LCMS-IT-TOF分析栀子炒焦前后化学成分的变化
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摘要
目的:分析焦栀子的化学成分,考察栀子炮制前后的化学成分变化情况,明确焦栀子的药效物质基础。方法:采用液相色谱-离子阱-飞行时间质谱技术(LCMS-IT-TOF),色谱条件为ACQUITY UPLC HSS T3色谱柱(2.1 mm×100 mm,1.8μm),流动相0.005%甲酸水溶液(A)-乙腈(B)梯度洗脱(0～5 min,10%～15%B; 5～8 min,15%B; 8～18 min,15%～95%B; 18～20 min,95%B; 20～22 min,95%～10%B; 22～25 min,10%B),柱温30℃,流速0.4 mL·min-1,进样量2μL;质谱分析使用电喷雾离子源(ESI),分别在正、负离子模式下扫描,扫描范围均为m/z 100～1 000。通过对照品比对、质谱数据分析、文献参考等对各离子峰进行鉴定,并比较炮制前后部分离子峰的峰面积,研究炮制后化学成分的变化情况。结果:共鉴定出了38个化合物,炮制后未产生新的化合物。炮制一定时间后,主要化合物的变化情况为栀子苷、京尼平-1-β-D-龙胆双糖苷、山栀子苷、绿原酸、西红花苷峰面积降低,京尼平苷酸、藏红花酸峰面积增高。结论:该方法能够快速准确地鉴别焦栀子中的化学成分,栀子炮制后环烯醚萜类和西红花苷类成分含量发生了显著变化,这可能与焦栀子的止血活性和心脑血管保护作用有关。
Objective:To rapidly analyze chemical compositions in raw products and stir-fried products of Gardeniae Fructus,and determine the pharmacodynamic material basis of Gardeniae Fructus Praeparatus.Method:Liquid chromatography-ion trap-time-of-flight-mass spectrometry(LCMS-IT-TOF) was performed on ACQUITY UPLC HSS T3 column(2.1 mm × 100 mm,1.8 μm),mobile phase was 0.005% formic acid aqueous solution(A)-acetonitrile(B) for gradient elution(0-5 min,10%-15% B;5-8 min,15% B;8-18 min,15%-95% B;18-20 min,95% B;20-22 min,95%-10% B;22-25 min,10% B),the column temperature was30 ℃ and the flow rate was 0.4 mL·min-1,volume of sample injection was 2 μL;electrospray ionization(ESI)was applied for mass spectrometric analysis under positive and negative ion mode,the scanning ranges were m/z100-1 000.The ion peaks were identified by comparison of control substances,mass spectrometry data analysis and literature references.The peak areas of some ion peaks before and after processing were compared,the changes of chemical compositions in Gardeniae Fructus after processing were investigated.Result:Based on the mass spectral data information and references,a total of 38 compounds were identified,no new compounds were produced after processing.The ion peak areas of main compounds were investigated during the stir-frying processing,the contents of geniposide,genipin-1-β-D-gentiobioside,shanzhiside,chlorogenic acid and crocin in Gardeniae Fructus Praeparatus were decreased;the contents of geniposidic acid and crocetin were increased.Conclusion:The method can rapidly and accurately identify the chemical constituents in Gardeniae Fructus Praeparatus.The changes of iridoids and crocins in Gardeniae Fructus during the stir-frying process may be related to hemostatic activity and protection of cardiovascular and cerebrovascular.
Objective:To rapidly analyze chemical compositions in raw products and stir-fried products of Gardeniae Fructus,and determine the pharmacodynamic material basis of Gardeniae Fructus Praeparatus.Method:Liquid chromatography-ion trap-time-of-flight-mass spectrometry(LCMS-IT-TOF) was performed on ACQUITY UPLC HSS T3 column(2.1 mm × 100 mm,1.8 μm),mobile phase was 0.005% formic acid aqueous solution(A)-acetonitrile(B) for gradient elution(0-5 min,10%-15% B;5-8 min,15% B;8-18 min,15%-95% B;18-20 min,95% B;20-22 min,95%-10% B;22-25 min,10% B),the column temperature was30 ℃ and the flow rate was 0.4 mL·min-1,volume of sample injection was 2 μL;electrospray ionization(ESI)was applied for mass spectrometric analysis under positive and negative ion mode,the scanning ranges were m/z100-1 000.The ion peaks were identified by comparison of control substances,mass spectrometry data analysis and literature references.The peak areas of some ion peaks before and after processing were compared,the changes of chemical compositions in Gardeniae Fructus after processing were investigated.Result:Based on the mass spectral data information and references,a total of 38 compounds were identified,no new compounds were produced after processing.The ion peak areas of main compounds were investigated during the stir-frying processing,the contents of geniposide,genipin-1-β-D-gentiobioside,shanzhiside,chlorogenic acid and crocin in Gardeniae Fructus Praeparatus were decreased;the contents of geniposidic acid and crocetin were increased.Conclusion:The method can rapidly and accurately identify the chemical constituents in Gardeniae Fructus Praeparatus.The changes of iridoids and crocins in Gardeniae Fructus during the stir-frying process may be related to hemostatic activity and protection of cardiovascular and cerebrovascular.
