基于UHPLC-QTOF MS的肉桂枝叶蒸油剩余物化学成分研究

doi:10.3969/j.issn.0253-2417.2020.06.007

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (6): 50-60.doi: 10.3969/j.issn.0253-2417.2020.06.007

基于UHPLC-QTOF MS的肉桂枝叶蒸油剩余物化学成分研究

程贤¹(), 毕良武¹^,*(), 曾维星¹, 赵振东¹, 陈玉湘¹, 张笮晦²^,³

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室; 江苏省林业资源高效加工利用协同创新中心, 江苏南京 210042
2. 广西中医药大学药学院广西中药药效研究重点实验室, 广西南宁 530200
3. 广西庚源香料有限责任公司, 广西东兴 538100

收稿日期:2020-06-09 出版日期:2020-12-28 发布日期:2020-12-29
通讯作者: 毕良武 E-mail:chengx9013@163.com;biliangwu@126.com
作者简介:毕良武, 研究员, 博士, 博士生导师, 从事天然产物化学与利用研究; E-mail:biliangwu@126.com
程贤(1990-), 女, 山东济宁人, 助理研究员, 博士, 从事天然产物化学与利用研究; E-mail:chengx9013@163.com
基金资助:
国家重点研发计划资助项目(2018YFD0600405);四川省院省校合作项目(2019YFSY0002);中国林科院林产化学工业研究所研究团队建设创新工程项目(LHSXKQ2)

Chemical Constituents of Distillation Residues from Cinnamon Twigs and Leaves by Using UHPLC-QTOF MS

Xian CHENG¹(), Liangwu BI¹^,*(), Weixing ZENG¹, Zhendong ZHAO¹, Yuxiang CHEN¹, Zuohui ZHANG²^,³

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province; Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing 210042, China
2. College of Pharmacy, Guangxi University of Chinese Medicine; Guangxi Key Laboratory of Efficacy Study on Chinese Materia Medica, Nanning 530200, China
3. Guangxi GengYuan Flavor and Fragrance Co. Ltd., Dongxing 538100, China

Received:2020-06-09 Online:2020-12-28 Published:2020-12-29
Contact: Liangwu BI E-mail:chengx9013@163.com;biliangwu@126.com

摘要/Abstract

摘要：

采用超高效液相色谱-四极杆飞行时间质谱联用（UHPLC-QTOF MS）技术对肉桂枝叶蒸油剩余物的化学成分进行扫描，在正、负离子模式下获取化合物准分子离子，同时获取准分子离子的二级特征离子碎片，并对化合物质谱裂解路径进行研究，最后基于高分辨数据和二级质谱信息对肉桂枝叶蒸油剩余物化学成分进行全面表征。研究结果表明：本方法可以对肉桂枝叶蒸油剩余物的化学成分进行快速的定性分析，在肉桂枝叶蒸油剩余物中鉴定出26个化学成分，包括2个酚类成分，3个黄酮类成分，5个糖苷类成分，4个醇类成分，3个醛类成分和9个酸类成分。

关键词: 肉桂枝叶, 液相色谱-质谱, 质谱裂解路径, 化学成分

Abstract:

Ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometer(UHPLC-QTOF MS) was applied to scan the main chemical constituents of distillation residues from cinnamon twigs and leaves. The molecular ion and characteristic fragment ions were detected in positive and negative ion modes. The fragmentation pathways of compounds were studied. The chemical constituents were characterized comprehensively by high resolution data and fragmentation of mass spectrometry. The results showed that UHPLC-QTOF MS can be used for rapid and comprehensive qualitative analysis of the chemical constituents from distillation residues. Total of 26 components of the residues were identified, including 2 polyphenols, 3 flavonoids, 5 glycosides, 4 alcohols, 3 aldehydes and 9 acids.

Key words: cinnamon leaves and twigs, UHPLC-MS, fragmentation pathway, chemical constituents

中图分类号:

TQ35

程贤, 毕良武, 曾维星, 赵振东, 陈玉湘, 张笮晦. 基于UHPLC-QTOF MS的肉桂枝叶蒸油剩余物化学成分研究[J]. 林产化学与工业, 2020, 40(6): 50-60.

Xian CHENG, Liangwu BI, Weixing ZENG, Zhendong ZHAO, Yuxiang CHEN, Zuohui ZHANG. Chemical Constituents of Distillation Residues from Cinnamon Twigs and Leaves by Using UHPLC-QTOF MS[J]. Chemistry and Industry of Forest Products, 2020, 40(6): 50-60.

