基于模拟退火优化的定量重聚INEPT方法

doi:10.11938/cjmr20233071

摘要/Abstract

摘要：

以重聚INEPT（不灵敏核的重聚极化转移增强）脉冲序列为基础，采用模拟退火算法，优化得到极化转移和重聚时间参数集，建立定量重聚INEPT方法．序列中引入组合脉冲，克服射频场不均匀性和频率偏置效应的影响，提高检测的可靠性．进一步利用模拟退火优化，实现重聚INEPT的定量谱编辑．采用青蒿素、辛伐他丁等模型化合物对上述方法进行了验证，应用Case I极化时间参数集，定量积分的相对标准偏差分别为1.6%和3.3%，表明方法有效可靠，可满足定量检测的要求．在实际应用方面，采用定量重聚INEPT方法测定大豆油中脂肪酸含量，其结果与常规定量¹³C NMR测定的含量相符合，但检测时间显著减少．本文提出的定量重聚INEPT方法在石油、高分子等复杂体系的快速定量检测方面具有广泛的应用前景．

关键词: 液体核磁共振, 定量检测, 重聚INEPT, 模拟退火

Abstract:

In this paper, we presented a quantitative refocused INEPT (Refocused Insensitive Nuclei Enhanced by Polarization Transfer) method based on simulated annealing optimization, which utilizes the optimized polarization transfer and refocus delay set to yield nearly uniform enhancement for CH, CH₂ and CH₃ groups. The 180° composite pulses are applied in ¹³C channel to overcome the inhomogeneity of B₁field and the offset effect to improve the measurement reliability. Simulated annealing optimization is further applied to achieve quantitative spectral editing of refocused INEPT. The above methods were validated using model compounds such as artemisinin and simvastatin, and the relative standard deviations of the quantitative integrals with Case I delay set were 1.6% and 3.3%, respectively. As an application of the proposed method, major fatty acid compositions in soybean oils were determined using quantitative refocused INEPT, and the results were consistent with those determined by conventional quantitative ¹³C NMR, while the measurement time was significantly reduced. The quantitative refocused INEPT method is particularly attractive for rapid, accurate detection of complex systems such as petroleum and polymers.

Key words: liquid-state NMR, quantitative detection, refocused INEPT, simulated annealing

中图分类号:

O482.53

陈雷, 刘红兵, 刘惠丽, 王立英. 基于模拟退火优化的定量重聚INEPT方法[J]. 波谱学杂志, 2024, 41(1): 30-42.

CHEN Lei, LIU Hongbing, LIU Huili, WANG Liying. Quantitative Refocused INEPT Method Based on Simulated Annealing Optimization[J]. Chinese Journal of Magnetic Resonance, 2024, 41(1): 30-42.

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参考文献 38

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编号	化学位移	基团	积分面积		倍数
编号	化学位移	基团	zgig45	Q-RINEPT	倍数
A1	93.74	CH	0.402±0.001	1.009±0.004	2.51
A2	50.08	CH	0.400±0.006	0.985±0.002	2.47
A3	44.97	CH	0.404±0.001	1.002±0.001	2.48
A4	37.54	CH	0.409±0.002	0.987±0.001	2.41
A5	35.92	CH₂	0.402±0.007	0.994±0.006	2.47
A6	33.61	CH₂	0.404±0.005	0.985±0.002	2.44
A7	32.92	CH	0.404±0.006	0.999±0.007	2.47
A8	25.23	CH₃	0.401±0.005	1.017±0.002	2.54
A9	24.86	CH₂	0.402±0.002	1.001±0.005	2.49
A10	23.42	CH₂	0.417±0.005	1.002±0.002	2.40
A11	19.86	CH₃	0.411±0.009	1.047±0.004	2.55
A12	12.60	CH₃	0.407±0.003	1.005±0.007	2.47
平均值±标准偏差			0.405±0.005	1.003±0.016	2.48
相对标准差			1.2%	1.6%

编号	化学位移	基团	积分面积
编号	化学位移	基团	A	平均值±标准偏差	B	平均值±标准偏差
S1	132.95	CH	1.002	0.976±0.033	0.871	0.875±0.027
S2	129.72	CH	0.993		0.913
S3	128.42	CH	0.990		0.896
S4	76.58	CH	0.970		0.877
S5	68.17	CH	1.035		0.887
S6	62.54	CH	0.910		0.804
S8	37.53	CH	0.995		0.872
S9	36.65	CH	0.945		0.873
S14	30.68	CH	0.957		0.874
S15	27.30	CH	0.965		0.884
S7	38.68	CH₂	0.936	0.970± 0.032	1.202	1.271±0.036
S10	36.12	CH₂	0.935		1.262
S11	33.05	CH₂	0.982		1.291
S12	33.01	CH₂	0.982		1.291
S13	32.90	CH₂	1.027		1.317
S18	24.36	CH₂	0.959		1.263
S16	24.83	CH₃	1.008	1.011±0.008	1.536	1.551±0.015
S17	24.81	CH₃	1.008		1.536
S19	23.10	CH₃	1.026		1.574
S20	13.93	CH₃	1.012		1.545
S21	9.39	CH₃	1.001		1.565

序号	化学位移	归属	序号	化学位移	归属
1	131.89	Ln:C16(=CH)	15	34.19, 34.05, 34.02	C2 (-OC-CH2-)
2	130.17	Ln:C9(=CH)	16	31.98, 31.96	-CH₂-CH₂-CH₃
3	130.15	L:C13(=CH)	17	31.57	L:C16(-CH₂-CH₂-CH₃)
4	130.00, 129.98	O:C10(=CH)	18	29.87~28.99	-(CH₂)-
5	129.95, 129.93	L:C9(=CH)	19	27.30~27.15	=CH-CH₂-CH₂-
6	129.69, 129.67	O:C9(=CH)	20	25.66	L:C11 (=CH-CH₂-HC=)
7	128.27	Ln:C13(=CH)	21	25.64	Ln:C11 (=CH-CH₂-HC=)
8	128.23, 128.22	Ln:C12(=CH)	22	25.56	Ln:C14 (=CH-CH₂-HC=)
9	128.10, 128.09	L:C10(=CH)	23	24.90, 24.87	C3(-OC-CH2-CH2-)
10	127.93, 127.91	L:C12(=CH)	24	22.73	-CH₂-CH₃
11	127.79, 127.78	Ln:C10(=CH)	25	22.62	L:C17 (-CH₂-CH₃)
12	127.14	Ln:C15(=CH)	26	20.58	Ln:C17 (-CH₂-CH₃)
13	68.94	甘油基, -OCH	27	14.30	Ln:C18 (-CH₃)
14	62.10	甘油基, -OCH₂	28	14.14, 14.10	-CH₃

样品	油酸（mol%）		亚油酸（mol%）		亚麻酸（mol%）		饱和脂肪酸（mol%）
样品	Q-RINEPT	zgig45	Q-RINEPT	zgig45	Q-RINEPT	zgig45	Q-RINEPT	zgig45
1	22.0	21.6	53.8	53.2	6.2	6.2	18.0	19.0
2	19.2	19.0	54.2	53.3	9.2	8.8	17.4	18.9
3	21.5	21.5	53.0	53.3	6.4	6.0	19.1	19.2