热解吸-电喷雾离子源-三重四极杆质谱法快速筛查火锅底料和肉汤中非法添加罂粟壳

doi:10.3724/SP.J.1123.2020.02002

摘要/Abstract

摘要：

通过简单的金属探针直接接触火锅底料和肉汤表面采集待测物，经热解吸离子源进一步热解吸和电喷雾离子化，最终进入三重四极杆质谱检测器在多反应监测模式下进行定性分析，实现了火锅底料和肉汤中罂粟壳的现场实时快速检测。结果表明，设置热解吸温度为260℃，以0.1%甲酸水溶液（含10 mmol/L甲酸铵-乙腈（1:1，v/v）作为注射溶剂、注射泵流速为200 μL/h时，仪器响应值最优，灵敏度最高；5种生物碱中罂粟碱、那可丁、蒂巴因在火锅底料和肉汤中的检出限均为2 μg/kg，可待因、吗啡在火锅底料中的检出限为10 μg/kg，在肉汤中的检出限为5 μg/kg。该法与罂粟壳胶体金卡片快检试剂盒相比，灵敏度具有明显优势。应用该法对50批次市售火锅底料、肉汤等样品进行检测，发现1批次鸡汤含有那可丁、罂粟碱、蒂巴因和吗啡4种生物碱，与高效液相色谱-三重四极杆质谱法的检测结果一致。由此说明该方法具有无需样品制备和色谱分离的特点，是一种快速、绿色、环保的分析方法，能够满足对食品中罂粟壳的快速定性分析。

关键词: 热解吸-电喷雾离子源, 三重四极杆质谱, 生物碱, 罂粟壳, 火锅底料, 肉汤, 快速筛查

Abstract:

A thermal desorption electrospray ionization-triple quadruple mass spectrometry (TD-ESI-MS/MS) method was developed for the rapid screening of poppy husk in hot pot sauce and soup. The solid surface or liquid sample was directly touched by a simple metal probe. The analytes collected on the probe were desorbed and ionized using a TD-ESI source, after which the analyte ions were detected by MS/MS in multiple reaction monitoring (MRM) mode. The results were compared with those of colloidal gold card rapid detection and verified by high performance liquid chromatography coupled with triple quadrupole mass spectrometry (HPLC-MS/MS). The instrument gave the best response with the highest sensitivity under the following conditions: thermal desorption temperature, 260 ℃; injection solvent, 0.1% formic acid aqueous solution containing 10 mmol/L formic ammonium-acetonitrile (1:1, v/v); flow rate, 200 μL/h. The limits of detection (LODs) for papaverine, noscapine, and thebaine in five alkaloids were 2 μg/kg, while those for codeine and morphine were 10 μg/kg in hot pot sauce and 5 μg/kg in soup. The sensitivity of this method was significantly superior to that of the colloidal gold card rapid detection. The method was applied to 50 batches of hot pot sauce and soup. Noscapine, papaverine, thebaine, and morphine were detected in a positive sample of chicken soup, which was consistent with the result of the HPLC-MS/MS method. This method without sample preparation and chromatographic separation is fast, green, and environmentally benign, thus being suitable for the rapid qualitative analysis of poppy husk in food.

Key words: thermal desorption electrospray ionization (TD-ESI), triple quadruple mass spectrometry (MS/MS), alkaloids, poppy husk, hot pot sauce, soup, rapid detection

张虹艳, 石晓峰, 邱国玉, 王小乔, 张彩霞, 张晓萍, 吴福祥, 许晓辉, 李晨曦, 潘秀丽. 热解吸-电喷雾离子源-三重四极杆质谱法快速筛查火锅底料和肉汤中非法添加罂粟壳[J]. 色谱, 2020, 38(7): 861-867.

ZHANG Hongyan, SHI Xiaofeng, QIU Guoyu, WANG Xiaoqiao, ZHANG Caixia, ZHANG Xiaoping, WU Fuxiang, XU Xiaohui, LI Chenxi, PAN Xiuli. Rapid screening of illegally added poppy husk in hot pot sauce and soup by thermal desorption electrospray ionization-triple quadruple mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(7): 861-867.

