核磁共振实验结合量子化学计算研究3/4/5-O-阿魏酰奎宁酸三维结构

doi:10.11938/cjmr20243115

摘要/Abstract

摘要：

3/4/5-O-阿魏酰奎宁酸（3/4/5-O-feruloylquinic acid, 3/4/5-O-FQA）具有抗氧化活性，对预防多种疾病和维持人体健康有益，然而其准确三维结构尚不清楚．本文采用核磁共振波谱技术，结合量子化学理论计算方法，研究了3/4/5-O-FQA分别在气相、D₂O溶液和DMSO-d₆溶液中的三维结构．结果表明，3-O-FQA在D₂O和DMSO-d₆两种溶液中的三维结构存在差异，主要表现在酯化位H-3位置处二面角τ (H3C3O1C9的不同，相差4.147°．这些结构差异导致了3-O-FQA在两种溶液中的¹H 核磁共振谱图中H-3质子裂分方式不同．该工作给出了3/4/5-O-FQA的精确结构信息，能够为进一步研究其性质和应用价值提供参考和帮助．

关键词: 三维结构, 核磁共振, 量子化学计算, 化学位移, 3/4/5-O-阿魏酰奎宁酸

Abstract:

3/4/5-O-feruloylquinic acids (3/4/5-O-FQA) have antioxidant activity, which is beneficial to disease prevention and human health maintenance, however, their exact 3D structures are still unknown. In the present work, the structures of 3/4/5-O-FQA in gas phase, D₂O solution and DMSO-d₆ solution are investigated respectively using ¹H nuclear magnetic resonance (NMR) spectroscopy combined with quantum chemistry calculation. We observed a difference of 4.147° in dihedral angle τ (H3C3O1C9) on the esterification site H-3 for 3-O-FQA in D₂O and DMSO-d₆ solutions, which can explain the difference on ¹H NMR spectra for H-3 atom of 3-O-FQA in the two solutions. This work presents the 3D structures of 3/4/5-O-FQA, offering valuable insights for further studies on their properties and potential applications.

Key words: 3D structure, NMR, quantum chemistry calculation, chemical shift, 3/4/5-O-feruloylquinic acid

中图分类号:

O482.53

张佳钰, 聂文博, 涂朝, 郑利敏, 王艳, 杨春升. 核磁共振实验结合量子化学计算研究3/4/5-O-阿魏酰奎宁酸三维结构[J]. 波谱学杂志, 2025, 42(1): 47-55.

ZHANG Jiayu, NIE Wenbo, TU Zhao, ZHENG Limin, WANG Yan, YANG Chunsheng. Three-Dimensional Structures of 3/4/5-O-feruloylquinic Acids by NMR Spectroscopy and Quantum Chemistry Calculation[J]. Chinese Journal of Magnetic Resonance, 2025, 42(1): 47-55.

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参考文献 19

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3-O-FQA		4-O-FQA		5-O-FQA
H₂O	DMSO	H₂O	DMSO	H₂O	DMSO
	12.47	1.93	15.38	15.19	12.58	12.85
	19.67	14.71	22.19	22.14	15.50	16.12
	31.81	29.02	25.61	25.43	29.57	30.10
	38.61	32.85	34.29	34.24	40.51	40.80
	53.25	50.29	54.94	55.32	44.85	45.36
	62.17	61.66	58.46	58.30	57.94	58.49
	72.09	71.09	64.52	64.65	69.16	69.59
	87.96	86.18	81.22	81.66	84.51	84.74
	89.33	89.63	118.58	118.16	102.86	102.94
	123.20	123.03	127.79	127.73	114.08	114.54

Method	¹H NMR												RMSD
Method	δ_H-2	δ_H-2’	δ_H-3	δ_H-4	δ_H-5	δ_H-6	δ_H-6’	δ_H’-2	δ_H’-5	δ_H’-6	δ_H’-7	δ_H’-8	RMSD
B972/ pcSseg-1	2.41	2.19	5.28	3.68	3.79	2.17	2.17	8.08	7.24	7.52	7.88	6.61	0.34
B3LYP/ 6-311++g(d,p)	2.33	2.26	5.30	3.90	3.91	2.37	2.30	8.14	7.16	7.52	8.17	6.79	0.39
revTPSS/ pcSseg-1	2.46	2.26	5.32	3.81	3.85	2.29	2.25	7.82	7.02	7.29	7.60	6.39	0.24
EXP^a	2.13	2.11	5.31	3.67	4.08	2.20	1.95	7.23	6.82	7.12	7.61	6.41

	3-O-FQA		4-O-FQA		5-O-FQA
	D₂O	DMSO-d₆	D₂O	DMSO-d₆	D₂O	DMSO-d₆
δ_H-3	5.25 (5.28)	5.34 (5.42)	4.21 (4.21)	3.71 (4.21)	4.14 (4.23)	3.99 (4.23)
δ_H-4	3.61 (3.68 )	3.67 (3.68)	4.77 (4.90)	4.79 (4.90)	3.75 (3.67)	3.48 (3.67)
δ_H-5	4.02 (3.79)	3.62 (3.78)	4.16 (3.90)	4.17 (3.90)	5.18 (5.39)	5.19 (5.40)
RMSD	0.13	0.10	0.17	0.33	0.13	0.21