不均匀不稳定磁场下高分辨液体核磁共振新技术的研究进展

摘要/Abstract

摘要：

高分辨核磁共振（Nuclear Magnetic Resonance，NMR）谱的获得通常需要高度稳定且均匀的强静磁场. 阻抗磁体或阻抗－超导混合磁体可获得比超导磁体高得多的磁场，但它们的磁场的稳定性与均匀性比较差；另一方面，在活体定域波谱研究中，样品内部组分的磁化率差异，运动或生理活动等作用将不可避免地导致磁场的不均匀不稳定，并且这些不稳定不均匀性无法通过锁场匀场等传统的方法消除. 基于分子间零量子相干的方法、空间编码单扫描快速方法、反卷积技术等日渐成为在不均匀不稳定磁场下获取高分辨率的NMR谱的研究热点.

关键词: 核磁共振（NMR）, 高分辨, 不稳定不均匀磁场, 空间编码, 分子间多量子相干

Abstract:

Strong and extremely homogeneous and stable static magnetic fields are usually required for high-resolution NMR. However, large inhomogeneity and drift of the magnetic fields exist in the resistive and hybrid magnets which can provide much higher magnetic fields than the superconducting counterpart. On the other hand, the susceptibility gradients and physiological motions in in vivo studies produce inhomogeneous and unstable magnetic fields. Therefore, the inhomogeneous and instable magnetic fields in the non-ideal condition are unavoidable and can hardly be eliminated by conventional methods such as shimming and locking. Some approaches had been proposed to obtain high-resolution NMR spectra in the inhomogeneous and instable field, such as intermolecular zero quantum coherences (iZQCs), spatially encoding single-scan scheme and deconvolution. In the paper, these four methods were discussed.

Key words: nuclear magnetic resonance, high-resolution, inhomogeneous and unstable magnetic fields, spatially encoding, intermolecular multiplequantum coherences

中图分类号:

O482.53

张志勇, 林美金, 林玉兰, 陈忠. 不均匀不稳定磁场下高分辨液体核磁共振新技术的研究进展[J]. 波谱学杂志, 2010, 27(3): 310-325.

ZHANG Zhi-Yong, LIN Mei-Jin, LIN Yu-Lan, CHEN Zhong. Progress of High-Resolution Liquid NMR Spectroscopy in Inhomogeneous and Unstable Fields[J]. Chinese Journal of Magnetic Resonance, 2010, 27(3): 310-325.

参考文献

[1] Sakellariou D, Meriles C A, Pines A. Advances in-ex-situ- nuclear magnetic resonance[J]. C R Phys, 2004, 5(3): 337-347.
[2] Eidmann G, Savelsberg R, Blümler P, et al. The NMR MOUSE, a mobile universal surface explorer[J]. J Magn Magn Series A, 1996, 122(1): 104-109.
[3] Blumich B, Perlo J, Casanova F. Mobile single-sided NMR \[J\]. Prog Nucl Magn Reson Spectrosc, 2008, 52(4): 197-269.
[4] Lin YY, Ahn S, Murali N, et al. High-resolution, >1 GHz NMR in unstable magnetic fields[J]. Phys Rev Lett, 2000, 85(17): 3 732-3 735.
[5] Shapira B, Shetty K, Brey W W, et al. Single-scan 2D NMR spectroscopy on a 25 T bitter magnet[J]. Chem Phys Lett, 2007, 442(46): 478-482.
[6] Haase J, Kozlov M, Muller K H, et al. NMR in pulsed high magnetic fields at 1.3 GHz[J]. J Magn Magn Mater, 2005, 290: 438-441.
[7] Haase J, Kozlov MB, Webb AG, et al. 2 GHz ¹H NMR in pulsed magnets[J]. Solid State Nucl Magn Reson, 2005, 27(3): 206-208.
[8] Katz-Brull R, Lenkinski R E. Frame-by-frame PRESS ¹H MRS of the brain at 3 T: The effects of physiological motion[J]. Magn Reson Med, 2004, 51(1): 184-187.
[9] Lin T, Sun H J, Chen Z, et al. Numerical simulations of motion-insensitive diffusion imaging based on the distant dipolar field effects[J]. Magn Reson Imaging, 2007, 25(10):1 409-1 416.
[10] Kennedy S D, Zhong J. Diffusion measurements free of motion artifacts using intermolecular dipole-dipole interactions[J]. Magn Reson Med, 2004, 52(1): 1-6.
[11] Iijima T, Takegoshi K, Hashi K, et al. High-resolution NMR with resistive and hybrid magnets: Deconvolution using a field-fluctuation signal[J]. J Magn Reson, 2007, 184(2): 258-262.
[12] Sigmund E E, Mitrovic V F, Calder E S, et al. Inductive shielding of NMR phase noise[J]. J Magn Reson, 2002, 159(2): 190-194.

[13] Lacey M E, Subramanian R, Olson D L, et al. High-resolution NMR spectroscopy of sample volumes from 1 nL ot 10 μL[J]. Chem Rev, 1999, 99(10): 3 133-3 152.

