同核或异核相关及自旋为1核的固体核磁共振方法研究

发布时间：2024-06-02 11:40

　　本论文的主要研究目的是开发固体核磁共振中用于检测核之间空间相邻性的同核或异核相关实验的新方法。还有一小部分涉及到利用组合脉冲实现氘核的宽带激发。第一章简要地介绍了固体样品中核自旋的哈密顿相互作用,并详细介绍了常见的若干同核/异核相关实验的方法。在下面的章节中将会涉及到其中的某些方法,并对这些方法进行了改进。第二章介绍了一种高场条件下的一阶(XY8)41超循环射频脉冲驱动重偶实验(first-order finite-pulse radio-frequency-driven recoupling:fp-RFDR)脉冲序列。这种相位超循环是通过相位翻转和四量子相循环来实现的。在高速或者超高速魔角旋转条件下,这种相位超循环的脉冲方法对以下若干影响因素具有很好的稳定性：(i)化学位移各向异性(CSA),(ii)化学位移的差异性,(iii)射频场的不均匀性,(iv)异核偶极耦合相互作用。我们通过模拟和实验对比了fp-RFDR-XY8、fp-RFDR-XY16和fp-RFDR-(XY8)41这三种方法在较大的射频脉冲偏转和强化学位移各项异性作用下的表现。在这些条件下,fp-RFDR-(XY8)41...

【文章页数】：181 页

【学位级别】：博士

【文章目录】：
摘要
ABSTRACT
Contents
Chapter 1:Introduction
    1.1 Nuclear Spin Interactions in Solids
        1.1.1 Chemical shift and Chemical shift anisotropy
        1.1.2 J-coupling
        1.1.3 Dipolar Coupling
        1.1.4 Quadrupolar interaction
    1.2 Through-space Homo-nuclear Correlation Spectroscopy
        1.2.1 SQ-SQ approach
        1.2.2 DQ-SQ aproach
    1.3 Through-space Hetero-nuclear Correlation Spectroscopy
    References
Chapter 2:Through-space Homo-nuclear Correlation Spectroscopy:fp-RFDR with(XY8)4¹ super-cycling
    2.1 Pulse sequence
    2.2 Numerical simulations
        2.2.1 Two spin-system
        2.2.2 Three spin-system:choice of rf-field
        2.2.3 Three spin-system:rf-inhomogeneity
        2.2.4 Three spin-system: CSA effect
        2.2.5 CIH-C2H2-H2 spin-system
    2.3 Experimental section
    2.4 Results and Discussion
        2.4.1 ¹³C-¹³C correlation
        2.4.2 ³¹P-³¹P correlations
    2.5 Conclusions
    References
Chapter 3:Through-space Homo-nuclear Correlation Spectroscopy:SHANGHAI+
    3.1 Numerical simulations
    3.2 Experimental verifications
    3.3 Conclusion
    References
Chapter 4:Through-space Hetero-nuclear Correlation Spectroscopy:improving theresolution
    4.1 Pulse sequence and theory
        4.1.1 The D-HMQC sequence
        4.1.2 The decoupling sequences
        4.1.3 Time increment optimization
    4.2 Numerical simulations
        4.2.1 Simulation parameters
        4.2.2 Decoupling efficiency
    4.3 Experimental demonstrations
        4.3.1 Sample and experimental conditions
        4.3.2 ¹H-{¹³C} D-HMQC 2D experiments at 9.4 T and v_R=32.3 kHz
        4.3.3 ¹H-{¹³C)D-HMQC 2D experiments at 18.8 T and 21.1 T using v_R≈62 kHz
        4.3.4 Application to ¹H-{¹⁴N} DANTE-D-HMQC at 21.1 T and v_R=62.1 kHz
    4.4 Conclusions
    References
Chapter 5:Through-space Hetero-nuclear Correlation Spectroscopy:detection of nucleiexperiencing large anisotropic interactions using frequency-selective pulses
    5.1 Pulse sequence
    5.2 Theory
        5.2.1 Coherence transfer
        5.2.2 Broadband excitation
        5.2.3 Sideband selective excitation
        5.2.4 Excitation of 2Q coherences
    5.3 Numerical simulations
        5.3.1 Simulation parameters
        5.3.2 Simulations for ¹⁹⁵Pt nucleus
        5.3.3 Simulations for ¹⁴N nucleus
    5.4 Experimental demonstration for ¹H-{¹⁴N} 1Q-HMQC
        5.4.1 Samples and experimental conditions
        5.4.2 Effect of rf-field and pulse length
        5.4.3 Sensitivity to rotor-synchronization
        5.4.4 Robustness to ¹⁴N offset
    5.5 Conclusions
    References
Chapter 6:Revisiting NMR composite pulses for broadband ²H excitation
    6.1 Pulse sequence and its implementation with composite pulse
    6.2 Numerical simulations
    6.3 Experimental
    6.4 Conclusions
    References
Chapter 7:Revisiting NMR composite pulses for broadband ²H excitation:Theoreticalcalculation by average Hamiltonian theory
    7.1 Analytical calculations of COM-Ⅱ
    7.2 Numerical simulations
    7.3 Conclusions
    References
Chapter 8:Resume
Acknowledgements
Curriculum Vitae and Publication



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