基于UHILIC-MS/MS和NIRS法的使君子仁中2个生物碱成分的含量测定研究  

Determination of two alkaloids in Quisqualis Fructus Semen by UHILIC-MS/MS and NIRS method

作　　者：汪丽娜 张颖 温秀萍[1] 徐伟[1] 余波 许文[1] 林羽[1] 陈在敏 WANG Li-na;ZHANG Ying;WEN Xiu-ping;XU Wei;YU Bo;XU Wen;LIN Yu;CHEN Zai-min(College of Pharmacy,Fujian University of Traditional Chinese Medicine,Fuzhou 350122,China;Fujian Institute for Food and Drug Quality Control,Fuzhou 350001,China)

机构地区：[1]福建中医药大学药学院,福州350122 [2]福建省食品药品质量检验研究院,福州350001

出　　处：《药物分析杂志》2023年第6期999-1011,共13页Chinese Journal of Pharmaceutical Analysis

基　　金：中央本级重大增减支项目(2060302);2019年医疗服务与保障能力提升补助资金(中医药事业传承与发展部分)“全国中药资源普查项目”(财社[2019]39号)。

摘　　要：目的:建立超高效亲水作用色谱串联三重四极杆质谱(UHILIC-MS/MS)法同时测定使君子仁中胡芦巴碱与使君子氨酸的含量,并建立其近红外光谱法(NIRS)快速定量模型,为使君子仁的质量控制提供新的技术手段。方法:采用UHILIC-MS/MS法,MRM正负切换离子模式进行含量测定,色谱条件为Waters ACQUITY BEH HILIC Amide色谱柱(2.1 mm×100 mm,1.7μm),流动相为0.1%甲酸水(A)-乙腈(B),梯度洗脱,流速为0.20 mL·min^(-1),柱温为45℃;扫描使君子仁粉末近红外光谱,在1000~1799 nm的波长范围内以10 cm^(-1)的分辨率获取每个光谱,采集方式漫反射,并运用偏最小二乘法(PLS)构建这2个成分的定量模型。结果:使君子仁中胡芦巴碱与使君子氨酸在5.20~260和8.50~425 ng·mL^(-1)浓度范围,呈良好的线性关系(r>0.9993),回收率分别为101.6%和100.2%,RSD分别为1.3%和2.0%;90批使君子仁所建立的模型NIRS预测值具有良好的线性关系(R分别为0.9769、0.9776),胡芦巴碱与使君子氨酸校正相关系数(Rc)分别为0.9770和0.9718,预测相关系数(Rp)分别为0.9553和0.9464,校正标准偏差(RMSEC)分别为0.3739和0.2848,预测标准偏差(RMSEP)分别为0.4902和0.3635。利用10批建模外使君子仁样品对模型进行验证,胡芦巴碱与使君子氨酸NIRS预测值与实测值的平均相对偏差分别为0.242%和0.252%。结论:本研究首次基于UHILIC-MS/MS建立使君子仁中胡芦巴碱与使君子氨酸的含量测定方法,快速、高效,首次构建使君子仁的胡芦巴碱和使君子氨酸近红外定量模型,定量准确,高效无损,可用于使君子仁的快速检测分析,为使君子仁的质控提供新的技术手段。Objective:To establish an ultra hydrophilic interaction chromatography-tandem mass spectrometry(UHILIC-MS/MS)for the simultaneous determination of trigonelline and quisqualic acid in Quisqualis Fructus Semen,then the rapid quantitative model of near infrared spectroscopy(NIRS)was established for the quality control of Quisqualis Fructus Semen.Methods:The UHILIC-MS/MS assay was performed on a Waters ACQUITY BEH HILIC Amide(2.1 mm×100 mm,1.7μm)column with 0.1%formic acid aqueous(A)-acetonitrile(B)as mobile phase by gradient elution at a flow rate of 0.20 mL·min^(-1),and the column temperature was set at 45℃.Positive and negative electrospray ionization were performed in multiple reaction monitoring(MRM)mode.The NIRS of Quisqualis Fructus Semen powder was obtained with a resolution of 10 cm^(-1)in the wavelength range of 1000-1799 nm.The collection method was diffuse reflection,and the quantitative models of these two components were constructed by partial least squares(PLS).Results:Under the UHILIC-MS/MS method,trigonelline and quisqualic acid showed good linear relationships within their tested ranges,which were 5.20-260 and 8.50-425 ng·mL^(-1),respectively(r>0.9993).The recoveries of trigonelline and quisqualic acid were 101.55% and 100.16%,and RSDs were 1.3% and 2.0%,respectively.There was a good linear relationship between the NIRS predicted values of trigonelline and quisqualic acid and the UHILIC-MS/MS measured values(R>0.9769).The corrected correlation coefficients(Rc)were 0.9770 and 0.9718,the predictive correlation coefficient(Rp)were 0.9553 and 0.9464,the calibration set cross-validation root mean square error(RMSEC)were 0.3739 and 0.2848,and the root square error of prediction(RMSEP)were 0.4902 and 0.3635,respectively.Then the model was validated by 10 batches of Quisqualis Fructus Semen samples beyond the established model,and the average relative deviation of the NIRS predictive value and measured values were 0.242% and 0.252%,respectively.Conclusion:It is the first report about simultaneous anal

关 键 词：使君子仁 近红外光谱 定量模型 超高效液相色谱串联三重四极杆质谱 含量测定 胡芦巴碱 使君子氨酸 

分 类 号：R917[医药卫生—药物分析学]