基于高分辨质谱-灰色关联度分析的丹参质量评价研究

A study on the quality evaluation of Salvae Miltiorrhizae Radix et Rhizoma by the HRMS and gray relational analysis

目的利用高分辨质谱(HRMS)和灰色关联度分析(GRA)法,研究建立可资评价丹参质量优劣的HRMS-GRA方法,并利用所建方法,评价陕西省内5产地丹参的质量优劣。方法采用HRMS法,分析测定不同产地丹参药材提取物中主要化学成分的质谱离子丰度;以质谱离子丰度数据为基础,通过相关GRA研究,建立预测丹参药材质量优劣的GRA评价方法模型,利用该模型预测评价不同产地丹参药材的质量优劣排序;同时,以8株临床细菌为受试菌,测试不同产地丹参提取物的抗菌活性,通过比较模型预测的质量优劣排序和抗菌活性强弱,考察所建HRMS-GRA法用于丹参质量评价的可行性。结果HRMS测试分析结果表明,陕西省内5个不同产地的丹参都含有11种主要化学成分,但各成分的质谱离子丰度在不同产地样品中变化明显,有较大地区差异性。其中,丹参素和丹酚酸E在各产地丹参中含量普遍较高,在5产地丹参中丹参素的质谱离子丰度均>44%,丹酚酸E的质谱离子丰度则均>58%。以这11种主要化学成分的质谱离子丰度数据为基础,研究建立了预测丹参药材质量优劣的GRA评价方法模型,并利用该模型预测评价了陕西省内5产地丹参的质量优劣,结果表明,5产地丹参药材的质量优劣排序为:灵宝(0.629)>商州(0.581)>洛南(0.542)>大荔(0.539)>丹凤(0.367)。抗菌活性测试结果表明,5个产地丹参提取物对8株受试菌均显示有一定抗菌活性,活性强弱与HRMS-GRA法预测的丹参质量优劣排序基本吻合。结论本文新建HRMS-GRA方法预测的陕西省内5产地丹参质量优劣排序与实际测试的抗菌活性强弱基本吻合,研究结果为丹参的鉴别和综合质量评价提供了可资借鉴和参考的新思路,所建HRMS-GRA法具有一定推广应用前景。

Objective To investigate the method for the quality evaluation of Salviae Miltiorrhizae Radix et Rhizoma(SMRR)by the high resolution mass spectrometry(HRMS)and the gray relational analysis(GRA),so as to establish a HRMS-GRA model for the SMRR quality evaluation and estimate the quality order of SMRRs from 5 different areas in the Shaanxi province of China.Methods The ion abundance determination was accomplished by the HRMS analysis for main chemical components in the extracts of SMRR samples from different areas. Based on the data of MS ion abundance,the GRA was conducted to create a model of GRA method for estimating the quality of SMRR,and the quality order for the SMRR samples from different areas was estimated using the GRA method model. Meanwhile,the antibacterial activity on 8 strains of clinical bacteria was assayed for the extracts of SMRR samples from different areas,and the results were compared with the quality order estimated by the GRA method model,in order to estimate the feasibility of the SMRR quality evaluation by the created HRMS-GRA method. Results As indicated by the HRMS analysis,all the SMRR samples from 5 different areas in the Shaanxi province of China contained 11 main chemical components,but the MS ion abundance of each component varied in the SMRR samples from different areas and showed quite a large regional difference. Among the 11 components,salvianic acid A and salvianolic acid E showed higher contents,with the more than 44% MS ion abundance for salvianic acid A and the more than 58% MS ion abundance for salvianolic acid E,in all of the SMRR samples from 5 different areas.On the basis of the data of MS ion abundance of the 11 components,a GRA model was created for the SMRR quality estimation with the relative correlation degree(ri),and the quality of the SMRR samples from the 5 different areas was estimated by the model to obtain an estimated quality order:Lingbao(ri=0.692)>Shangzhou(ri=0.581)>Luonan(ri=0.542)>Dali(ri=0.539)>Danfeng(ri=0.367). The results of the antibacterial test for the SMRR samples from the 5 different areas coincided with the quality order estimated by the GRA model. Conclusion The quality order estimated with the newly created HRMS-GRA method for the SMRR samples from5 different areas in the Shaanxi province of China coincided with the antibacterial test results for the same SMRR samples. The present work provides a reference for the work on the identity and quality evaluation of SMRR,and the HRMS-GRA method is expected to have potential applications.