引文
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[16]张阿琴,李迩娜,张仓,等.LC-MS分析消癌平注射液中有机酸类成分[J].中国实验方剂学杂志,2012,18(4):88-90.
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[20]陈向阳,张乐,吴莹,等.LCMS-IT-TOF法快速分析薄荷黄酮部位的主要化学成分[J].北京中医药大学学报,2015,38(8):546-550.
[21]张忠立,左月明,杨雅琴,等.栀子中的黄酮类化学成分研究[J].中国实验方剂学杂志,2013,19(4):79-81.
[22]潘凌云,徐敏,王亿,等.UPLC-ESI-MS/MS法分析藤黄炮制前后化学成分的变化[J].中成药,2016,38(5):1098-1103.
[23]颜晓静,郑博文,张毅达,等.UPLC-Q-TOF/MS分析孟河医派特色猪心血丹参炮制前后化学成分的变化[J].中国实验方剂学杂志,2019,25(9):109-116.
[24]王恩力,董方,姚景春.栀子苷药理学和毒理学研究进展[J].中国药房,2015,26(19):2730-2733.
[25]吴婷,鄢连和,朱美晓.栀子的炮制沿革及炮制品现代研究进展[J].中国药师,2015,18(6):1011-1014.
[26]WANG P,WANG Q,LUO C,et al.Iridoid glycosides extracted from Zhizi(Fructus Gardeniae)decrease collagen-induced platelet aggregation and reduce carotid artery thrombosis in an in vivo rat model[J].J Tradit Chin Med(Engl Ed),2013,33(4):531-534.
[27]王亭.中药栀子有效成分及药理作用的研究进展[J].中国药师,2015,18(10):1782-1784.
[28]SHENG L,QIAN Z,ZHENG S,et al.Mechanism of hypolipidemic effect of crocin in rats:crocin inhibits pancreatic lipase[J].Eur J Pharmacol,2006,543(1/3):116-122.
[29]Lee I A,Lee J H,Baek N I,et al.Antihyperlipidemic effect of crocin isolated from the fructus of Gardenia jasminoides and its metabolite crocetin[J].Biol Pharm Bull,2005,28(11):2106-2110.
[30]TANG F T,QIAN Z Y,LIU P Q,et al.Crocetin improves endothelium-dependent relaxation of thoracic aorta in hypercholesterolemic rabbit by increasing e NOS activity[J].Biochem Pharmacol,2006,72(5):558-565.
[31]Nam K N,Choi Y S,Jung H J,et al.Genipin inhibits the inflammatory response of rat brain microglial cells[J].Int Immunopharmacol,2010,10(4):493-499.
[32]黄滔,穆淑珍,郝小江.栀子化学成分研究[J].中药材,2012,35(12):1950-1952.
[33]马丽.浅论焦栀子的药理作用及用其治疗血证的效果[J].当代医药论丛,2016,14(9):21-22.
[2]王恩力,董方,姚景春.栀子苷药理学和毒理学研究进展[J].中国药房,2015,26(19):2730-2733.
[3]邵坚,罗光明,朱继孝,等.栀子炮制前后7种成分的比较研究[J].中草药,2015,46(11):1629-1633.
[4]陈雁,杨中林,张雷红,等.HPLC-ELSD法测定栀子不同炮制品中栀子苷、藏红花素和藏红花酸的含量[J].中药材,2011,34(5):687-690.
[5]CHEN Q C,ZHANG W Y,YOUN U,et al.Iridoid glycosides from Gardeniae Fructus for treatment of ankle sprain[J].Phytochemistry,2009,70(6):779-784.
[6]HAN Y,WEN J,ZHOU T,et al.Chemical fingerprinting of Gardenia jasminoides Ellis by HPLC-DAD-ESI-MScombined with chemometrics methods[J].Food Chem,2015,188:648-657.
[7]WANG L,LIU S,ZHANG X,et al.A strategy for identification and structural characterization of compounds from Gardenia jasminoides by integrating macroporous resin column chromatography and liquid chromatography-tandem mass spectrometry combined with ion-mobility spectrometry[J].J Chromatogr A,2016,1452:47-57.
[8]YANG L,PENG K,ZHAO S,et al.2-Methyl-L-erythritol glycosides from Gardenia jasminoides[J].Fitoterapia,2013,89:126-130.
