研究论文

核自旋单重态的制备及其转化效率和寿命的影响因素分析

  • 刘慧霞 ,
  • 辛家祥 ,
  • 魏达秀 ,
  • 姚叶锋
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  • 上海市磁共振重点实验室, 华东师范大学 物理与材料科学学院, 上海 200062

收稿日期: 2019-03-22

  网络出版日期: 2019-05-13

基金资助

上海市自然科学基金资助项目(16ZR1448300).

Preparation of Nuclear Spin Singlet States and Analysis of Influencing Factors on Their Conversion Efficiency and Lifetime

  • LIU Hui-xia ,
  • XIN Jia-xiang ,
  • WEI Da-xiu ,
  • YAO Ye-feng
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  • Shanghai Key Laboratory of Magnetic Resonance, College of Physics and Materials Science, East China Normal University, Shanghai 200062, China

Received date: 2019-03-22

  Online published: 2019-05-13

摘要

长寿命核自旋单重态(LLS)因具有寿命较长这一特性而具有广泛的应用前景.本文在一个三肽样品(alanylglycylgcine,AGG)的水溶液中,对结构中离手性碳较远的二自旋体系进行核自旋单重态的制备,并探究了样品浓度、温度、射频发射中心位置、自旋体系之间的J耦合常数,以及磁场不均匀性五个因素对LLS的转化效率及其寿命的影响.实验结果表明,核自旋单重态的转化效率和寿命均不受样品浓度以及磁场不均匀性的影响.寿命会随实验温度的升高不断增加,转化效率随温度的下降而减小.射频中心位置在小范围内变化时,核自旋单重态制备所受影响不明显;但当变化较大时,其转化效率与寿命明显减小.同时,核自旋单重态对J耦合的变化则比较敏感,当J值选择不精准时,转化效率及寿命都出现明显降低.

本文引用格式

刘慧霞 , 辛家祥 , 魏达秀 , 姚叶锋 . 核自旋单重态的制备及其转化效率和寿命的影响因素分析[J]. 波谱学杂志, 2020 , 37(2) : 182 -192 . DOI: 10.11938/cjmr20192725

Abstract

The long-life nuclear spin singlet states (LLSs) have broad application prospects due to the unique nature of their long lifetime. Herein, in a solution of alanylglycylgcine (AGG), the nuclear spin singlet state of a two-spin system far from the chiral carbon in the structure is prepared. Then, the effects of sample concentration, temperature, radiofrequency (RF) center, J-coupling value and magnetic field inhomogeneity on conversion efficiency and lifetime of the LLSs were investigated. The experimental results showed that the conversion efficiency and lifetime of the singlet state were not affected by the sample concentration and magnetic field inhomogeneity, but increased with increasing experimental temperature. The influence of the position of RF center on the singlet state was not obvious when it changed within a small range, but the conversion efficiency and lifetime reduced significantly when the changes were large. Moreover, the singlet state was found to be sensitive to the changes of J-coupling value. The conversion efficiency and lifetime reduced significantly with choose of non-accurate J-coupling constant.

