傅立叶变换离子回旋共振质谱法对赤灵芝的化学成分鉴定和指纹图谱研究

建立了基于傅立叶变换离子回旋共振超高分辨质谱(FTICR-MS)的赤灵芝化学成分鉴定和指纹图谱分析方法,并应用于不同产地赤灵芝样品的来源区分。样品采用50%甲醇进行回流提取后,以流动注射的进样方式进行直接质谱分析。以ESI离子源在负离子模式下进行检测,质荷比扫描范围为100～1 000 Da。采用精确分子量测定和碰撞诱导解离实验进行化学成分鉴定,通过与文献进行比对,共鉴定出63种化学成分(1种萜烯醛、3种糖、4种三萜醇、6种有机酸和49种三萜酸类成分)。采用聚类分析和主成分分析(PCA)对所获得的质谱指纹图谱进行统计学分析,在95%的置信区间下,多个批次不同产地的赤灵芝样品得到了较好的来源区分。研究结果表明该方法可实现赤灵芝的直接、快速、高效分析和指纹图谱研究,在中药分析领域有着广阔的应用前景。

Identification of Chemical Constituents in Ganoderma lucidum by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Its Fingerprinting Analysis

A Fourier transform ion cyclotron resonance mass spectrometry(FTICR-MS) with cluster analysis and principal components analysis(PCA) was developed for the identification of chemical constituents in Ganoderma lucidum and the analysis of its fingerprintings used for origin differentiation.The Ganoderma lucidum samples were extracted with a reflux using 50% methanol as solvent,then analyzed directly by FTICR-MS.The MS spectra were recorded at m/z 100-1 000 Da with ESI source under a negative ion detection mode.The chemical constituents in Ganoderma lucidum were identified by accurate mass determination in MS/MS experiments,and total of sixty-three active ingredients,including one terpene aldehyde,three sugars,four triterpene alcohols,six organic acids and forty-nine triterpene acids,were identified by comparing their mass spectrometric inforamtion with those of reference compounds and literatures.The Ganoderma lucidum samples derived from different origins were distinguished by cluster analysis and PCA,and a good origin differentiation was obtained under 95% confidence interval.Experimental results showed that the developed method could be applied in the rapid,direct and efficient analysis of Ganoderma lucidum and its fingerprintings,and was a promising approach for analysis of traditional Chinese medicine.