LC-TOF/MS快速鉴定女贞子4种环烯醚萜苷类化合物模拟清蒸品的化学成分
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摘要
目的:通过LC-TOF/MS快速鉴定女贞子4种环烯醚萜苷类化合物(特女贞苷、新女贞苷、橄榄苦苷、女贞苷)模拟清蒸品的化学成分,探讨女贞子蒸制过程中环烯醚萜苷类成分的转化机制。方法:色谱条件为流动相乙腈(A)-0.1%甲酸溶液(B)梯度洗脱(0~5 min,7%~12%A;5~20 min,12%~25%A;20~30 min,25%~40%A;30~35 min,40%~100%A),流速0.2 m L·min-1,柱温25℃,进样量3μL,检测波长240 nm;质谱使用Agilent 6230型LC-TOF/MS联用系统,在ESI/MS正离子模式下采集数据。通过对照品定位、质谱数据及文献参照分析4种环烯醚萜苷类化合物模拟清蒸品的化学成分。结果:4种环烯醚萜苷类化合物模拟清蒸品中均检出了橄榄酸;特女贞苷模拟清蒸品中还检出红景天苷和2种特女贞苷异构体;新女贞苷模拟清蒸品中鉴定出了3,4-二羟基苯乙基-β-D-葡萄糖苷;橄榄苦苷和女贞苷模拟清蒸品中分别检出其各自的苷元羟基酪醇和酪醇。结论:女贞子中环烯醚萜苷类成分性质不稳定,加水、加热可使其水解生成次级苷或者苷元,特女贞苷在模拟炮制过程中可转化为其异构体。女贞子酒蒸后补肝肾药效增强与其环烯醚萜苷类成分水解密切相关。
Objective: To identify chemical components in Ligustri Lucidi Fructus by simulation of its steamed products with four secoiridoid glycosides,and discuss transformation mechanism of secoiridoid glycosides in Ligustri Lucidi Fructus during steaming process. Method: HPLC was employed with mobile phase of acetonitrile-0. 1% formic acid solution for gradient elution and detection wavelength at 240 nm. Agilent 6230 LCTOF / MS coupling system was adopted. Chemical components in Ligustri Lucidi Fructus by simulation of its steamed products with four secoiridoid glycosides were determined by reference positioning,mass spectrometry data and literature reference. Result: Olivanic acid was determined in four simulation of steamed products; salidroside and two kinds of specnuezhenide isomers were detected in specnuezhenide simulation of steamed products; 3,4-dihydroxy-ethyl-β-D-glucoside was identified in neonuezhenide simulation of steamed products; oleuropein and ligustroside simulation of steamed products were detected their respective glycosides of hydroxytyrosol and tyrosol.Conclusion: Property of secoiridoid glycosides in Ligustri Lucidi Fructus is instable,water and heating can make them hydrolysis to produce its secondary glycosides or glycosides, specnuezhenide can convert into its isomer during simulation process. The enhancement of tonifying liver and kidney efficacy of Ligustri Lucidi Fructus is closely related to hydrolysis of its secoiridoid glycosides.
Objective: To identify chemical components in Ligustri Lucidi Fructus by simulation of its steamed products with four secoiridoid glycosides,and discuss transformation mechanism of secoiridoid glycosides in Ligustri Lucidi Fructus during steaming process. Method: HPLC was employed with mobile phase of acetonitrile-0. 1% formic acid solution for gradient elution and detection wavelength at 240 nm. Agilent 6230 LCTOF / MS coupling system was adopted. Chemical components in Ligustri Lucidi Fructus by simulation of its steamed products with four secoiridoid glycosides were determined by reference positioning,mass spectrometry data and literature reference. Result: Olivanic acid was determined in four simulation of steamed products; salidroside and two kinds of specnuezhenide isomers were detected in specnuezhenide simulation of steamed products; 3,4-dihydroxy-ethyl-β-D-glucoside was identified in neonuezhenide simulation of steamed products; oleuropein and ligustroside simulation of steamed products were detected their respective glycosides of hydroxytyrosol and tyrosol.Conclusion: Property of secoiridoid glycosides in Ligustri Lucidi Fructus is instable,water and heating can make them hydrolysis to produce its secondary glycosides or glycosides, specnuezhenide can convert into its isomer during simulation process. The enhancement of tonifying liver and kidney efficacy of Ligustri Lucidi Fructus is closely related to hydrolysis of its secoiridoid glycosides.
