柚皮素7-O-葡萄糖苷非对映异构体的NMR波谱分析

doi:10.11938/cjmr20152418

波谱学杂志 ›› 2017, Vol. 34 ›› Issue (4): 465-473.doi: 10.11938/cjmr20152418

柚皮素7-O-葡萄糖苷非对映异构体的NMR波谱分析

孙丽娟¹, 胡小芳¹, 程寻¹, 罗立廷², 刘红兵², 陈雷²

1. 湖北大学, 中药生物技术省重点实验室, 生物资源绿色转化湖北省协同创新中心, 湖北武汉 430062;
2. 波谱与原子分子物理国家重点实验室, 武汉磁共振中心(中国科学院武汉物理与数学研究所), 湖北武汉 430071

收稿日期:2015-03-11 修回日期:2017-10-24 出版日期:2017-12-05 发布日期:2017-11-29
通讯作者: 刘红兵,Tel:027-87197794,E-mail:hbliu1212@163.com;陈雷,Tel:027-87199737,E-mail:chenlei@wipm.ac.cn E-mail:hbliu1212@163.com;chenlei@wipm.ac.cn
基金资助:
国家自然科学基金资助项目（31400304）；波谱与原子分子物理国家重点实验室开放项目（T151203）；中国科学院仪器设备功能开发技术创新项目（YG2012108，YG2012110，YG2011095）.

NMR Characterization of Flavanone Naringenin 7-O-Glycoside Diastereomer

SUN Li-juan¹, HU Xiao-fang¹, CHENG Xun¹, LUO Li-ting², LIU Hong-bing², CHEN Lei²

1. Hubei Province Key Laboratory of Biotechnology of Chinese Traditional Medicine, Hubei Collaborative Innovation Center for Green Transformation of Bio-Resources, Hubei University, Wuhan 430062, China;
2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan(Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China

Received:2015-03-11 Revised:2017-10-24 Online:2017-12-05 Published:2017-11-29

摘要/Abstract

摘要： 二氢黄酮糖苷化后产生的R与S构型非对映异构体在¹H NMR谱上会呈现一些差别，但文献对其差别描述非常有限.为便于利用¹H NMR谱图判断二氢黄酮糖苷的R与S构型非对映异构体，本文首先在植物药皂荚提取物中分离得到一种二氢黄酮苷-柚皮素7-O-葡萄糖苷R与S构型混合物，分析其氘代二甲亚砜（DMSO-d₆）溶液的¹H NMR、¹³C NMR、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC谱，对其¹H和¹³C NMR谱峰进行了归属；然后，采用手性色谱柱对该混合物进行分离，结合圆二色光谱（CD）技术确定构型；最后，为鉴别R与S构型柚皮素7-O-葡萄糖苷在¹H NMR谱中特征差别谱峰，避免葡萄糖残基质子对二氢黄酮苷元质子化学位移的影响，采集了R与S构型柚皮素7-O-葡萄糖苷及其混合物氘代乙腈（CD₃CN）溶液的NMR谱，结果显示葡萄糖残基端基质子H-1″化学位移差别最为明显，为9.4 Hz；5-位酚羟基质子化学位移差别为5.8 Hz，C环上3个质子化学位移差也较明显．

关键词: 核磁共振(NMR), 柚皮素7-O-葡萄糖苷, 非对映异构体, 圆二色光谱, 结构解析

Abstract: To discriminate R and S flavanone glycoside using NMR, the mixture of R and S naringenin 7-O-glycoside was first isolated from Gleditsia sinensis. ¹H and ¹³C NMR data of the mixture were recorded with ¹H NMR, ¹³C NMR, ¹H-¹H COSY, ¹H-¹³C HSQC and ¹H-¹³C HMBC in DMSO-d₆ solution. The two diastereomers were then separated with chiral chromatographic isolation, with their absolute configurations determined by circular dichroism. To avoid the disturbance of protons from glucose residues to dihydroflavonoid, ¹H NMR spectra were acquired for pure R and S naringenin 7-O-glycoside and their mixture in CD₃CN. The two diastereomers showed the largest proton chemical shift differences at the end group of glucose residue (H-1") with a chemical shift difference of 9.4 Hz. The OH-5 proton showed a chemical shift difference of 5.8 Hz. The chemical shift of the three protons on ring C were all influenced by configuration.

Key words: NMR, naringenin 7-O-glycoside, diastereomer, circular dichroism, structure analysis

中图分类号:

O482.53

孙丽娟, 胡小芳, 程寻, 罗立廷, 刘红兵, 陈雷. 柚皮素7-O-葡萄糖苷非对映异构体的NMR波谱分析[J]. 波谱学杂志, 2017, 34(4): 465-473.

SUN Li-juan, HU Xiao-fang, CHENG Xun, LUO Li-ting, LIU Hong-bing, CHEN Lei. NMR Characterization of Flavanone Naringenin 7-O-Glycoside Diastereomer[J]. Chinese Journal of Magnetic Resonance, 2017, 34(4): 465-473.

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柚皮素7-O-葡萄糖苷非对映异构体的NMR波谱分析

NMR Characterization of Flavanone Naringenin 7-O-Glycoside Diastereomer

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