用遗传算法优化灵敏度增强的定量13C NMR实验

doi:10.11938/cjmr20233057

摘要/Abstract

摘要：

定量核磁共振（qNMR）是NMR分析的重要组成部分，在组分分析、化合物结构鉴定等方面发挥着重要作用．碳原子组成了有机物的框架，而¹³C NMR具有化学位移分布范围宽、谱峰窄、可宽带去耦等优点，因此¹³C NMR在有机物分析中具有独特优势．但¹³C核天然丰度低、旋磁比小、纵向弛豫时间较长，阻碍了定量¹³C NMR的更广泛应用．在此前的工作中，我们提出了Q-DEPT⁺脉冲序列，设计了读脉冲翻转角和极化转移时间双重循环，使得CH、CH₂、CH₃三种碳核在较宽的¹J_CH范围内获得均匀的灵敏度增强，并可用于定量¹³C NMR实验．在本文中，我们利用遗传算法进一步优化了Q-DEPT⁺实验的极化转移时间和读取脉冲的脉宽，并将¹³C通道的180°硬脉冲改为对频偏效应有补偿作用的G5组合脉冲，优化后的序列称为Q-DEPT⁺⁺．对胆固醇乙酸酯的氘代氯仿溶液分别使用常规反门控去耦（zgig）、Q-DEPT⁺和Q-DEPT⁺⁺脉冲序列进行了定量实验，并将三者的定量准确性和灵敏度进行了对比．结果显示Q-DEPT⁺⁺脉冲序列在定量准确性和灵敏度两方面均有明显提高．

关键词: 液体核磁共振, 定量核磁共振, 核磁共振碳谱, DEPT, 遗传算法, 灵敏度增强

Abstract:

Quantitative NMR experiments are an essential part of NMR analysis, which play a critical role in component analysis and compound structure identification. Carbon atoms form the framework of organic compounds, and ¹³C NMR has unique advantages in organic analysis due to its wide chemical shift range, narrow spectral peaks, and broadband decoupling capability. However, the low natural abundance, low gyromagnetic ratio, and long longitudinal relaxation time of ¹³C nuclei hinder its wider application in quantitative experiments. In our previous work, we proposed the Q-DEPT⁺ pulse sequence and designed a double loop of pulse flip angle and polarization transfer time, which allows for uniform sensitivity enhancement for the three types of carbon nuclei, CH, CH₂, and CH₃, within a wide ¹J_CH range, making it suitable for quantitative ¹³C NMR. In this study, we further optimized the polarization transfer time and read pulse width of the Q-DEPT⁺ experiment by using a genetic algorithm, and replaced the 180° hard pulse in the ¹³C channel with a G5 composite pulse that compensates for the frequency offset effect. The optimized pulse sequence was named Q-DEPT⁺⁺. Quantitative experiments were performed on cholesterol acetate in CDCl₃by using the reverse-gated decoupling pulse sequence (zgig), Q-DEPT⁺, and Q-DEPT⁺⁺ respectively, and the quantification accuracy and sensitivity of the three pulse sequences were compared. The results showed that Q-DEPT⁺⁺ has obvious improvement in both quantification accuracy and sensitivity.

Key words: liquid-state NMR, quantitative NMR, ¹³C NMR, DEPT, genetic algorithm, sensitivity enhancement

中图分类号:

O482.53

宋林红, 柴鑫, 张许, 蒋滨, 刘买利. 用遗传算法优化灵敏度增强的定量¹³C NMR实验[J]. 波谱学杂志, 2023, 40(4): 365-375.

SONG Linhong, CHAI Xin, ZHANG Xu, JIANG Bin, LIU Maili. Optimizing Sensitivity-enhanced Quantitative ¹³C NMR Experiment by Genetic Algorithm[J]. Chinese Journal of Magnetic Resonance, 2023, 40(4): 365-375.

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	Δ/ms	θ/°
Q-DEPT⁺	1.384, 1.536, 2.173, 3.319, 3.319, 4.234, 5.331, 7.041	35.3, 48, 50.6, 78.5, 87.5, 87.9
Q-DEPT⁺⁺	3.892, 1.693, 2.834, 2.759, 4.409, 2.496, 5.413, 1.719, 2.071, 7.998, 5.164, 6.197	38.2, 39.82, 78.1, 67.4, 90.0, 87.7, 16.7, 46.8, 35.8, 56.4, 70.3, 78.3

用遗传算法优化灵敏度增强的定量¹³C NMR实验

Optimizing Sensitivity-enhanced Quantitative ¹³C NMR Experiment by Genetic Algorithm

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