参考文献

[1] ARDENKJæR-LARSEN J H, GOLMAN K, GRAM A, et al. Increase of signal-to-noise of more than 10,000 times in liquid state NMR[J]. Discov Med, 2003, 3(19):37-39.
[2] ADAMS R W, AGUILAR J A, ATKINSON K D, et al. Reversible interactions with para-hydrogen enhance NMR sensitivity by polarization transfer[J]. Science, 2009, 323(5922):1708-1711.
[3] BOWERS C R, WEITEKAMP D P. Parahydrogen and synthesis allow dramatically enhanced nuclear alignment[J]. J Am Chem Soc, 1987, 109(18):5541-5542.
[4] WANG W Y, HU H, XU J, et al. Hydrogenation reaction on pd-cu bimetallic catalysts:a parahydrogen-induced polarization study[J]. Chinese J Magn Reson, 2018, 35(3):269-279. 王伟宇, 胡涵, 徐君, 等. Pd-Cu双金属催化剂上加氢反应的仲氢诱导超极化研究[J]. 波谱学杂志, 2018, 35(3):269-279.
[5] CARRAVETTA M, JOHANNESSEN O G, LEVITT M H. Beyond the T1 limit:singlet nuclear spin states in low magnetic fields[J]. Phys Rev Lett, 2004, 92(15):153003.
[6] CARRAVETTA M, LEVITT M H. Long-lived nuclear spin states in high-field solution NMR[J]. J Am Chem Soc, 2004, 126(20):6228-6229.
[7] FENG Y, DAVIS R M, WARREN W S. Accessing long-lived nuclear singlet states between chemically equivalent spins without breaking symmetry[J]. Nat Phys, 2012, 8(11):831-837.
[8] CARRAVETTA M, LEVITT M H. Theory of long-lived nuclear spin states in solution nuclear magnetic resonance. I. Singlet states in low magnetic field[J]. J Chem Phys, 2005, 122(21):214505.
[9] PILEIO G. Relaxation theory of nuclear singlet states in two spin-1/2 systems[J]. Prog Nucl Mag Res Sp, 2010, 56(3):217-231.
[10] PILEIO G, LEVITT M H. Theory of long-lived nuclear spin states in solution nuclear magnetic resonance. II. Singlet spin locking[J]. J Chem Phys, 2009, 130(21):214501.
[11] PILEIO G. Singlet state relaxation via intermolecular dipolar coupling[J]. J Chem Phys, 2011, 134(21):214505.
[12] PILEIO, G. Singlet state relaxation via scalar coupling of the second kind[J]. J Chem Phys, 2011, 135(17):174502.
[13] TAYLER M C D, LEVITT M H. Paramagnetic relaxation of nuclear singlet states[J]. Phys Chem Chem Phys, 2011, 13(20):9128-9130.
[14] VINOGRADOV E, GRANT A K. Long-lived states in solution NMR:Selection rules for intramolecular dipolar relaxation in low magnetic fields[J]. J Magn Reson, 2007, 188(1):176-182.
[15] PILEIO G, LEVITT M H. J-stabilization of singlet states in the solution NMR of multiple-spin systems[J]. J Magn Reson, 2007, 187(1):141-145.
[16] GRANT A K, VINOGRADOV E. Long-lived states in solution NMR:Theoretical examples in three-and four-spin systems[J]. J Magn Reson, 2008, 193(2):177-190.
[17] KARABANOV A A, BRETSCHNEIDER C, KÖCKENBERGER W. Symmetries of the master equation and long-lived states of nuclear spins[J]. J Chem Phys, 2009, 131(20):204105-204110.
[18] PILEIO G, CONCISTRÈ M, CARRAVETTA M, et al. Long-lived nuclear spin states in the solution NMR of four-spin systems[J]. J Magn Reson, 2006, 182(2):353-357.
[19] AHUJA P, SARKAR R, VASOS P R, et al. Long-lived states in multiple-spin systems[J]. Chem Phys Chem, 2010, 10(13):2217-2220.
[20] MEIER B, DUMEZ J N, STEVANATO G, et al. Long-lived nuclear spin states in methyl groups and quantum-rotor-induced polarization[J]. J Amer Chem Soc, 2013, 135(50):18746-18749.
[21] PRAVDIVTSEV A N, YURKOVSKAYA A V, ZIMMERMANN H, et al. Magnetic field dependent long-lived spin states in amino acids and dipeptides[J]. Phys Chem Chem Phys, 2014, 16(16):7584-7594.
