枳壳药材挥发油的GC—MS指纹图谱研究

　　中图分类号 R927.2 文献标志码 A 文章编号 1001-0408（2018）04-0461-05
　　DOI 10.6039/j.issn.1001-0408.2018.04.08
　　摘 要 目的：建立枳壳药材挥发油的气相色谱-质谱（GC-MS）指纹图谱。方法：采用GC-MS法，色谱柱为RTX-5MS毛细管柱，进样口温度为250 ℃，载气为高纯氦气（≥99.999%），流速为1.0 mL/min，分流比为10 ∶ 1，进样量为1 μL（程序升温）；采用电子轰击离子源，离子源温度为230 ℃，检测器温度为250 ℃，溶剂延迟时间为3 min，扫描范围为m/z 35～550。以月桂烯为参照，测定21批药材挥发油样品的GC-MS图谱，采用《中药色谱指纹图谱相似度评价系统》（2004 A版）进行相似度评价，确定共有峰，采用LC Solution 2质谱库（NIST05.LIB和NIST05s.LIB）确定共有峰成分，并采用面积归一化法测定共有峰的相对含量。结果：21批药材挥发油样品的GC-MS图谱有20个共有峰，相似度均>0.90；经验证，21批药材挥发油样品GC-MS图谱与对照指纹图谱具有较好的一致性。枳壳药材挥发油主要成分为柠檬烯、萜品烯、月桂烯和D-Cadinene。结论：所建指纹图谱可为枳壳药材挥发油的真伪鉴别和质量评价提供参考。
　　关键词 枳壳；挥发油；气相色谱-质谱指纹图谱；道地药材
　　ABSTRACT OBJECTIVE： To establish GC-MS fingerprint of volatile oil from Citrus aurantium. METHODS： GC-MS method was adopted. The determination was performed on RTX-5MS capillary column with injector temperature of 250 ℃， high pure helium as carrier gas（≥99.999%）， flow rate of 1.0 mL/min， split ratio of 10 ∶ 1， and sample size of 1 μL （temperature programming）. Mass spectrum condition included electron bombardment ion source， ion source temperature of 230 ℃， detector temperature of 250 ℃， 3 min solvent delay， scanning range of m/z 35-550. GC-MS chromatograms of 21 batches of volatile oil samples were determined using Laurene as reference. The similarity of them was evaluated by using TCM Chromatographic Fingerprint Similarity Evaluation System （2004 A edition）， and common peak was determined. The components of common peak were determined by LC Solution 2 mass database （NIST05.LIB and NIST05s.LIB）. Relative content of common peak was determined with area normalization. RESULTS： There were 20 common peaks in GC-MS chromatograms of 21 batches of volatile oil samples， and the similarity was higher than 0.90. After validation， GC-MS chromatograms of 21 batches of volatile oil samples were in good agreement with control fingerprint. The main constituents of the volatile oil of C. aurantium were Limonene，Terpinene， Laurene and D-Cadinene. CONCLUSIONS： Established fingerprint can provide reference for identification and quality evaluation of volatile oil of C. aurantium.
　　KEYWORDS Citrus aurantium； Volatile oil； GC-MS fingerprint； Genuine regional drug
　　枳殼为芸香科植物酸橙（Citrus aurantium L.）及其栽培变种的干燥未成熟果实[1]，有理气宽中之功效，多用于食积不化、脘腹胀满等症状[2]。现代药理学研究表明，枳壳具有抗炎、抗菌、抗病毒、抗肿瘤、抗溃疡、减少毛细血管脆性等作用[3]。
　　我国枳壳药材3个道地产区为湖南沅江、江西新干和重庆江津，市场多以药材出处加以区分，分别称为湘枳壳、江枳壳和川枳壳。中药指纹图谱是一种综合的、可量化的鉴定手段，主要用于评价中药材以及中药制剂半成品质量的真实性、优良性和稳定性[4-5]。现有研究对枳壳药材的气相色谱-质谱（GC-MS）指纹图谱报道较少，本试验收集了全国不同产地的21批枳壳药材，采用GC-MS法建立了其挥发油指纹图谱，旨在为枳壳药材的鉴别和中成药的质量控制提供科学依据。