图/表 8

图1 热解吸-电喷雾离子源工作原理

Fig. 1 Principle of thermal desorption (TD)-ESI source

表1 5种生物碱的CAS号、化学式、监测离子、碎裂电压、碰撞能

Table 1 CAS Nos., chemical formula, monitoring ions, fragmentor and collision energies (CEs) of five alkaloids

Compound	CAS No.	Chemical formula	Precursor ion (m/z)	Daughter ions (m/z)	Fragmentor/eV	CEs/eV
Noscapine	912-60-7	C₂₂H₂₃NO₇	414.2	220.1, 353.0	120	18, 22
Papaverine	58-74-2	C₂₀H₂₁NO₄	340.2	202.1, 324.1	130	26, 30
Thebaine	115-37-7	C₁₉H₂₁NO₃	312.0	58.2, 251.1	80	10, 26
Codeine	76-57-3	C₁₈H₂₁NO₃	300.2	152.0, 215.1	125	80, 26
Morphine	57-27-2	C₁₇H₁₉NO₃	286.1	128.1, 180.0	130	74, 74

图2 注射泵不同流速对响应响度的影响

Fig. 2 Effect of different rates of pump on the response intensity Source: TD-ESI, positive; gas temperature: 300 ℃; gas flow: 3 L/min; nebulizer: 34.5 kPa; capillary: 4000 V; temperature of thermal desorption: 260 ℃; solvent of injection: 0.1% formic acid aqueous solution containing 10 mmol/L formic ammonium-acetonitrile (1:1, v/v).

表2 5种生物碱的检出限

Table 2 LODs for the five alkaloids

Compound	LODs/(μg/kg)
Compound	Hot pot sauce	Soup
Noscapine	2.0	2.0
Papaverine	2.0	2.0
Thebaine	2.0	2.0
Codeine	10.0	5.0
Morphine	10.0	5.0

图3 肉汤中5种生物碱6次重复试验的谱图

Fig. 3 MRM spectra of a mixture of the five alkaloid standards in soup by six repetitive test Rate of injection: 200 μL/h; other conditions are the same as those in Fig. 2.

图4 不同浓度生物碱胶体金卡片的快检结果

Fig. 4 Results of the five alkaloids in different contents tested by colloidal gold card

图5 实际样品的测定结果

Fig. 5 Detection results of the real samples Conditions are the same as those in Fig. 3.

表3 不同方法检测5种生物碱的结果对比

Table 3 Comparison for the five alkaloids tested with different methods

Compound	Results
Compound	TD-ESI-MS/MS	LC-MS/MS/(μg/kg)
Noscapine	positive	56.4
Papaverin	positive	30.1
Thebaine	positive	91.1
Codeine	positive	622
Morphine	negative	not detected

