基于多指标成分定量联合化学计量学、加权TOPSIS与灰色关联度融合模型评价不同产地缬草药材质量

目的 建立多指标成分定量联合化学计量学、加权 TOPSIS 与灰色关联度融合模型评价不同产地缬草 Valeriana officinalis L. 质量差异的方法。方法 采用高效液相色谱法，以 Phenomenex Gemini C₁₈色谱柱为固定相，乙腈-0.05% 磷酸为流动相，梯度洗脱，对 16 批缬草中橙皮苷、香叶木素、缬草三酯、乙酰缬草三酯、氯化缬草素、羟基缬草烯酸、乙酰氧基缬草酸、缬草烯酸、β-谷甾醇和熊果酸含量进行同步检测。结合化学计量学、加权 TOPSIS 与灰色关联度分析（GRA）融合模型进行质量差异的全面评价。结果 HPLC 方法学验证符合中国药典要求，10 种成分在各自范围内线性关系良好（R²＞0.999），平均加样回收率（n＝9）在 96.83%～100.08%（RSD＜2.0%）。化学计量学结果显示 16 批缬草明显分为 3 类，乙酰氧基缬草酸、橙皮苷、缬草三酯和羟基缬草烯酸为贡献度较大的差异性标志物。加权 TOPSIS 与灰色关联度融合结果显示16 批样品的相对贴近度为 0.279 2～0.666 5，湖北和贵州产地的缬草整体质量较好（相对贴近度为 0.5790～0.6665）。结论 以橙皮苷等 10 种成分含量为评价指标，采用化学计量学、加权 TOPSIS 与灰色关联度融合模型可用于评价缬草的质量。

Evaluation of quality of Valeriana officinalis from different origins based on multi indicator component quantitative combined chemometrics, weighted TOPSIS, and grey relational degree fusion model

Objective To establish a method to evaluate the quality difference of Valeriana officinalis from different producing areas by multi-index component quantitative combined with chemometrics, weighted TOPSIS and grey correlation degree fusion model. Methods Using HPLC to detection the contents of hesperidin, diosmetin, valtrate, acevaltrate, valechlorine, hydroxyvalerenic acid, acetoxyvalerenic acid, valerenic acid, β-sitosterol and ursolic acid in 16 batches of V. officinalis samples with Phenomenex Gemini C₁₈ column, and mobile phase was consisted of acetonitrile-0.05% phosphoric acid solution, gradient elution. The quality difference was comprehensively assessed by chemometrics, weighted TOPSIS and GRA fusion models. Results The validation of HPLC methodology met the requirements of Chinese Pharmacopoeia. The 10 components showed good linearity in their ranges (R² > 0.999), and the average recovery (n＝ 9) were 96.83%—100.08% (RSD < 2.0%). The results of chemometrics analysis showed that 16 batches of Valeriana officinalis were divided into three categories, and acetoxyvalerenic acid, hesperidin, valtrate and hydroxyvalerenic acid were the main markers of the quality differences. The results of weighted TOPSIS and grey correlation degree fusion technology showed that the relative closeness of 16 batches of samples was 0.279 2—0.666 5, and the overall quality of Valerian from Hubei and Guizhou provinces was good (relative closeness was 0.579 0—0.666 5). Conclusion With the content of 10 components such as hesperidin as the evaluation index, the fusion model of chemometrics, weighted TOPSIS and grey relational analysis fusion model can be used to evaluate the quality of Valeriana Officinalis.