[9]汪航,冯芳,王学全.栀子大黄汤化学成分的HPLC-PDA-ESI-MS/MS分析[J].中国药科大学学报,2009,40(3):232-237.
[10]乐文,冯芳,王娅.栀子甘草豉汤的LC-PDA-MS/MS分析及抗抑郁作用研究[J].中国药科大学学报,2009,40(4):342-347.
[11]王晓燕,张丽,王添琦,等.栀子化学成分的UHPLC-Q-TOFMS分析[J].中药材,2013,36(3):407-410.
[12]李玲云,王云,刘梦娇,等.栀子金花丸化学成分的UPLC-Q-TOF-MS/MS快速鉴定与分析[J].中国实验方剂学杂志,2017,23(14):1-11.
[13]刘青,曹瑞军,赵欣,等.栀子水提物的HPLC-ESI-MSn分析[J].中成药,2007,29(11):1651-1654.
[14]李存满,骆亚薇,田宝勇.环烯醚萜类化合物的质谱裂解规律研究进展[J].河北师范大学学报:自然科学版,2015,39(6):522-526.
[15]李存满,梁鑫淼,薛兴亚.电喷雾离子源正离子模式下环烯醚萜苷的质谱裂解行为[J].高等学校化学学报,2013,34(3):567-572.
[16]张阿琴,李迩娜,张仓,等.LC-MS分析消癌平注射液中有机酸类成分[J].中国实验方剂学杂志,2012,18(4):88-90.
[17]于金英,王云红,刘国强,等.LC-ESI-MS/MS鉴定菥蓂中芥子油苷及有机酸类成分[J].天然产物研究与开发,2015,27(1):67-72.
[18]于澎,张虹.HPLC-ESI-MS法同时测定虎杖提取物中的17种成分[J].沈阳药科大学学报,2011,28(12):963-968.
[19]田丰,陈婷,王晔尘,等.HPLC-ESI-TOF-MS法快速分离与鉴别益母草药材中的多种化学成分[J].上海中医药大学学报,2014,28(4):86-89.
[20]陈向阳,张乐,吴莹,等.LCMS-IT-TOF法快速分析薄荷黄酮部位的主要化学成分[J].北京中医药大学学报,2015,38(8):546-550.
[21]张忠立,左月明,杨雅琴,等.栀子中的黄酮类化学成分研究[J].中国实验方剂学杂志,2013,19(4):79-81.
[22]潘凌云,徐敏,王亿,等.UPLC-ESI-MS/MS法分析藤黄炮制前后化学成分的变化[J].中成药,2016,38(5):1098-1103.
[23]颜晓静,郑博文,张毅达,等.UPLC-Q-TOF/MS分析孟河医派特色猪心血丹参炮制前后化学成分的变化[J].中国实验方剂学杂志,2019,25(9):109-116.
[24]王恩力,董方,姚景春.栀子苷药理学和毒理学研究进展[J].中国药房,2015,26(19):2730-2733.
[25]吴婷,鄢连和,朱美晓.栀子的炮制沿革及炮制品现代研究进展[J].中国药师,2015,18(6):1011-1014.
[26]WANG P,WANG Q,LUO C,et al.Iridoid glycosides extracted from Zhizi(Fructus Gardeniae)decrease collagen-induced platelet aggregation and reduce carotid artery thrombosis in an in vivo rat model[J].J Tradit Chin Med(Engl Ed),2013,33(4):531-534.
[27]王亭.中药栀子有效成分及药理作用的研究进展[J].中国药师,2015,18(10):1782-1784.
[28]SHENG L,QIAN Z,ZHENG S,et al.Mechanism of hypolipidemic effect of crocin in rats:crocin inhibits pancreatic lipase[J].Eur J Pharmacol,2006,543(1/3):116-122.
[29]Lee I A,Lee J H,Baek N I,et al.Antihyperlipidemic effect of crocin isolated from the fructus of Gardenia jasminoides and its metabolite crocetin[J].Biol Pharm Bull,2005,28(11):2106-2110.
[30]TANG F T,QIAN Z Y,LIU P Q,et al.Crocetin improves endothelium-dependent relaxation of thoracic aorta in hypercholesterolemic rabbit by increasing e NOS activity[J].Biochem Pharmacol,2006,72(5):558-565.
[31]Nam K N,Choi Y S,Jung H J,et al.Genipin inhibits the inflammatory response of rat brain microglial cells[J].Int Immunopharmacol,2010,10(4):493-499.
[32]黄滔,穆淑珍,郝小江.栀子化学成分研究[J].中药材,2012,35(12):1950-1952.
[33]马丽.浅论焦栀子的药理作用及用其治疗血证的效果[J].当代医药论丛,2016,14(9):21-22.