图/表 8

图1

表1

肉桂枝叶蒸油剩余物中化学成分的定性分析"

序号 No.	保留时间 /min retention time	一级 MS¹	误差 error	分子式 formula	二级 MS²	化合物 compounds
1	16.25	165.1/[M+H]⁺	0.8	C₁₀H₁₂O₂	105.1	丁香酚eugenol
2	21.78	417.1/[M-H]^-	1.2	C₂₂H₂₆O₈	166.0/181.0/387.1	丁香脂素syringaresinol
3	17.19	303.0/[M+H]⁺	-0.1	C₁₅H₁₀O₇	153.0/229.0	槲皮素quercetin
4	18.77	287.0/[M+H]⁺	1.0	C₁₅H₁₀O₆	121.0/153.0/165.0/213.0/258.0	山柰酚kaempferol
5	19.17	287.0/[M+H]⁺	1.0	C₁₅H₁₀O₆	153.0/157.0/213.0/241.0/258.0	木犀草素luteolin
6	11.92	611.1/[M+H]⁺	1.5	C₂₇H₃₀O₁₆	303.0/325.1/356.0	芦丁rutin
7	12.12	327.1/[M-H]^-	2.7	C₁₅H₂₀O₈	103.0/147.0/165.0	木犀草苷dihydromelilotoside
8	12.97	595.1/[M+H]⁺	-0.7	C₂₇H₃₀O₁₅	287.0/449.1	烟花苷nicotiflorine
9	16.45	465.1/[M+H]⁺	-0.4	C₂₁H₂₀O₁₂	267.1/303.0	金丝桃苷hyperoside
10	16.80	435.1/[M+H]⁺	-0.2	C₂₀H₁₈O₁₁	303.0	槲皮素-3-O-木糖苷quercetin-3-O-xyloside
11	12.21	135.1/[M+H]⁺	0	C₉H₁₀O	103.1	肉桂醇cinnamyl alcohol
12	13.65	381.2/[M-H]^-	1.7	C₂₀H₃₀O₇	167.1/271.2/333.2	肉桂萜醇A cinncassiol A
13	18.45	365.2/[M-H]^-	1.6	C₂₀H₃₀O₆	215.1/285.2	无水桂二萜醇anhydrocinnzeylanol
14	26.64	407.2/[M-H]^-	3.3	C₂₂H₃₂O₇	215.1/285.2/329.2/347.2/365.2	脱水锡兰肉桂素anhydrocinnzeylanine
15	2.82	179.1/[M+H]⁺	-1.7	C₁₀H₁₀O₃	107.1/119.1/147.1	松柏醛coniferaldehyde
16	5.14	133.1/[M+H]⁺	2.2	C₉H₈O	105.1/115.1	肉桂醛cinnamaldehyde
17	9.56	163.1/[M+H]⁺	0.4	C₁₀H₁₀O₂	105.1/107.0/131.0/135.1	邻甲氧基肉桂醛2-methoxy cinnamaldehyde
18	4.82	167.0/[M-H]^-	-0.5	C₈H₈O₄	108.0/137.0	香草酸vanillic acid
19	5.98	153.0/[M-H]^-	2.4	C₇H₆O₄	109.0	原儿茶酸protocatechuic acid
20	8.30	225.1/[M+H]⁺	-0.7	C₁₁H₁₂O₅	165.1/193.0	芥子酸sinapic acid
21	9.90	163.0/[M-H]^-	0.4	C₉H₈O₃	117.0/119.1	对香豆酸p-coumaric acid
22	9.60	179.0/[M-H]^-	-1.6	C₉H₈O₄	135.0	咖啡酸caffeic acid
23	10.17	355.1/[M+H]⁺	-4.7	C₁₆H₁₈O₉	145.0/163.0/193.0	绿原酸chlorogenic acid
24	12.97	163.0/[M-H]^-	0.4	C₉H₈O₃	117.0/119.1	邻香豆酸o-coumaric acid
25	22.08	149.1/[M+H]⁺	-0.7	C₉H₈O₂	103.1/131.0	肉桂酸cinnamic acid
26	52.42	339.3/[M-H]^-	-0.7	C₂₂H₄₄O₂	183.0/197.0	山嵛酸behenic acid

表1

图2

图3

图4

图5

图6

图7

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基于UHPLC-QTOF MS的肉桂枝叶蒸油剩余物化学成分研究

Chemical Constituents of Distillation Residues from Cinnamon Twigs and Leaves by Using UHPLC-QTOF MS

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