基于UPLC-Q-Exactive-MS/MS的藜麦皂苷提取物及入血成分分析

王伟宏; 胡菊丽; 吴定涛; 王诗洁; 蒋红; 邹亮; 胡一晨

doi:10.13386/j.issn1002-0306.2022050100

基于UPLC-Q-Exactive-MS/MS的藜麦皂苷提取物及入血成分分析

doi: 10.13386/j.issn1002-0306.2022050100

农业农村部杂粮加工重点实验室，四川省杂粮产业化工程技术研究中心，成都大学食品与生物工程学院，四川成都 610106

基金项目: 内蒙古自治区科学技术厅中央引导地方科技发展资金项目（2022ZY0138）；农业国家标准和行业标准制修订项目（HYB-20357）。

详细信息

作者简介:
王伟宏（1997−），男，硕士研究生，研究方向：食品加工与安全，E-mail：617737751@qq.com

通讯作者:
胡一晨（1987−），女，博士，副教授，研究方向：食品功能营养因子评价与分析，E-mail：huyichen0323@126.com

中图分类号: TS219
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出版历程
- 收稿日期: 2022-05-11
- 刊出日期: 2023-05-01

Analysis of Quinoa Saponin Extract and Blood Constituents Based on UPLC-Q-Exactive-MS/MS

Key Laboratory of Coarse Cereal Processing of Ministry of Agriculture and Rural Affairs, Sichuan Engineering and Technology Research Center of Coarse Cereal Industrialization, College of Food and Biological Engineering, Chengdu University, Chengdu 610106, China

摘要

摘要: 运用超高效液相色谱-四级杆-静电场轨道离子阱联用质谱（UPLC-Q-Exactive-MS/MS）对藜麦皂苷提取物的主要化学成分及大鼠口服入血成分进行分析鉴定。采用Hypersil Gold VANQUISH C₁₈色谱柱（2.1 mm×100 mm，1.8 μm），流动相为甲酸水-甲酸乙腈梯度洗脱，柱温30 ℃，分析时间35 min，流速0.3 mL·min⁻¹。采用电喷雾离子源（ESI），正、负离子源，Full ms/dd-ms²模式检测。结果显示方法的回收率、基质效应、精密度和稳定性等均符合生物样品的测定要求。在藜麦皂苷提取物中共鉴定到15种皂苷，按苷元构型分为齐墩果酸型皂苷3种，常春藤型皂苷5种，商陆酸型皂苷6种，Serjanic acid型皂苷1种。选用雄性Sprague-Dawley（SD）大鼠，以175.5 mg·kg⁻¹灌胃给予藜麦皂苷提取物，于给药后0、0.5、1、2、4 h下，眼眶取血，大鼠血浆以盐酸丁螺环酮为内标，用甲醇沉淀蛋白，离心，微孔滤膜过滤后进样分析。结果显示在入血成分中共检测到6种原型皂苷以及微量水解后的常春藤皂苷元和Serjanic acid苷元。通过对提取物组成成分及入血成分分析，共鉴定出藜麦皂苷中15个皂苷类化合物及裂解规律，发现了大鼠血浆入血成分相对含量变化情况。初步阐明了藜麦三萜皂苷的化学组成以及体内代谢特征，为藜麦进一步研究和开发应用提供理论依据。
- 超高效液相色谱-四级杆-静电场轨道离子阱联用质谱 /
- 藜麦 /
- 皂苷提取物 /
- 代谢物
Abstract: The main chemical components of saponins extracted from quinoa and the components in the blood of rat after oral administration were analyzed and identified by ultra-performance liquid chromatography coupled with Q-Exactive mass spectrometry (UPLC-Q-Exactive-MS/MS). Hypersil Gold VANQUISH C₁₈ column (2.1 mm×100 mm, 1.8 μm) was used. The mobile phase was formic acid water-formic acid acetonitrile gradient elution, the column temperature was 30 ℃, the analysis time was 35 min, the flow rate was 0.3 mL·min⁻¹. Electrospray ion source (ESI), positive and negative ion sources and Full ms/dd-ms² mode were used for detection. The results showed that the recovery rate, matrix effect, precision and stability of the method met the requirements of biological samples. A total of 15 saponins were identified in the saponin extract of quinoa, which were divided into three oleanolic acid saponin types, five hederagenin saponin types, six phytolaccagenic acid saponin types and one serjanic acid saponin type according to the configuration of aglycones. Male Sprague Dawley (SD) rats were selected as the experimental object, after intragastric administration of quinoa saponin extract at 175.5 mg·kg⁻¹, at 0, 0.5, 1, 2 and 4 hours after administration, blood was taken from the orbit, the plasma of rats took buspirone hydrochloride as the internal standard, precipitated protein with methanol, centrifuged, filtered by microporous membrane, and then injected for analysis. The results showed that six prototype saponins and trace hydrolyzed hederagenin and serjanic acid glycosides were detected in the blood components of rat plasma. Through the analysis of the components of the extract and the components entering the blood, 15 saponins in quinoa saponins were identified and their cleavage laws were found, and the changes in the relative contents of the components into the blood of rat plasma were found. The chemical composition and metabolic characteristics of triterpenoid saponins in quinoa were preliminaries elucidated, which provided a theoretical basis for further research and application of quinoa.
- ultra performance liquid chromatography coupled with q-exactive mass spectrometry (UPLC-Q-Exactive-MS/MS) /
- quinoa /
- saponin extracts /
- metabolite

