UPLC-LTQ-Orbitrap HRMS法结合特征裂解途径分析玄参水提物中化学成分
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摘要
目的采用UPLC-LTQ-Orbitrap HRMS法结合不同化学成分群的特征裂解途径对玄参水提物中的化学成分进行快速定性分析。方法采用Acquity UPLC~?BEH C_(18)柱(100 mm×2.1 mm,1.7μm),以甲醇-0.1%甲酸水溶液为流动相,梯度洗脱,体积流量为0.2 mL/min,质谱使用ESI离子源,正离子模式下采集数据。结果根据对照品质谱数据总结出环烯醚萜类和苯丙素类成分的裂解规律。通过分析玄参水提物的质谱数据及化合物元素组成,并结合裂解规律和相关文献及Clog P值等,鉴定出61个化合物,包括28个环烯醚萜类、27个苯丙素类以及6个其他类。其中3个乙酰化安格洛苷C和methoxylscrophuloside B4为新化合物,stegioside Ⅲ为玄参中首次发现。结论 UPLC-LTQ-Orbitrap HRMS法能够对玄参水提物中化学成分进行快速、全面地分析,为玄参的药效物质基础阐明和质量控制提供参考。
Objective To rapidly identify the chemical constituents from the aqueous extract of Scrophulariae Radix by UPLC-LTQOrbitrap HRMS combined with cleavage pathways of different chemical constituent cluster. Methods The analysis was performed on an Acquity UPLC~? BEH C_(18) column(100 mm ×2.1 mm, 1.7 μm). The mobile phase consisted of methanol and 0.1% formic acid aqueous solution was used for gradient elution, with a flow rate of 0.20 mL/min. ESI ion source was applied for mass spectra under positive mode. Results The cleavage pathways of iridoids and phenylpropanoids were summarized based on mass data of standards.The constituents of the aqueous extract of Scrophulariae Radix were further analyzed by using the mass data and element compositions analysis, and referring with the cleavage pathways, literatures and Clog P value. A total of 61 constituents were identified, including 28 iridoids, 27 phenylpropanoids, and six others. Among them, three acetylangoroside C and methoxylscrophuloside B4 were new compounds, and stegioside Ⅲ was identified from Scrophulariae Radix for the first time. Conclusion UPLC-LTQ-Orbitrap HRMS can rapidly and comprehensively characterize the chemical constituents of the aqueous extract of Scrophulariae Radix, which provides a reference for the clarification of efficacy material basis and quality control of Scrophulariae Radix.
Objective To rapidly identify the chemical constituents from the aqueous extract of Scrophulariae Radix by UPLC-LTQOrbitrap HRMS combined with cleavage pathways of different chemical constituent cluster. Methods The analysis was performed on an Acquity UPLC~? BEH C_(18) column(100 mm ×2.1 mm, 1.7 μm). The mobile phase consisted of methanol and 0.1% formic acid aqueous solution was used for gradient elution, with a flow rate of 0.20 mL/min. ESI ion source was applied for mass spectra under positive mode. Results The cleavage pathways of iridoids and phenylpropanoids were summarized based on mass data of standards.The constituents of the aqueous extract of Scrophulariae Radix were further analyzed by using the mass data and element compositions analysis, and referring with the cleavage pathways, literatures and Clog P value. A total of 61 constituents were identified, including 28 iridoids, 27 phenylpropanoids, and six others. Among them, three acetylangoroside C and methoxylscrophuloside B4 were new compounds, and stegioside Ⅲ was identified from Scrophulariae Radix for the first time. Conclusion UPLC-LTQ-Orbitrap HRMS can rapidly and comprehensively characterize the chemical constituents of the aqueous extract of Scrophulariae Radix, which provides a reference for the clarification of efficacy material basis and quality control of Scrophulariae Radix.
引文
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[12]赵新峰,李平,孙毓庆.熟地黄的高效液相色谱/电喷雾电离-质谱分析[J].药物分析杂志,2007,27(6):874-876.
[13]王静哲,刘震,马立满,等.基于UPLC-Q-TOF MS分析加工炮制对玄参化学成分的影响[J].质谱学报,2016,37(1):1-9.
[14]Dinda B,Debnath S,Harigaya Y.Naturally occurring iridoids.[J].Chem Pharm Bull,2007,55(2):159-222.
