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近零场磁共振波谱和成像是一个快速发展的前沿领域, 其在化学样品快速分析和便携式磁共振诊断方面拥有巨大的应用潜力, 伴随着其核心部件原子磁力计的成熟, 国际上许多学者已提出相关的临床应用方案与计划. 近年来, 超极化技术的快速发展弥补了近零场磁共振信号强度不足的问题. 溶解动态核极化(dDNP)、仲氢超极化(PHIP/SABRE)、化学诱导动态核极化(CIDNP)以及自旋交换光抽运(SEOP)等超极化技术在近零场磁共振中已得到初步应用. 结合极化技术, 可以摆脱磁铁, 显著提高磁共振信号强度, 从而推动近零场磁共振在化学分析与人体成像中的应用, 为快速的化学样品分析和基于磁共振成像的快速诊断提供更便携的工具. 本文将综述近零场磁共振与超极化技术的相关研究进展.
Near-zero-field nuclear magnetic resonance (NMR) has become a rapidly developing spectroscopic and imaging method, providing promising opportunities for portable diagnostics and fast chemical analysis. A key technology is the atomic magnetometer, and its ongoing improvements have sparked growing interest in potential clinical applications. The near-zero-field NMR has long been limited by weak signal strength, but recent developments in the hyperpolarization method have provided an effective solution to this problem. Dissolution dynamic nuclear polarization (dDNP), parahydrogen-based polarization schemes (PHIP/SABRE), chemically induced dynamic nuclear polarization (CIDNP), and spin-exchange optical pumping (SEOP) have all demonstrated preliminary feasibility in this context. By combining such hyperpolarization strategies with near-zero-field detection, strong signals can be obtained without the need of traditional high-field magnets. This capability opens new pathways for applying near-zero-field NMR to both chemical sensing and biomedical imaging, enabling compact tools for rapid analysis and diagnostic applications. Here, we review the recent progress of the intersection of near-zero-field NMR and hyperpolarization techniques. -
Keywords:
- near-zero-field NMR /
- hyperpolarization /
- magnetometer /
- MRI
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图 2 零场到超低场(ZULF)核磁共振中的化学交换场景[9] (a) 影响整个J耦合网络的化学交换, 分子中的所有原子的相互作用都可以破坏化学键, 例如对称分子(如H2O和$ {\text{NH}}_{4}^{+} $); (b) 影响J耦合网络子系统的化学交换, 其中自旋系统的一部分交换, 而分子的其余部分保持完整, 如具有多个耦合核的分子中的质子交换, 一旦解离, 氢(浅蓝色表示)可以附着在不同的分子上, 使交换发生分子间
Fig. 2. Chemical exchange scenarios in zero- to ultralow-field (ZULF) NMR[9]: (a) Exchange affecting the entire J-coupled network, where all atoms in a molecule can break chemical bonds. Examples include symmetric molecules like H2O and $ {\text{NH}}_{4}^{+} $; (b) exchange affecting a subsystem of the J-coupled network, where part of the spin system exchanges while the rest of the molecule remains intact. An example is proton exchange in molecules with multiple coupled nuclei. Once dissociated, hydrogen (light blue) can attach to a different molecule, making the exchange intermolecular.
图 4 原子磁力计示意图 (a) NMOR原子磁力计; (b) 小型化原子磁力计
Fig. 4. Schematic diagram of atomic magnetometers: (a) NMOR-based atomic magnetometer; (b) miniaturized atomic magnetometer.
图 6 用于近零场磁共振的线圈 (a) 柔性线圈设计图(内部); (b) 柔性线圈设计图(内部); (c) 马鞍形线圈; (d) 亥姆霍兹线圈
Fig. 6. Coils used for near-zero-field NMR: (a) Flexible coil for shielding; (b) photo of flexible coil; (c) saddle-shaped coil; (d) Helmholtz coil.
图 11 可逆交换信号放大(SABRE)过程示意图
Fig. 11. Schematic diagram of the signal amplification by reversible exchange (SABRE) process.
图 12 连续仲氢诱导超极化与近零场磁共振的结合[44] (a) 以吡啶为底物的SABRE反应; (b) 计算机控制仲氢通过SABRE样品的实验装置
Fig. 12. Combination of continuous parahydrogen-induced hyperpolarization and near-zero-field NMR[44]: (a) SABRE reaction scheme with pyridine as substrate; (b) experimental setup of computer controlled p-H2 bubbling through a SABRE sample.
图 14 129Xe的弱自旋交换光泵浦示意图[58] (a) 含有400 Torr N2和200 Torr Xe(129Xe为26.4%)的气体混合物通过泵室和探针室, 最终从出口室流出; 进入泵室的非极化129Xe通过与光泵浦87Rb的自旋交换变得极化, 并随后进入探针室; (b) 硅芯片尺寸为3 cm×1 cm, 厚度1 mm; (c) 129Xe的泵浦和探测序列
Fig. 14. Schematic diagram of weak spin-exchange optical pumping of 129Xe (a) A gas mixture containing 400 Torr N2 and 200 Torr Xe (with 129Xe at 26.4%) flows through the pumping chamber and probe chamber, and eventually exits the output chamber. The depolarized 129Xe entering the pumping chamber becomes polarized through spin exchange with optical pumping of 87Rb, and then moves into the probe chamber. (b) The silicon chip has dimensions of 3 cm×1 cm and a thickness of 1 mm. (c) Pumping and detection sequence for 129Xe.
图 15 近零场磁共振与超极化技术的结合及应用
Fig. 15. Combination and application of Near-Zero-Field NMR and hyperpolarization technology.
图 16 近零场下的磁共振成像 (a) 近零场下对样品管的成像; (b) 人脑的近零场磁共振成像; (c) 近零场磁共振对流动液体的成像
Fig. 16. Combination of continuous parahydrogen-induced hyperpolarization and near-zero-field NMR: (a) Imaging of sample tubes at ZULF; (b) ZULF MRI of human brain; (c) imaging of flowing liquids using ZULF NMR.
图 18 近零场磁共振中特征谱峰可以达到亚赫兹的线宽水平
Fig. 18. The characteristic spectral peak in ZULF NMR can reach a line width of sub-Hertz.
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