab code including documentation can be downloaded from www.models.life.ku.dk.     

Numerical simulation of PRESS localized MR spectroscopy

Numerical simulations of NMR spectra can provide a rapid and convenient method for optimizing acquisition sequence parameters and generating prior spectral information required for parametric spectral analysis. For spatially resolved spectroscopy, spatially dependent variables affect the resultant spectral amplitudes and phases, which must therefore be taken into account in any spectral simulation model. In this study, methods for numerical simulation of spectra obtained using the PRESS localization pulse sequence are examined. A comparison is made between three different simulation models that include different levels of detail regarding the spatial distributions of the excitation functions, and spin evolution during application of the pulses. These methods were evaluated for measurement of spectra from J-coupled spin systems that are of interest for in vivo proton spectroscopy and results compared with experimental data. It is demonstrated that for optimized refocusing pulses it is sufficient to account for chemical shift effects only, although there is some advantage to implementing a more general numerical simulation approach that includes information on RF pulse excitation profiles, which provides sufficient accuracy while maintaining moderate computational requirements and flexibility to handle different spin systems.     

An Efficacious Target-Field Approach to Design Shim Coils for Halbach Magnet of Mobile NMR Sensors

The main magnetic fields of mobile nuclear magnetic resonance (NMR) magnets differ from those of conventional NMR and magnetic resonance imaging (MRI) magnets. In the Halbach magnet, the main field B ₀ is perpendicular to the longitudinal axis, the symmetry of the current distribution with respect to the symmetry of the magnetic field differs from that in conventional target-field applications, and the current distribution on the coil surface cannot be expressed in terms of periodic basis functions. To obtain the winding pattern of the coil, an efficacious target-field approach. The surface of a coil is divided into small discrete elements, where each element is represented by a magnetic dipole. From the stream function of the elements, the resultant magnetic field is calculated. The optimization strategy follows an objective function defined by the power dissipation or efficiency of the coil. This leads to the optimum stream function on the coil surface, whose contour lines define the winding patterns of the coil. This paper shows winding patterns designed of shim coils for Halbach magnet and illustrates the craft of a shim coil using flexible printed circuit board. The performance of the coils is verified by simulating the fields they produce over the sensitive volume.