基质固相分散和HPLC-IT-TOF/MS联用研究漆树木材中多酚成分

doi:10.3969/j.issn.0253-2417.2022.01.002

林产化学与工业 ›› 2022, Vol. 42 ›› Issue (1): 10-20.doi: 10.3969/j.issn.0253-2417.2022.01.002

基质固相分散和HPLC-IT-TOF/MS联用研究漆树木材中多酚成分

陈虹霞¹(), 周昊¹^,², 陶冉¹, 齐志文¹, 李文君¹, 王成章¹^,²^,*()

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. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2021-01-04 出版日期:2022-02-28 发布日期:2022-03-11
通讯作者: 王成章 E-mail:shirenyahui@126.com;wangczlhs@sina.com
作者简介:王成章, 研究员, 博士生导师, 主要从事天然产物研究与利用方面的研究; E-mail: wangczlhs@sina.com
陈虹霞(1983-), 女, 浙江舟山人, 助理研究员, 博士, 从事天然产物化学方面的研究; E-mail: shirenyahui@126.com
基金资助:
国家重点研发计划资助项目(2017YFD0601305);江苏省生物质能源与材料重点实验室开放基金资助项目(JSBEM-S-201908)

Study on Polyphenols in Lacquer Tree by Matrix Solid-phase Dispersion and HPLC-IT-TOF/MS

Hongxia CHEN¹(), Hao ZHOU¹^,², Ran TAO¹, Zhiwen QI¹, Wenjun LI¹, Chengzhang WANG¹^,²^,*()

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. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2021-01-04 Online:2022-02-28 Published:2022-03-11
Contact: Chengzhang WANG E-mail:shirenyahui@126.com;wangczlhs@sina.com

摘要/Abstract

摘要：

采用基质固相分散(MSPD)技术进行漆树木中多酚化合物的提取，根据单因素试验得到优化工艺条件为：ZSM-22为吸附基质，吸附基质与样品的质量比为2∶1，洗脱溶剂为体积分数70%甲醇，洗脱溶剂用量8 mL，研磨时间2 min。在此条件下，漆树木多酚提取得率为(466±2.05) mg/g (以没食子酸计)。采用高效液相色谱-离子阱-飞行时间质谱(HPLC-IT/TOF-MS)联用技术，建立高效、准确鉴定漆树木中多酚化学成分的方法，根据质谱图和裂解规律信息，并结合文献，共鉴定10个化合物，包括3个没食子酸(GAC)类化合物和7个黄酮类化合物，分别是没食子酸、没食子酸甲酯、没食子酸乙酯、黄颜木素、花旗松素、3，4', 7-三羟基黄烷酮、异鼠李素、槲皮苷、漆黄素和硫黄菊素。利用基质固相分散和HPLC-IT/TOF-MS技术有利于漆树木中化合物的发现和鉴别，对漆树提取物的质量评价和后续分析具有重要的意义。

关键词: 基质固相分散, 漆树, 多酚, 高效液相色谱-离子阱-飞行时间质谱

Abstract:

Matrix solid-phase dispersion was proposed to extract polyphenols in Toxicodendron vernicifluum (Stokes) F. A. Barkl. (Shaanxi lacquer tree). The MSPD conditions to extract polyphenols established by the single factor test were ZSM-22 as the adsorbent, adsorbent/sample ratio of 2:1 (g: g), grinding for 2 min, and use of 8 mL of 70% methanol as the elution solvent. Under these conditions, the polyphenols content of MSPD extraction was (466 ±2. 05)mg/g(calculated by gallic acid). An efficient and accurate method for identification of polyphenols in Shaanxi lacquer tree was established by HPLC-IT-TOF/MS. According to mass spectrometry, fragmentation pathway combined with published reports, total of 10 components were identified, including 3 gallic acid derivatives and 7 flavonoids as follows: gallic acid, methyl gallate, ethyl gallate, fustin, taxifolin, garbanzol, isorhamnetin, quercitrin, fisetin, sulfuretin. It was beneficial to the discovery and identification of compounds in Shaanxi lacquer tree by matrix solid-phase dispersion coupled with HPLC-IT-TOF/MS, and it could be significance for the analysis and quantification of extracts from Shaanxi lacquer tree samples.