[22] STEVANATO G, SINGHA ROY S, HILL-COUSINS J, et al. Long-lived nuclear spin states far from magnetic equivalence[J]. Phys Chem Chem Phys, 2015, 17(8):5913-5922.
[23] DUMEZ J N, HÅKANSSON P, MAMONE S, et al. Theory of long-lived nuclear spin states in methyl groups and quantum-rotor induced polarisation[J]. J Chem Phys, 2015, 142(4):044506.
[24] GUO H Q, XIN J X, LIU H X, et al. Preparation of long-lived nuclear singlet states in three-spin systems[J]. Chinese J Magn Reson, 2018, 35(3):345-352. 郭海清, 辛家祥, 刘慧霞, 等. 三自旋体系长寿命核自旋单重态的制备[J]. 波谱学杂志, 2018, 35(3):345-352.
[25] EMONDTS M, LEDBETTER M P, PUSTELNY S, et al. Long-lived heteronuclear spin-singlet states in liquids at a zero magnetic field[J]. Phys Rev Lett, 2014, 112(7):077601.
[26] PILEIO G, DUMEZ J N, POP I A, et al. Real-space imaging of macroscopic diffusion and slow flow by singlet tagging MRI[J]. J Magn Reson, 2015, 252:130-134.
[27] STEVANATO G, HILL-COUSINS J T, HÅKANSSON P, et al. A nuclear singlet lifetime of more than one hour in room-temperature solution[J]. Angew Chem Int Ed Eng, 2015, 54(12):3740-3743.
[28] PILEIO G, CARRAVETTA M, HUGHES E, et al. The Long-lived nuclear singlet state of 15N-nitrous oxide in solution[J]. J Amer Chem Soc, 2008, 130(38):12582-12583.
[29] AHUJA P, SARKAR R, VASOS P R, et al. Diffusion coefficients of biomolecules using long-lived spin states[J]. J Amer Chem Soc, 2009, 131(22):7498-7499.
[30] SARKAR R, VASOS P R, BODENHAUSEN G. Singlet-state exchange NMR spectroscopy for the study of very slow dynamic processes[J]. J Am Chem Soc, 2007, 129(2):328-334.
[31] VASOS P R, COMMENT A, SARKAR R, et al. Long-lived states to sustain hyperpolarized magnetization[J]. Pro Natl Acad Sci USA, 2009, 106(44):18469-14632.
[32] KOVTUNOV K V, TRUONG M L, BARSKIY D A, et al. Long-lived spin states for low-field hyperpolarized gas MRI[J]. Chemistry, 2014, 20(45):14629-14632.
[33] ROY S S, MAHESH T S. Initialization of NMR quantum registers using long-lived singlet states[J]. Phys Rev A, 2010, 82(5):3249-3253.
[34] DEVIENCE S J, WALSWORTH R L, ROSEN M S. Probing scalar coupling differences via long-lived singlet states.[J]. J Magn Reson, 2016, 262:42.
[35] SALVI N, BURATTO R, BORNET A, et al. Boosting the sensitivity of ligand-protein screening by NMR of long-lived states[J]. J Amer Chem Soc, 2012, 134(27):11076-11079.
[36] JONES J A, HORE P J. Spin-selective reactions of radical pairs act as quantum measurements[J]. Chem Phys Lett, 2010, 488(1-3):90-93.
[37] CAI J, CARUSO F, PLENIO M B. Quantum limits for the magnetic sensitivity of a chemical compass[J]. Phys Rev A, 2012, 85(4):124-130.
[38] PEARSON J, FENG G R, ZHENG C, et al. Experimental quantum simulation of avian compass in a nuclear magnetic resonance system[J]. Sci China Phys Mech, 2016, 59(12):120312.
[39] DEVIENCE S J, WALSWORTH R L, ROSEN M S. Preparation of nuclear spin singlet states using spin-lock induced crossing[J]. Phys Rev Lett, 2013, 111(17):173002.
[40] FENG Y. Accessing Long-lived nuclear spin states in chemically equivalent spin systems:theory, simulation, experiment and implication for hyperpolarization[D]. Durham:Duke University, 2014.
[41] MCROBBIE D W, MOORE E A, GRAVESM J, et al. MRI:from picture to proton[M]. New York:Cambridge university Press, 2003.
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