基于近红外光谱法快速测定丹参中5种成分模型的建立

Model establishment for rapid determination the content of five components in Salvia miltiorrhiza based on NIRS spectroscopy

目的采用近红外光谱(NIRS)技术结合偏最小二乘法(PLS)建立丹参中多种成分的快速无损检测方法,以更好地控制丹参药材和饮片的质量。方法共收集来自不同产地的丹参样品106批。采用前期研究所建立的UPLC方法测定所有丹参样品中丹参素、原儿茶醛、咖啡酸、迷迭香酸、紫草酸、丹酚酸B、丹酚酸A、二氢丹参酮、隐丹参酮、丹参酮I和丹参酮IIA共11种化学成分的含量;以积分球漫反射模式采集丹参样品的NIRS图;通过PLS等化学计量学手段,分别对校正集和验证集的选择、不同预处理方法、不同光谱区段以及因子数的确定进行优化,尝试建立近红外光谱与待测成分含量间的线性关系模型,从而实现用NIRS对待测成分含量的快速计量。结果丹参中丹酚酸B、二氢丹参酮、丹参酮I、隐丹参酮和丹参酮IIA 5种成分的NIRS预测值与UPLC实测值之间具有良好的线性关系,模型预测效果良好,其相关系数分别为0.981 1、0.936 3、0.960 5、0.910 9、0.978 0;预测均方差(RMSEP)分别为0.957 0、0.037 7、0.041 6、0.114 0、0.063 9;其余成分的近红外建模未达到定量要求。结论 NIRS法结合PLS可以快速、无损地对丹参中的丹酚酸B、二氢丹参酮、丹参酮I、隐丹参酮和丹参酮IIA进行定量分析。这为开发丹参药材、饮片的快速现场检测方法奠定了基础。

Objective To establish a rapid and nondestructive method for the determination of multi-components in Salvia miltiorrhiza to improve the quality control of S. miltiorrhiza based on Near infrared spectroscopy combined with partial least squares（PLS） method. Methods A total of 106 batches of S. miltiorrhiza samples from different origins were collected. The content of 11 components（tanshinol sodium, protocatechuic aldehyde, caffeic acid, rosmarinic acid, alkannic acid, salvianolic acid B, salvianolic acid A, dihydrotanshinone, tanshinone I, cryptotanshinone, and tanshinone IIA） in all of the samples which was conducted as the reference value were determined by a UPLC method established in the previous research. And the NIRS spectrum were obtained under the integrating sphere diffuse reflection mode. The different processes of modeling were optimized by partial least squares（PLS） and other chemometrics methods, including the selection of calibration set and validation set, different pretreatment method, different spectral section, and the determination of factors. A linear quantitative calibration model between the near infrared spectrum and the content of the components to be measured was tried to be established so that the content of the components could be measured by NIRS rapidly. Results The predicted value of NIRS and the measured value of UPLC of five components in S. miltiorrhiza, including salvianolic acid B, dihydrotanshinone, tanshinone I, cryptotanshinone, and tanshinone IIA, presented a good linearity, indicating the calibration models had a preferable forecast results. The correlation coefficient were 0.981 1, 0.936 3, 0.960 5, 0.910 9, 0.978 0 respectively, and the mean and square deviation of the prediction set（RMSEP） were 0.957 0, 0.037 7, 0.041 6, 0.114, 0.063 9, respectively; But the model of the other constituents failed to reach the quantitative level. Conclusion The content of salvianolic acid B, dihydrotanshinone, tanshinone I, cryptotanshinone, tanshinone IIA in S. miltiorrhiza can be determined rapidly and nondestructive by the NIRS combined with PLS method, which lays a foundation for the rapid and field determination method for the medicinal materials and decoction pieces of S. miltiorrhiza.