引文
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[16]李转梅,张学兰,李慧芬,等.女贞子酒蒸过程中新女贞苷、木樨榄苷-11-甲酯和女贞酸的动态变化[J].中国实验方剂学杂志,2014,20(12):14-17.
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[18]梁晓,吴鹏,张学兰,等.女贞子不同炮制品HPLC指纹图谱色谱峰的归属与比较[J].中药材,2015,38(11):2288-2291.
[19]占方玲,张学兰,蒋海强,等.女贞子生制品化学成分的HPLC-ESI/MS分析[J].中成药,2013,35(12):2707-2710.
[2]徐苹,张学兰.女贞子炮制历史沿革研究[J].山东中医药大学学报,2008,32(3):263-265.
[3]赵丽丽,冯毅凡.女贞子中三萜类和环烯醚萜类成分研究进展[J].广东药学院学报,2012,28(1):107-111.
[4]刘净,梁敬钰,谢韬.环烯醚萜类化合物近年研究进展[J].海峡药学,2004,16(1):14-19.
[5]乔卫,张彦文,吴寿金.天然环烯醚萜类化合物的生物活性[J].国外医学·植物药分册,2001,16(2):65-67.
[6]蔡溱,石力夫,胡晋红,等.特女贞甙体外对小鼠脾淋巴细胞转化和自然杀伤细胞活性的影响[J].第二军医大学学报,1998,19(1):76-78.
[7]Han J,Talorete T P,Yamada P,et al.Anti-proliferative and apoptotic effects of oleuropein and hydroxytyrosol on human breast cancer MCF-7 cells[J].Cytotechnology,2009,59(1):45-53.
[8]Al-Azzawie H F,Alhamdani M S.Hypoglycemic and antioxidant effect of oleuropein in alloxan-diabetic rabbits[J].Life Sci,2006,78(12):1371-1377.
[9]张奕,刘永刚.红景天苷抗肝纤维化的实验研究[J].中国药房,2006,17(11):813-815.
[10]张明发,沈雅琴.红景天苷及其苷元酪醇的心血管保护作用[J].中国新药杂志,2012,21(21):2521-2525.
[11]Hashim Y Z,Rowland I R,Mc Glynn H,et al.Inhibitory effects of olive oil phenolics on invasion in human colon adenocarcinoma cells in vitro[J].Int J Cancer,2008,122(3):495-500.
[12]Hamden K,Allouche N,Damak M,et al.Hypoglycemic and antioxidant effects of phenolic extracts and purified hydroxytyrosol from olive mill waste in vitro and in rats[J].Chem Biol Interact,2009,180(3):421-432.
[13]Zhi L,Liu Z B,Feng Z H,et al.Hydroxytyrosol protects against oxidative damage by pigment simultaneous activation of mitochondrial biogenesis and phaseⅡdetoxifying enzyme systems in retinal epithelial cells[J].J Nutr Biochem,2010,21(11):1089-1098.
[14]Hagiwara K,Goto T,Araki M,et al.Olive polyphenol hydroxytyrosol prevents bone loss[J].Eur J Pharmacol,2011,662(1/3):78-84.
[15]姜秋,蒋海强,张学兰,等.女贞子酒蒸过程中4种裂环环烯醚萜苷类成分的动态变化[J].中成药,2014,36(12):2561-2564.
[16]李转梅,张学兰,李慧芬,等.女贞子酒蒸过程中新女贞苷、木樨榄苷-11-甲酯和女贞酸的动态变化[J].中国实验方剂学杂志,2014,20(12):14-17.
[17]姜秋,蒋海强,张学兰,等.女贞子酒蒸过程中5种苯乙醇类成分的变化规律[J].中国实验方剂学杂志,2014,20(16):60-63.
[18]梁晓,吴鹏,张学兰,等.女贞子不同炮制品HPLC指纹图谱色谱峰的归属与比较[J].中药材,2015,38(11):2288-2291.
[19]占方玲,张学兰,蒋海强,等.女贞子生制品化学成分的HPLC-ESI/MS分析[J].中成药,2013,35(12):2707-2710.