[15]Nguyen A T,Fontaine J,Malonne H,et al.A sugar ester and an iridoid glycoside from Scrophularia ningpoensis[J].Phytochemistry,2005,66(10):1186-1191.
[16]Gu W L,Chen C X,Huang X Y,et al.The effect of angoroside C on pressure overload-induced ventricular remodeling in rats[J].Phytomedicine,2015,22(7/8):705-712.
[17]Yang Z,Wu Q Q,Xiao Y,et al.Aucubin protects against myocardial infarction-induced cardiac remodeling via n NOS/NO-regulated oxidative stress[J].Oxid Med Cell Long,2018,2018:1-15.
[18]Zhao J,Liu T,Ma L,et al.Protective effect of acteoside on immunological liver injury induced by Bacillus Calmette-Guerin plus lipopolysaccharide[J].Planta Med,2009,75(14):1463-1469.
[2]胡瑛瑛,黄真.玄参的化学成分及药理作用研究进展[J].浙江中医药大学学报,2008,32(2):268-270.
[3]Wu Q,Yuan Q,Liu E H,et al.Fragmentation study of iridoid glycosides and phenylpropanoid glycosides in Radix Scrophulariae by rapid resolution liquid chromatography with diode-array detection and electrospray ionization time-of-flight mass spectrometry[J].Biomed Chromatogr,2010,24(8):808-819.
[4]Chen Y H,Qi J,Hua J,et al.Structural characterization and identification of major constituents in Radix Scrophulariae by HPLC coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry[J].Chin J Nat Med,2014,12(1):47-54.
[5]王静哲,徐风,刘震,等.玄参化学成分的HPLC-ESI-IT-TOF-MS分析[J].中国中药杂志,2016,41(7):1257-1268.
[6]Gu W L,Chen C X,Wu Q,et al.Effects of chinese herb medicine Radix Scrophulariae on ventricular remodeling[J].Pharmazie,2010,65(10):770-775.
[7]顾伟梁,陈长勋,王樱,等.玄参水提物对心室重构大鼠心肌纤维化的影响[J].中草药,2008,39(9):1371-1374.
[8]顾伟梁,陈长勋,王樱.玄参和附子抗鼠心肌肥厚作用的对比实验研究[J].中西医结合学报,2008,6(4):376-380.
[9]刘冠璋,董婉茹,于卉,等.玄参水提物对CCl4所致大鼠急性肝损伤的保护作用研究[J].吉林中医药,2015,35(5):504-507.
[10]Lin L,Lin H,Zhang M,et al.Types,principle,and characteristics of tandem high-resolution mass spectrometry and its applications[J].RSC Adv,2015,5(130):107623-107636.
[11]徐露露,焦其树,杨佳颖,等.UPLC-LTQ-Orbitrap HRMS法结合特征裂解途径分析鉴定薄荷水提物中4种类群化学成分[J].质谱学报,2018,39(4):424-432.
[12]赵新峰,李平,孙毓庆.熟地黄的高效液相色谱/电喷雾电离-质谱分析[J].药物分析杂志,2007,27(6):874-876.
[13]王静哲,刘震,马立满,等.基于UPLC-Q-TOF MS分析加工炮制对玄参化学成分的影响[J].质谱学报,2016,37(1):1-9.
[14]Dinda B,Debnath S,Harigaya Y.Naturally occurring iridoids.[J].Chem Pharm Bull,2007,55(2):159-222.
[15]Nguyen A T,Fontaine J,Malonne H,et al.A sugar ester and an iridoid glycoside from Scrophularia ningpoensis[J].Phytochemistry,2005,66(10):1186-1191.
[16]Gu W L,Chen C X,Huang X Y,et al.The effect of angoroside C on pressure overload-induced ventricular remodeling in rats[J].Phytomedicine,2015,22(7/8):705-712.
[17]Yang Z,Wu Q Q,Xiao Y,et al.Aucubin protects against myocardial infarction-induced cardiac remodeling via n NOS/NO-regulated oxidative stress[J].Oxid Med Cell Long,2018,2018:1-15.
[18]Zhao J,Liu T,Ma L,et al.Protective effect of acteoside on immunological liver injury induced by Bacillus Calmette-Guerin plus lipopolysaccharide[J].Planta Med,2009,75(14):1463-1469.