在线能量分辨质谱结合量子化学计算分析山奈素的多级质谱行为

引用本文: 管朋维, 宋青青, 张珂, 李婷, 李玮, 屠鹏飞, 李军, 宋月林. 在线能量分辨质谱结合量子化学计算分析山奈素的多级质谱行为[J]. 分析化学, 2020, 48(10): 1428-1433. doi: 10.19756/j.issn.0253-3820.201192 shu

Citation: GUAN Peng-Wei, SONG Qing-Qing, ZHANG Ke, LI Ting, LI Wei, TU Peng-Fei, LI Jun, SONG Yue-Lin. Investigation of Tandem Mass Spectrometric Behavior of Kaempferide by Online Collision Energy-resolved Mass Spectrometry-Structural Calculation[J]. Chinese Journal of Analytical Chemistry, 2020, 48(10): 1428-1433. doi: 10.19756/j.issn.0253-3820.201192 shu

在线能量分辨质谱结合量子化学计算分析山奈素的多级质谱行为

管朋维 ^1, ,
宋青青 ^1, ,
张珂 ^1, ,
李婷 ^1, ,
李玮 ^1, ,
屠鹏飞 ^1, ,
李军 ^1,2, ,
宋月林 ^1,2,

1.
北京中医药大学中药学院中药现代研究中心, 北京 100029;
2.
北京中医药大学中药品质评价北京市重点实验室, 北京 100029
基金项目:
本文系国家重点研发计划项目（No.2018YFC1707300）、国家自然科学基金项目（Nos.81773875，81530097）、中国科协青年人才托举工程项目（No.2017QNRC001）和北京中医药大学青年科学家培育计划项目（No.BUCM-2019-QNKXJB006）资助

摘要: 在多级质谱中，母离子碎裂成子离子的实质是在气态情况下，较高能量的中性气体分子与离子发生碰撞，转移能量，使化学键发生断裂。利用在线能量分辨质谱（Online ER-MS），逐步改变碰撞能，可以观察到子离子信号产生和消失的过程，结合量子化学计算可以准确归属子离子信号。本研究以黄酮类化合物山奈素为例，对其多级质谱行为进行深入分析。在串联离子阱-飞行时间质谱正离子模式下，母离子m/z 301.0712（[M+H]⁺）主要通过自由基裂解和Retro-Diels-Alder裂解（RDA裂解）生成子离子m/z 286.0518、272.0454、165.0155、161.0573、153.0192和139.0381。为了阐明关键离子m/z 161.0573的来源，在三重四极杆质谱中构建离子对m/z 301>161，进一步派生出一组拟离子对（PITs），对应一组递进式的碰撞能，利用多反应检测模式采集各拟离子对的相对峰面积，绘制裂解曲线。裂解曲线呈"M"型，表明m/z 161.0573有两种生成方式。结合结构计算推断"M"型裂解曲线的第一波峰由低裂解能的C环杂环裂解断裂1，4键继而中性丢失CH₄产生，第二波峰由高裂解能的C环RDA裂解断裂0，4键继而中性丢失CH₃OH产生。通过在线能量分辨质谱与量子化学计算的结合可以对化合物的多级质谱行为进行深入分析。

关键词:

English

Investigation of Tandem Mass Spectrometric Behavior of Kaempferide by Online Collision Energy-resolved Mass Spectrometry-Structural Calculation

1.
Modern Research Center for Traditional Chinese Medicine, School of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing 100029, China;
2.
Beijing Key Lab for Quality Evaluation of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing 100029, China
Received Date: 09 April 2020
Revised Date: 04 August 2020
Fund Project:
This work was supported by the National Key Research and Development Plan (No. 2018YFC1707300), the National Natural Science Foundation of China (Nos. 81773875, 81530097), the Young Elite Scientists Sponsorship Program by CAST (No. 2017QNRC001) and the Young Scientist Program by Beijing University of Chinese Medicine (No. BUCM-2019-QNKXJB006).

Abstract: Regarding tandem mass spectrometry (MS/MS), the theory of the transition from precursor ion to product ion is actually chemical bond dissociation in gas phase resulted from the collision between ions and collision gas molecules with high energy. It is feasible to observe the generation and disappearance of ions via gradually varying the collision energy, which is the mechanism of online collision energy-resolved mass spectrometry (ER-MS). Afterwards, the assignment of fragmentation pathways to the ions-of-interest can be achieved through combining online ER-MS and structural calculation. In current study, the application of online ER-MS towards in-depth clarification of tandem mass spectrometric pattern was illustrated by employing kaempferide as a representative case. Under positive ionization mode, the precursor ion, actually the protonated molecular ion ([M+H]⁺), was generated at m/z 301.0712 in MS¹ spectrum, which resulted in primary product ions, such as m/z 286.0518, 272.0454, 165.0155, 161.0573, 153.0192 and 139.0381 in MS² spectrum. To clarify the generation of m/z 161.0573, a precursor>product ion transition was subsequently constructed as m/z 301>161. A set of pseudo-ion transitions (PITs) was afterwards derived, and assigned a batch of progressive collision energies. The peak areas of all PITs were acquired under multiple reaction monitoring mode on triple quadrupole mass spectrometer (QqQ-MS), and normalized within the PITs set to construct the breakdown graphs. Except for m/z 301>161, the breakdown graphs of the other ion transitions fitted for Gaussian curve. "M"-type breakdown graph consisting of two Gaussian curves was observed for m/z 301>161. Following structural calculation, the former Gaussian curve was primarily generated by C-ring hetero-ring fission (HRF) at 1,4-bond coupled with CH₄ neutral loss, whereas the latter one corresponded to C-ring RDA fission at 0,4-bond coupled with CH₃OH neutral loss. Above all, the combination of online ER-MS and structural calculation is able to provide meaningful information for the in-depth clarification of tandem mass spectrometric patterns of chemical compounds.

Key words:

Online collision energy-resolved mass spectrometry
/ Kaempferide
/ Retro-Diels-Alder dissociation
/ Breakdown graph

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沈阳化工大学材料科学与工程学院沈阳 110142

在线能量分辨质谱结合量子化学计算分析山奈素的多级质谱行为

English

Investigation of Tandem Mass Spectrometric Behavior of Kaempferide by Online Collision Energy-resolved Mass Spectrometry-Structural Calculation

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

在线能量分辨质谱结合量子化学计算分析山奈素的多级质谱行为

English

Investigation of Tandem Mass Spectrometric Behavior of Kaempferide by Online Collision Energy-resolved Mass Spectrometry-Structural Calculation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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