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,1.7 μm),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100 0~179 9 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>0.999 3),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0.976 9、0.977 6),胡芦巴碱与使君子氨酸校正相关系数(Rc)分别为0.977 0和0.971 8,预测相关系数(Rp)分别为0.955 3和0.946 4,校正标准偏差(RMSEC)分别为0.373 9和0.284 8,预测标准偏差(RMSEP)分别为0.490 2和0.363 5。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。
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