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图 1 藜麦三萜皂苷中四种主要苷元

注：Ⅰ：齐墩果酸型皂苷元；Ⅱ：常春藤型皂苷元；Ⅲ：商陆酸型皂苷元；Ⅳ：Serjanic acid型皂苷元。

Figure 1. Four main aglycones in triterpene saponins of quinoa

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图 2 空白溶液（A）和藜麦皂苷（B）的基峰色谱图

Figure 2. Base peak chromatogram of blank solution (A) and quinoa saponin (B)

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图 3 在Full ms/dd-ms²扫描模式和正离子模式下的7号商陆酸型皂苷的质谱图与结构图

注：A：7号化合物的结构式；B：正离子模式下商陆酸型皂苷元裂解质谱图；C：正离子模式下7号化合物裂解质谱图；D：7号化合物裂解途径。

Figure 3. Mass spectrum and structure diagram of Phytolaccagenic acid saponins No.7 in Full ms/dd-ms²scanning mode and positive ion mode

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图 4 在Full ms/dd-ms²扫描模式和正离子模式下的9号常春藤型皂苷的质谱图与结构图

注：A：9号化合物的结构式；B:正离子模式下常春藤型皂苷元裂解质谱图；C：正离子模式下9号化合物裂解质谱图；D：9号化合物裂解途径。

Figure 4. Mass spectrum and structure diagram of Hederagenin saponins No.9 in Full ms/dd-ms²scanning mode and positive ion mode

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图 5 在Full ms/dd-ms²扫描模式和正离子模式下的12号齐墩果酸型皂苷的质谱图与结构图

注：A：12号化合物的结构式；B：正离子模式下齐墩果酸型皂苷元裂解质谱图；C：正离子模式下12号化合物裂解质谱图；D：12号化合物裂解途径。

Figure 5. Mass spectrum and structure diagram of Oleanolic acid saponin No.12 in Full ms/dd-ms²scanning mode and positive ion mode

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图 6 在Full ms/dd-ms²扫描模式和正离子模式下的13号Serjania acid型皂苷质谱图与结构图

注：A：13号化合物的结构式；B：正离子模式下齐Serjania acid型皂苷元裂解质谱图；C：正离子模式下13号化合物裂解质谱图；D：13号化合物裂解途径。

Figure 6. Mass spectrum and structure diagram of Serjania acid saponin No.13 in Full ms/dd-ms²scanning mode and positive ion mode