Key words: matrix solid-phase dispersion, lacquer tree, polyphenols, HPLC-ESI-TOF-MS

中图分类号:

TQ351

陈虹霞, 周昊, 陶冉, 齐志文, 李文君, 王成章. 基质固相分散和HPLC-IT-TOF/MS联用研究漆树木材中多酚成分[J]. 林产化学与工业, 2022, 42(1): 10-20.

Hongxia CHEN, Hao ZHOU, Ran TAO, Zhiwen QI, Wenjun LI, Chengzhang WANG. Study on Polyphenols in Lacquer Tree by Matrix Solid-phase Dispersion and HPLC-IT-TOF/MS[J]. Chemistry and Industry of Forest Products, 2022, 42(1): 10-20.

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峰号 No.	t/min	准分子离子峰 quasi-molecular ion peak	负离子模式下碎片峰 fragment peak in negative ion mode	分子式 molecular formula	鉴定结果 appraisal result
1	1.133	169.0173[M-H]^-	125.0277	C₇H₆O₅	没食子酸 gallic acid
2	3.187	183.0321[M-H]^-	125.0192	C₈H₈O₅	没食子酸甲酯 methyl gallate
3	6.200	197.0482[M-H]^-	169.0171, 124.9759	C₉H₁₀O₅	没食子酸乙酯 ethyl gallate
4	7.400	287.0564[M-H]^- 289.0703[M+H]⁺	269.0497, 254.9302, 226.9803, 150.9935	C₁₅H₁₂O₆	黄颜木素 fustin
5	9.587	303.0521[M-H]^- 305.0668[M+H]⁺	275.0532, 271.0604, 242.9193, 179.0254, 150.9933	C₁₅H₁₂O₇	花旗松素 taxifolin
6	10.760	271.0631[M-H]^- 273.0755[M+H]⁺	243.0669, 238.9312, 226.9801, 162.9949	C₁₅H₁₂O₅	3, 4′, 7-三羟基黄烷酮 garbanzol
7	11.933	315.0512[M-H]^- 317.0651[M+H]⁺	301.0479, 255.0420, 178.9299, 150.9933	C₁₆H₁₂O₇	异鼠李素 isorhamnetin
8	13.453	447.0941[M-H]^- 449.1070[M+H]⁺	300.0273, 271.2206, 255.0471, 242.9359	C₂₁H₂₀O₁₁	槲皮苷 quercitrin
9	14.720	285.0405[M-H]^- 287.0552[M+H]⁺	257.0923, 228.9805, 162.9942	C₁₅H₁₀O₆	漆黄素 fisetin
10	17.920	269.0454[M-H]^- 271.0597[M+H]⁺	240.9241, 222.9809, 136.9943	C₁₅H₁₀O₅	硫黄菊素 sulfuretin

提取方法 extraction method	分析方法 analysis method	分析物¹⁾ analyte	样品量/g sample dose	溶剂solvent		条件condition		参考文献 reference
提取方法 extraction method	分析方法 analysis method	分析物¹⁾ analyte	样品量/g sample dose	种类 type	用量 dose/mL	时间/min time	温度/℃ temp.	参考文献 reference
热回流提取 heat reflux extraction	UV	总多酚 total polyphenols	1	水 water	25	555	89.95	[22]
热回流提取 heat reflux extraction	LC-MS/MS	主要化学成分 main chemical	3	60%乙醇水溶液alcohol solution	90	600	85	[6]
热回流提取 heat reflux extraction	LC-MS/MS	主要化学成分 main chemical	100	水water	1000	180	100	[15]
负压提取 vacuum extraction	UV	总多酚 total polyphenols	5	83%乙醇水溶液 alcohol solution	100	90	—	[7]
MSPD	UV+ HPLC-IT-TOF/MS	总多酚，主要化学成分 total polyphenols, main chemical	0.2	70%甲醇水溶液 methanol solution	8	30	常温 room temp.	本研究 this study

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基质固相分散和HPLC-IT-TOF/MS联用研究漆树木材中多酚成分

Study on Polyphenols in Lacquer Tree by Matrix Solid-phase Dispersion and HPLC-IT-TOF/MS

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