基于UHPLC-Q-TOF MS/MS的胆南星中胆汁酸类成分的质谱裂解规律研究  

Study on the Fragmentation Behavior of Bile Acidsin Bile Arisaema by UHPLC-Q-TOF MS/MS

作　　者：单国顺[1] 赵启苗 潘多 陶鑫[1] 高慧[1] 许枬[1] 贾天柱[1] SHAN Guo-shun;ZHAO Qi-miao;PAN Duo;TAO Xin;GAO Hui;XU Nan;JIA Tian-zhu(School of Pharmacy,Liaoning University of Traditional Chinese Medicine,Dalian 116600,China;School of Xinglin,Liaoning University of Traditional Chinese Medicine,Shenyang 110167,China)

机构地区：[1]辽宁中医药大学药学院,辽宁大连116600 [2]辽宁中医药大学杏林学院,辽宁沈阳110167

出　　处：《质谱学报》2020年第4期340-350,共11页Journal of Chinese Mass Spectrometry Society

基　　金：国家发改委行业专项课题(201507004-03);科技部中药标准化项目(ZYBZH-Y-ZY-45)资助。

摘　　要：采用超高效液相色谱-四极杆-飞行时间串联质谱(UHPLC-Q-TOF MS/MS)法研究胆南星中4种类型25种胆汁酸类成分在电喷雾离子源正、负离子模式下的质谱裂解规律。结果表明,一级质谱中,25种胆汁酸类成分均可得到加氢(脱氢)的准分子离子峰[M+H]+([M—H]^-);二级质谱中,不同类型胆汁酸类成分(包含多种同分异构体)的裂解途径大多是脱去母核上的取代基产生H 2O及CO 2的中性碎片丢失。尤其是甾体母核C17位的功能基团更易裂解,产生一系列特征性碎片离子。游离胆汁酸在正离子模式下可发生A环和C环开裂,产生m/z 175.1123、161.0966、147.0814离子;在负离子模式下可发生中性丢失,形成[M—H—CO 2]^-、[M—H—H 2CO 2]^-、[M—H—H 2O—H 2CO 2]^-离子。此外,在正离子模式下,牛磺酸型胆汁酸可形成牛磺酸基裂解碎片离子m/z 126.0226,甘氨酸型胆汁酸可形成甘氨酸基裂解碎片离子m/z 158.0818;在负离子模式下,牛磺酸型胆汁酸侧链断裂可产生丰度较强的磺酸基m/z 79.9568、牛磺酸基m/z 124.0073和牛磺酸脱氨m/z 106.9803碎片离子,甘氨酸型胆汁酸侧链断裂可产生丰度较强的m/z 74.0426碎片离子。在负离子模式下,单酮基胆汁酸母核裂解还可形成带有酮基的特征离子m/z 402.3013,而胆汁酸酯则难以形成稳定的负离子,在正离子模式下则可产生甘氨酸甲酯离子m/z 90.0557。这些质谱裂解规律有助于对胆南星中其它胆汁酸类化合物的结构进行解析与推断,也可为快速分析和鉴定含有胆汁酸类成分的样品提供依据。The fragmentation pathways of 4 types and 25 species bile acids in Bile Arisaema were investigated using ultra performance liquid chromatography-quadrupole-time of flight mass spectrometer(UHPLC-Q-TOF MS/MS)by electrospray ionization at positive and negative ion mode.The protonated[M+H]+or deprotonated[M—H]-were observed by ESI-MS,from which the molecular weights were deduced.The MS/MS data of[M+H]+or[M—H]-ions provided fragmentation information of the compounds.The main and typical fragmentation pathways of different bile acids were neutral losses of H 2O and CO 2 units in the substituent on the mother nucleus.In particular,the functional groups in the C17 position of steroid mother nucleus were broken and provided characteristic fragmentation information.Meanwhile,the cleavages of A and C ring were also observed at the positive ion mode of the free bile acids.The common fragment ions of m/z 175,161 and 147 were characteristic ions.The ions of neutral loss were also observed at the negative ion mode of the free bile acids,generating ions of[M—H—CO2]^-,[M-H-H2CO2]^-and[M—H—H2O—H2CO2]^-.Taurine type bile acid could be broken and provided taurine group fragment ion m/z 126.0226 at the positive ion mode.Glycine type of bile acid could also be broken and provided glycine group fragment ion m/z 158.0818 at the positive ion mode.Taurine type bile acid could be broken and provided high abundance of[SO 3]-fragment ion m/z 79.9568,[NH 2—CH 2—CH 2—SO 3]-fragment ion m/z 124.0073 and[CH 2=CH 2—SO 3]-fragment ion m/z 106.9803 at the negative ion mode.Glycine type of bile acid could also be broken and provided high abundance of[NH 2—CH 2—COO]-fragment ion m/z 74.0426 at the negative ion mode.In addition,the characteristic ion of m/z 402.3013 with ketone group would be formed by the cleavage of single ketone group bile acid at the negative ion mode.It was difficult to form stable ions for bile acid esters at the negative ion mode.It could be broken and provided[NH 2—CH 2—COOCH 3]+fragment ion m/z

关 键 词：超高效液相色谱-四极杆-飞行时间串联质谱(UHPLC-Q-TOF MS/MS) 胆南星 胆汁酸 裂解规律 

分 类 号：O657.63[理学—分析化学]