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图 7 大鼠血浆入血成分相对峰面积

注：A_s：待测物峰面积；A_i：内标物峰面积。

Figure 7. Relative peak area of rat plasma entry components

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表 1 稳定性、精密度、重复性和回收率结果

Table 1. Results of stability, precision, repeatability and recovery

对照品	稳定性（n=6）			精密度（n=6）			重复性（n=6）			回收率（n=6）
对照品	A_s	A_s/A_i	RSD（%）	A_s	A_s/A_i	RSD（%）	A_s	A_s/A_i	RSD（%）	回收率	平均值（%）	RSD（%）
常春藤皂苷元	65276793	0.6509051	5.13%	58776618	0.5860888	8.17	55589876	0.5543124	4.87	108.35	106.38	7.32
	68449264	0.7079094		54238415	0.5609393		57209525	0.5916668		105.68
	71622412	0.6908903		69137173	0.6669170		62144197	0.5994607		108.35
	36914345	0.7173293		28240396	0.5487748		29428614	0.5718646		106.92
	66643096	0.6265274		56605792	0.5321644		56595046	0.5320633		103.65
	68784785	0.6893669		58026145	0.5815429		53844778	0.5396369		105.33
齐墩果酸	81124476	0.8089297	7.22%	117086024	1.1675190	9.26	98908215	0.9862596	8.56	88.68	91.36	8.63
	71172099	0.7360692		102842673	1.0636096		91812677	0.9495362		92.25
	88617222	0.8548272		125210202	1.2078136		94167436	0.9083661		89.51
	39899715	0.7753418		53468272	1.0390096		45216655	0.8786620		89.37
	96098748	0.9034470		103893203	0.9767245		84544198	0.7948199		94.59
	80677821	0.8085600		96340014	0.9655278		80717047	0.8089531		93.81
注：A_s：待测物峰面积；A_i：内标物峰面积。

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表 2 UPLC-Q-Exactive-MS/MS鉴定藜麦三萜皂苷类成分的质谱数据

Table 2. Identification of triterpenoid saponins from quinoa by UPLC-Q-Exactive-MS/MS

编号	化合物鉴定	化学式	正离子模式[M+H]⁺	保留时间（min）	dd-MS²扫描模式下碎片离子（m/z）
编号	化合物鉴定	化学式	正离子模式[M+H]⁺	保留时间（min）	Ⅰ	Ⅱ	Ⅲ	Ⅳ
1	Hederagenin 3-O-[α-L-arabinopyranosyl-(1,3)-β-D-glucuronopyranosyl]-28-O-β-D-glucopyranoside 常春藤皂苷元3-O-[α-L-吡喃阿拉伯糖-（1,3）-β-D-吡喃葡萄糖]-28-O-β-D-吡喃葡萄糖苷	C₄₇H₇₆O₁₈	929.51093	8.52	767.45898	635.41531	473.36304
2	Phytolaccagenic acid 3-O-α-L-arabinopyranosyl-28-O-β-D-glucopyranoside 商陆酸3-O-α-L-吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖苷	C₄₂H₆₆O₁₅	811.44692	8.79	649.39771	517.35339
3	Phytolaccagenic acid 3-O-[β-D-glucopyranosyl-(1,4)-β-D-glucopyranosyl-(1,4)-β-D-glucopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃葡萄糖-（1,4）-β-D-吡喃葡萄糖-（1,4）-β-D-吡喃葡萄糖]-28-O-β-D-吡喃葡萄糖苷	C₅₅H₈₈O₂₆	1165.56128	9.12	1003.51030	841.45740	679.40479	517.35272
4	Phytolaccagenic acid 3-O-[β-D-galactopyranosyl-(1,3)-β-D-glucopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃半乳糖-（1,3）-β-D-吡喃葡萄糖]-28-O-β-D-吡喃葡萄糖苷	C₄₉H₇₈O₂₁	1003.51044	9.47	841.45624	679.40515	517.35291
5	Phytolaccagenic acid 3-O-[β-D-glucopyranosyl-(1,3)-β-D-galactopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃葡萄糖-（1,3）-β-D-吡喃半乳糖]-28-O-β-D-吡喃葡萄糖苷	C₄₉H₇₈O₂₁	1003.51013	9.86	841.45844	679.40558	517.35321
6	Phytolaccagenic acid 3-O-[β-D-glucopyranosyl-(1,2)-β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃葡萄糖-（1,2）-β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₅₄H₈₆O₂₅	1135.55347	10.29	973.50056	811.44745	649.39423	517.35278
7	Phytolaccagenic acid 3-O-[β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₄₈H₇₆O₂₀	973.50055	11.05	811.44836	649.39435	517.35333
8	Hederagenin 3-O-[β-D-glucopyranosyl-(1,3)-α-L-galactopyranosyl]-28-O-β-D-glucopyranoside 常春藤皂苷元3-O-[β-D-吡喃葡萄糖-（1,3）-α-L-吡喃半乳糖]-28-O-β-D-吡喃葡萄糖苷	C₄₈H₇₈O₁₉	959.51984	11.27	797.46783	635.41577	473.36346
9	Hederagenin 3-O-[β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 常春藤皂苷元3-O-[β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₄₇H₇₆O₁₈	929.51099	11.73	767.45789	605.40521	473.36298
10	Hederagenin 3-O-[β-D-glucopyranosyl-(1,2)-β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 常春藤皂苷元3-O-[β-D-吡喃葡萄糖-（1,2）-β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₅₃H₈₆O₂₃	1091.56128	12.05	929.5116	767.45801	605.40508	473.36319
11	Hederagenin 3-O-α-L-arabinopyranosyl-28-O-β-D-glucopyranoside 常春藤皂苷元3-O-α-L-吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖苷	C₄₁H₆₆O₁₃	767.45764	12.35	605.40472	473.36237
12	Oleanolic acid 3-O-[β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 齐墩果酸3-O-[β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₄₇H₇₆O₁₇	913.51752	12.48	751.46002	589.40045	457.36682
13	Serjanic acid 3-O-[β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside Serjanic acid 3-O-[β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₄₈H₇₆O₁₉	957.50568	13.41	795.45209	633.39984	501.35756
14	Oleanolic acid 3-O-β-D-glucuronopyranosyl-28-O-β-D-glucopyranoside 齐墩果酸3-O-β-D-吡喃葡萄糖-28-O-β-D-吡喃葡萄糖苷	C₄₂H₆₆O₁₄	795.45297	13.44	633.39948	457.36593
15	Oleanolic acid 3-O-[α-L-arabinopyranosyl-(1,3)-β-D-glucuronopyranosyl]-28-O-β-D-glucopyranoside 齐墩果酸3-O-[α-L-吡喃阿拉伯糖-（1,3）-β-D-吡喃葡萄糖]-28-O-β-D-吡喃葡萄糖苷	C₄₇H₇₄O₁₈	927.49304	14.02	765.44299	633.39995	457.36887

