基于数据融合和多指标定量对滇龙胆产地鉴别和质量评价

Data fusion and multi-components quantitative analysis for identification and quality evaluation of Gentiana rigescens from different geographical origins

中药次生代谢产物积累和产地密切相关，产地鉴别以及多指标评价对保证药材质量具有重要意义。该实验采用高效液相色谱（HPLC）与傅里叶变换红外光谱（FTIR）数据融合结合偏最小二乘判别分析对滇龙胆进行产地鉴别，辅以多指标成分含量分析，以期为滇龙胆药材建立一种全面准确的鉴别和质量评价方法，为滇龙胆最佳产区筛选提供参考。采集云南、四川、广两、贵州共169份样品的阿IR和HPLC指纹图谱，并对PFIR进行多元散射校正、标准正态变量（SNV）、Savitzky-Golay（SG）卷积求导等预处理；比较FTIR，HPLC及低级、中级数据融合鉴别效果；利用HPLC分析样品中龙胆苦苷、獐牙菜苦苷、马钱苷酸与当药苷含量。结果发现，不同产地滇龙胆FTIR图谱存在差异，最佳预处理为SNV＋SG求导（二阶求导，窗口参数为15，多项式次数为2次）。低级、中级数据融合预测集正确率为96．43％，高于PI＇IR，HPLC预测集正确率94．64％；低级数据融台训练集正确率为100％，优于中级数据融合99．12％。云南滇龙胆4种环烯醚萜苷含量均高于其他省份，其中药典指标性成分龙胆菁片平均质量分数为47．40mg·g^-1，最大值达到79．83mg·g^-1，且龙胆苦苷、马钱苷酸与当药苛含量同其他省份含量差异挂著（P〈0．05）。云南省不同地区滇龙胆4种环烯醚萜苷总含量比较发现，大理洱源、丽江玉龙较高，分别为68．59，66．68mg·g^-1，蚓笼雄武定、土溪澄汀、昆明寻甸（52．99，52．29，46．71mg·g^-1）差异显著（P〈0．05），可作为滇龙胆栽培和优良种质资源筛选的参考地。FTIR-HPLC数据融合定性分析结合HPLC定量分析方法为不同产地滇龙胆鉴别和质量评价提供一种全面准确的新思路，为滇龙胆资源开发与利用提供科学依据。

The accumulation of secondal7 metabolites of traditional Chinese medicine （ TCM ） is closely related to its origins. The identification of origins and muhi-components quantitative evaluation are of great significance to ensure the quality of medicinal materi- als. In this study, the identification of Gentiana rigescens from different geographical origins was conducted by data fusion of Fourier transform inflared （FTIR） spectroscopy and high performance liquid chromatography （HPLC） in combination of partial least squares discriminant analysis; meanwhile quantitative analysis of index components was conducted to provide an accurate and comprehensive identification and quality evaluation strategy for selecting the best production areas of G. rigescens. In this study, the FTIR and HPLC information of 169 G. rigescens samples from Yunnan, Sichuan, Guangxi and Guizhou Provinces were collected. The raw infrared spec- tra were pre-treated by multiplicative scatter correction, standard normal variate （SNV） and Savitzky-Golay （SG） derivative. Then the performances of FTIR, HPLC, and low-level data fusion and mid-level data fusion for identification were compared, and the contents of gentiopicroside, swertiamarin, loganic acid and sweroside were determined by HPLC. The results showed that the FTIR spectra of G. rigescens from different geographical origins were different, and the best pre-treatment method was SNV ＋ SG-derivative （ second deriva- tive, 15 as the window parameter, and 2 as the polynomial order）. The results showed that the accuracy rate of low- and mid-level data fusion （96.43%） in prediction set was higher than that of FTIR and HPLC （94.64%） in prediction set. In addition, the accuracy of low-level data fusion （ 100% ） in the training set was higher than that of mid-level data fusion （99.12%） in training set. The contents of the iridoid glycosides in Yunnan were the highest among different provinces. The average content of gentiopicroside, as a bioactive marker in Chinese pharmacopoeia, was 47.40 mg·g-1, and the maximum was 79.83 mg·g- i. The contents of loganic acid, sweroside and gentiopicroside in Yunnan were significantly different from other provinces （ P 〈 0.05 ）. In comparison of total content of iridoid glycosides in G. rigescens with different geographical origins in Yunnan, it was found that the amount of iridoid glycosides was higher in Eryuan Dali （ 68.59 mg- g- L ） and Yulong Lijiang （ 66.68 mg. g^-1 ）, significantly higher than that in Wttding Cbuxiong （ 52.99 mg· g^-1） , Chengiiang Yuxi （52.29 mg.g^-1 ） and Xundian Kunming （46.71 mg·g^-1 ） （P〈0.05）, so these two places can be used as a reference region for screening cultivation and excellent gennplasm resources of G. rigescens. A comprehensive and accurate method was established by data fusion of HPLC-FTIR and quantitative analysis of HPLC for identification and quality evaluation of G. rigescens, which could provide a support for the development and utilization of G. rigeseens.