[14] Pelupessy P, Rennella E, Bodenhausen G. High-resolution NMR in magnetic fields with unknown spatiotemporal variations[J]. Science, 2009, 324(5935): 1 693-1 697.
[15] Iijima T, Takegoshi K. Compensation of effect of field instability by reference deconvolution with phase reconstruction[J]. J Magn Reson, 2008, 191(1): 128-134.
[16] Gan Z, Kwak H T, Bird M, et al. High-field NMR using resistive and hybrid magnets[J]. J Magn Reson, 2008, 191(1): 135-140.
[17] Warren W S, Richter W, Andreotti A, et al. Generation of impossible cross-peaks between bulk water and biomolecules in solution NMR[J]. Science, 1993, 262(5142): 2 005-2 009.
[18] Jeener J. Equivalence between the “classical” and the “Warren” approaches for the effects of long range dipolar couplings in liquid nuclear magnetic resonance[J]. J Chem Phys, 2000, 112(11): 5 091-5 094.
[19] Chen Z, Cai S H, Chen Z W, et al. Fast acquisition of high-resolution NMR spectra in inhomogeneous fields via intermolecular double-quantum coherences[J]. J Chem Phys, 2009, 130(8): 84 504-84 514.
[20] Vathyam S, Lee S, Warren W S. Homogeneous NMR spectra in inhomogeneous fields[J]. Science, 1996, 272(5258): 92-96.
[21] Chen Z, Chen Z W, Zhong J. High-resolution NMR spectra in inhomogeneous fields via IDEAL (Intermolecular Dipolar-Interaction Enhanced All Lines) method[J]. J Am Chem Soc, 2004, 126(2): 446-447.
[22] Huang Y Q, Cai S H, Chen X, et al. Intermolecular single-quantum coherence sequences for high-resolution NMR spectra in inhomogeneous fields[J]. J Magn Reson, 2010, 203(1): 100-107.
[23] Lin Y Q, Gu T L, Chen Z, et al. High-resolution MRS in the presence of field inhomogeneity via intermolecular double-quantum coherences on a 3 T whole-body scanner[J]. Magn Reson Med, 2010, 63(2): 303-311. 
[24] Peng L, Zheng Z Y, Huang Y Q, et al. High-resolution NMR spectra in inhomogeneous and unstable fields via three-pulse method[J]. Mol Phys, 2010, In press.
[25] Lin M J, Chen X, Cai C B, et al. High-resolution MR spectroscopy in unstable fields via intermolecular zeroquantum coherences[J]. Phys Chem Chem Phys, 2010, 12: 6 014-6 020.
[26] Frydman L, Lupulescu A, Scherf T. Principles and features of single-scan two-dimensional NMR spectroscopy [J]. J Am Chem Soc, 2003, 125(30): 9 204-9 217.
[27] Shapira B, Frydman L. Spatial encoding and the acquisition of high-resolution NMR spectra in inhomogeneous magnetic fields[J]. J Am Chem Soc, 2004, 126(23): 7 184-7 185.
[28] Nagayama K, Wüthrich K, Ernst RR. Two-dimensional spin echo correlated spectroscopy (SECSY) for ¹H NMR studies of biological macromolecules[J]. Biochem Biophys Res Commun, 1979, 90(1): 305-311.
[29] Wokaun A, Ernst R R. Selective detection of multiple quantum transitions in NMR by two-dimensional spectroscopy[J]. Chem Phys Lett, 1977, 52(3): 407-412.
[30] Pelupessy P. Adiabatic single scan two-dimensional NMR spectrocopy[J]. J Am Chem Soc, 2003, 125(40): 12 34-5-12 350.
[31] Wu C, Zhao MF, Cai S H, et al. Ultrafast 2D COSY with constant-time phase-modulated spatial encoding[J]. J Magn Reson, 2010, 204(1): 82-90.
[32] Shrot Y, Frydman L. Spatial encoding strategies for ultrafast multidimensional nuclear magnetic resonance [J]. J Chem Phys, 2008, 128(5): 1 089-7 690.
[33] Giraudeau P, Akoka S. A new detection scheme for ultrafast 2D J-resolved spectroscopy[J]. J Magn Reson, 2007, 186(2): 352-357.
[34] Galiana G, Branca RT, Warren WS. Ultrafast intermolecular zero quantum spectroscopy[J]. J Am Chem Soc, 2005, 127(50): 17 574-17 575.
[35] Giraudeau P, Akoka S. Sensitivity losses and line shape modifications due to molecular diffusion in continuous encoding ultrafast 2D NMR experiments[J]. J Magn Reson, 2008, 195(1): 9-16.
[36] Huang Y Q, Cai S H, Lin Y Q, et al. An intermolecular single-quantum coherence detection scheme for highresolution two-dimensional J-resolved spectroscopy in inhomogeneous fields[J]. Appl Spectrosc, 2010, 64(2): 235-240.
[37] Huang Y Q, Chen X, Cai S H, et al. High-resolution two-dimensional correlation spectroscopy in inhomogeneous fields: New application of intermolecular zero-quantum coherences[J]. J Chem Phys, 2010, 132(13): 134 507-134 515.
[38] Huang Y Q, Zhang W, Cai S H, et al. Homonuclear decoupled proton NMR spectra in modest to severe inhomogeneous fields via distant dipolar interactions[J]. Chem Phys Lett, 2010, 492(1-3): 174-178.