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表 3 大鼠血浆入血成分相对峰面积

Table 3. Relative peak area of rat plasma entry components

编号	化合物鉴定	化学式	模式[M-H]⁻	保留时间t_R（min）	相对峰面积（A_s/A_i）
编号	化合物鉴定	化学式	模式[M-H]⁻	保留时间t_R（min）	0.5 h	1 h	2 h	4 h
2	Phytolaccagenic acid 3-O-α-L-arabinopyranosyl-28-O-β-D-glucopyranoside 商陆酸3-O-α-L-吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖苷	C₄₂H₆₆O₁₅	809.43289	11.27	0.17098± 0.02866	0.14143± 0.05608	0.14780± 0.04169	0.04774
5	Phytolaccagenic acid 3-O-[β-D-glucopyranosyl-(1,3)-β-D-galactopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃葡萄糖-（1,3）-β-D-吡喃半乳糖]-28-O-β-D-吡喃葡萄糖苷	C₄₉H₇₈O₂₁	1001.49628	9.88	0.12522± 0.02067	0.07786± 0.00196	0.03245± 0.00825
6	Phytolaccagenic acid 3-O-[β-D-glucopyranosyl-(1,2)-β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃葡萄糖-（1,2）-β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₅₄H₈₆O₂₅	1133.53854	10.28	0.12859± 0.03949	0.05083± 0.00175	0.00794± 0.00563
7	Phytolaccagenic acid 3-O-[β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 商陆酸3-O-[β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₄₈H₇₆O₂₀	971.48572	10.34	0.10510± 0.01793	0.08419± 0.03161	0.04042± 0.01253	0.03210
10	Hederagenin 3-O-[β-D-glucopyranosyl-(1,2)-β-D-glucopyranosyl-(1,3)-α-L-arabinopyranosyl]-28-O-β-D-glucopyranoside 常春藤皂苷元3-O-[β-D-吡喃葡萄糖-（1,2）-β-D-吡喃葡萄糖-（1,3）-α-L-吡喃阿拉伯糖]-28-O-β-D-吡喃葡萄糖苷	C₅₃H₈₆O₂₃	1089.54871	11.42	0.09150± 0.00513	0.04665± 0.00243	0.05090± 0.02008
14	Oleanolic acid 3-O-β-D-glucuronopyranosyl-28-O-β-D-glucopyranoside 齐墩果酸3-O-β-D-吡喃葡萄糖-28-O-β-D-吡喃葡萄糖苷	C₄₂H₆₆O₁₄	793.43798	12.69	0.17367± 0.02133	0.17086± 0.04170	0.09452± 0.01630

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