基于实时直接分析质谱技术快速鉴别及测定制马钱子及其制剂中马钱子生物碱类成分  

Rapid characterisation and determination of Strychnos alkaloids in processed Strychni Semen and its compound preparations by DART-MS

作　　者：张皓月 陈岩 潘斯涵 陈依琳 李林楠 熊爱珍[1] 王峥涛[1] 陈凯先 杨莉[1,2] ZHANG Hao-yue;CHEN Yan;PAN Si-han;CHEN Yi-lin;LI Lin-nan;XIONG Ai-zhen;WANG Zheng-tao;CHEN Kai-xain;YANG Li(MOE Key Laboratory for Standardization of Chinese Medicines,Institute of Chinese Materia Medica,Shanghai University of Traditional Chinese Medicine,Shanghai 201203,China;Institute of Interdisciplinary Integrative Medicine Research,Shanghai University of Traditional Chinese Medicine,Shanghai 20123,China;School of Pharmacy,Shanghai University of Traditional Chinese Medicine,Shanghai 201203,China;Shanghai Institute of Materia Medica,Chinese Academy of Sciences,Shanghai 201203,China)

机构地区：[1]上海中医药大学中药研究所中药标准化教育部重点实验室暨上海市复方中药重点实验室,上海201203 [2]上海中医药大学交叉科学研究院,上海201203 [3]上海中医药大学中药学院,上海201203 [4]中国科学院上海药物研究所,上海201203

出　　处：《药物分析杂志》2023年第10期1692-1701,共10页Chinese Journal of Pharmaceutical Analysis

基　　金：上海市人才发展资金(2020099);上海中医药大学“杏林学者”计划(B1-GY21-409-04-06);上海中医药大学大学生创新活动计划(S202110268113)。

摘　　要：目的:建立实时直接分析质谱法(DART-MS法)快速鉴别及测定制马钱子及其复方制剂中马钱子生物碱类成分。方法:采用实时直接分析离子源结合离子阱质谱,在正离子模式下,全扫描采集制马钱子的DART-MS特征图谱及二级图谱,与已报道的制马钱子化学成分的质谱数据比对确证马钱子生物碱类成分。利用内标法,选用野百合碱为内标物,对制马钱子及其复方制剂中马钱子碱和士的宁进行定量分析。传送管间距为7.5 mm,样品居中,毛细管温度350℃,气加热温度350℃,毛细管电压10 V,套管透镜电压80 V。结果:通过对制马钱子DART-MS一级质谱图及二级质谱图分析,共鉴别出12个马钱子生物碱类成分。马钱子碱质量浓度在62.80~3140.00 ng·mL^(-1)范围内线性关系良好,r为0.9995,平均回收率为93.8%;士的宁质量浓度在68.00~3400.00 ng·mL^(-1)范围内线性关系良好,r为0.9988,平均回收率为89.1%。马钱子碱的检测限和定量限分别为1.57和3.14 ng·mL^(-1),士的宁的检测限和定量限分别为1.70和3.40 ng·mL^(-1)。制马钱子及腰痛宁胶囊、平消胶囊、风湿马钱片、伤科接骨片、疏风定痛丸、舒筋丸、伸筋丹胶囊、伸筋活络丸、疏风活络丸、风寒双离拐胶囊中马钱子碱和士的宁的含量范围分别为0.03~9.07、0.14~20.25 mg·g^(-1)。结论:本方法简单、快速,灵敏度高,试剂耗费少,适用于马钱子的快速鉴别及多种含马钱子的中药制剂中马钱子碱与士的宁的快速测定。Objective:To establish a real-time direct analysis mass spectrometry(DART-MS)method for the rapid characterisation and determination of Strychnos alkaloids in processed Strychni Semen and its preparations.Methods:The DART-MS characteristic spectrum of processed Strychni Semen was collected in the positive ion mode by full scan,using direct analysis in real time ionization source combined with ion trap mass spectrometry.And comparing the exact mass with the reported chemical constituents of Strychni Semen to confirm the Strychnos alkaloids of processed Strychni Semen.Internal standard method and monocrotaline was used as the internal standard to determine the content of brucine and strychnine in traditional Chinese patent medicines containing Strychni Semen.The distance between the ceramic tube of DART ion source to the MS inlet was 7.5 mm,the sample was centered,the capillary temperature was set to 350℃,the gas heating temperature was 350℃,the capillary voltage was 10 V,and the tube lens voltage was 80 V.Results:Different alkaloids were identified by analyzing the DART-MS spectrum of processed Strychni Semen.Brucine showed good linear relationships within the ranges of 62.80-3140.00 ng·mL^(-1),the r was 0.9995,and the average recovery rate was 93.8%.The linear range of strychnine was 68.00-3400.00 ng·mL^(-1),the r was 0.9988,and the average recovery rate was 89.1%.The limit of detection(LOD)and limit of quantitation(LOQ)of brucine were 1.57 and 3.14 ng·mL^(-1),respectively.The LOD and LOQ of strychnine were 1.70 and 3.40 ng·mL^(-1),respectively.The contents of brucine and strychnine in processed Strychni Semen,Yaotongning capsules,Pingxiao capsules,Fengshi Maqian tablets,Shangke Jiegu tablets,Shufeng Dingtong pills,Shujin pills,Shenjindan capsules,Shenjin Huoluo pills,Shufeng Huoluo pills,Fenghan Shuangliguai capsules were 0.03-9.07 mg·g^(-1),0.14-20.25 mg·g^(-1),respectively.Conclusion:The method is simple,rapid,high in sensitivity and low in reagent consumption,can be used for the rapid characterisati

关 键 词：实时直接分析质谱 马钱子生物碱 中药制剂 快速鉴别 含量测定 原位电离质谱 

分 类 号：R917[医药卫生—药物分析学]