基于高效液相色谱-四极杆/静电场轨道阱高分辨率质谱的寡糖轮廓分析用于蜂蜜中淀粉糖浆的掺假鉴别研究  

Identification of Starch Syrup in Honey Adulteration Based on Oligosaccharide Profiling Test by High Performance Liquid Chromatography-Quadrupole/Electrostatic Field Orbitrap High Resolution Mass Spectrometry

作　　者：张睿[1] 刘芸[1] 丁涛[1] 吴斌[1] 沈崇钰[1] 费晓庆[1] 桂茜雯[1] 王艳[1] 郭玲[1] 季美泉 王栩璐 邓晓军[2] 郭德华[2] 

机构地区：[1]江苏出入境检验检疫局,江苏南京210001 [2]上海出入境检验检疫局,上海200135

出　　处：《分析测试学报》2016年第12期1628-1633,共6页Journal of Instrumental Analysis

基　　金：江苏出入境检验检疫局科技计划(2016KJ05);上海长三角科技合作项目(15395810100)

摘　　要：采用高效液相色谱-四极杆/静电场轨道阱高分辨率质谱（HPLC-Q/Orbitrap MS）建立了寡糖轮廓分析的方法。通过对纯天然蜂蜜和淀粉类糖浆中的麦芽三糖、麦芽四糖、麦芽五糖、麦芽六糖和麦芽七糖进行定性定量分析,发现淀粉类糖浆中含有未被酶解完全的微量麦芽类寡糖,且麦芽七糖在所有检测样本中干扰小,对结果的定量无影响,而其他寡糖类物质的定性和定量结果会存在干扰。最终选择麦芽七糖作为蜂蜜中掺入淀粉糖浆的典型标志物。在实际样品分析中,根据麦芽七糖的保留时间和离子对的相对丰度比可以定性判断蜂蜜中是否掺有淀粉糖浆;通过标准曲线法可以定量测定样液中麦芽七糖的含量。在20,50,100 mg/kg 3个加标水平下,麦芽七糖的平均回收率为75%-82%,相对标准偏差（RSD,n=5）为3.1%-6.7%,方法检出限为0.1μg/m L。应用该方法可在10 min内完成整个分析过程,且样品前处理简单,结果可靠,灵敏度高,可用于纯天然蜂蜜中掺入淀粉糖浆的快速确证和检测。A method of oligosaccharide profiling test was developed based on high performance liquid chromatography -quadrurpole/electrostatic field orbitrap high resolution mass spectrometry （HPLC - Q/Orbitrap MS）. Through qualitative and quantitative analysis of mahotriose, maltotetraose, malto- pentaose, mahohexaose and maltoheptaose in pure natural honey and starch syrup, trace of malt oli- gosaccharides that was not totally enzymatic hydrolyzed were found in starch syrup. Furthermore, the interference of mahoheptaose in all test samples was the smallest and had no impact on the quantitative analysis results. While, the qualitative or quantitative analysis of other oligosaccharides were inter- fered more or less. In the analysis of real samples, the starch syrup in honey adulteration could be judged by the retention time and relative abundance ratio of maltoheptaose, therefore the content of mahoheptaose in sample solution could be quantitatively determined through standard curve method. By adding standard test, the average recoveries of maltoheptaose at three spiked levels of 20, 50 and 100 mg/kg were in the range of 75% -82% with relative standard deviations （RSD, n = 5） of 3.1% - 6. 7%. The detection limit of this method was 0. 1 μg/mL. The whole analysis time could be limitedin 10 min. The method had the advantages of simple processing procedure, high accuracy, reliabili- ty, sensitivity, therefore it could be applied in the rapid detection of starch syrup in honey.

关 键 词：蜂蜜掺假 寡糖轮廓分析 高效液相色谱-四极杆/静电场轨道阱高分辨率质谱 

分 类 号：O657.63[理学—分析化学] S896.1[理学—化学]