参考文献

1	Chen W , Qiao Y S , Dong G J . Science and Technology of Cereals Oils and Foods, 2015 (6): 89
1	陈伟, 乔勇升, 董贵军. 粮油食品科技, 2015 (6): 89
2	Fan X , Feng J L , Chen D Y , et al. Chinese Journal of Health Laboratory Technology, 2015, 25 (14): 2296
2	范翔, 冯家力, 陈东洋, et al. 中国卫生检验杂志, 2015, 25 (14): 2296
3	Xu L H , Wang J Q , Tao Q , et al. Journal of Instrumental Analysis, 2011, 30 (12): 1387
3	徐丽红, 王建清, 陶秋, et al. 分析测试学报, 2011, 30 (12): 1387
4	Shen P , Xie C M , Xie Y X . Physical Testing and Chemical Analysis Part B:Chemical Analysis, 2016, 52 (1): 48
4	沈平, 谢朝梅, 谢燕湘. 理化检验:化学分册, 2016, 52 (1): 48
5	Li X G , Qiao Y S , Chen W , et al. Journal of Instrumental Analysis, 2018, 37 (4): 446
5	李兴根, 乔勇升, 陈伟, et al. 分析测试学报, 2018, 37 (4): 446
6	Zhang X Y , Cai X X , Zhang X Y , et al. Chinese Journal of Chromatography, 2017, 35 (11): 1137
6	张秀尧, 蔡欣欣, 张晓艺, et al. 色谱, 2017, 35 (11): 1137
7	Lin D Q , Wang T T , Wan C B , et al. Journal of Chinese Mass Spectrometry Society, 2017, 38 (2): 239
7	林黛琴, 王婷婷, 万承波, et al. 质谱学报, 2017, 38 (2): 239
8	Ning H Y , Huang X L , Lai Z Y , et al. China Brewing, 2019, 38 (11): 190
8	宁焕焱, 黄秀丽, 赖政炀, et al. 中国酿造, 2019, 38 (11): 190
9	Liu M M , Zhang C Z , Li Y Z , et al. Food Research and Development, 2013, 34 (1): 91
9	刘敏敏, 张朝正, 李延志, et al. 食品研究与开发, 2013, 34 (1): 91
10	Zhu W X , Sun Z L , Yuan P , et al. Chinese Journal of Chromatography, 2014, 32 (12): 1333
10	祝伟霞, 孙转莲, 袁萍, et al. 色谱, 2014, 32 (12): 1333
11	Wang L Q , Li M H , Li J Q , et al. Food and Fermentation Industries, 2012, 38 (8): 168
11	王力清, 郦明浩, 李锦清, et al. 食品与发酵工业, 2012, 38 (8): 168
12	Zhang L T , Huang S Y , Lu Y N , et al. Chinese Journal of Analysis Laboratory, 2014, 33 (6): 722
12	张林田, 黄少玉, 陆奕娜, et al. 分析试验室, 2014, 33 (6): 722
13	Hua L , Ye P , Lu J , et al. China Condiment, 2018, 43 (8): 142
13	花露, 叶平, 陆杰, et al. 中国调味品, 2018, 43 (8): 142
14	Ma K , Yang C B , Huang Y Q , et al. Food Industry, 2019, 40 (9): 145
14	马凯, 杨昌彪, 黄永桥, et al. 食品工业, 2019, 40 (9): 145
15	Chao Y Y , Chen Y L , Lin H Y , et al. Anal Chim Acta, 2018, 1010 (20): 44
16	Chao Y Y , Chen Y L , Chen W C , et al. Food Chem, 2018, 252 (30): 189
17	Su H , Lin Y P , Yang S C , et al. Anal Chim Acta, 2019, 1066 (20): 69
18	Huang Y L , Huang Z P , Watanabe C C , et al. J Anal Appl Pyrol, 2019, 137: 227
19	Kumara P M , Shaanker R U , Pradeepa T , et al. Phytochemistry, 2019, 159: 20
20	Zhang B L , Gao L H , Xie Y S , et al. Chinese Journal of Chromatography, 2017, 35 (7): 724
20	张百乐, 高黎红, 解迎双, et al. 色谱, 2017, 35 (7): 724
21	Cheng S C , Lee R H , Jeng J Y , et al. Anal Chim Acta, 2020 1102
22	Wang C H , Su H , Chou J H , et al. Anal Chim Acta, 2018 1021
23	Chiang C H , Lee H H , Chen B H , et al. J Food Drug Anal, 2019, 27 (2): 439

[1]	王园媛, 李璐璐, 吕佳, 陈永艳, 张岚. 固相萃取-超高效液相色谱-三重四极杆质谱法测定饮用水中13种卤代苯醌类消毒副产物[J]. 色谱, 2023, 41(6): 482-489.
[2]	李鑫玉, 赵芳, 平华, 马智宏, 李冰茹, 马挺军, 李成. 稳定同位素稀释气相色谱-三重四极杆质谱法测定水产品中15种卤代多环芳烃[J]. 色谱, 2023, 41(6): 527-534.
[3]	陈佳, 刘玉龙, 徐斌, 刘勤, 谢剑炜. 顶空固相微萃取-气相色谱-质谱法快速筛查油性基质中化学武器公约相关化合物[J]. 色谱, 2023, 41(4): 348-358.
[4]	曲涛, 陈阳, 杨长军, 刘其耸, 陈惠, 何志勇, 王召君, 陈洁, 曾茂茂. 松花粉干预卵巢早衰大鼠肝脏的广泛靶向代谢组学分析[J]. 色谱, 2023, 41(1): 47-57.
[5]	刘洪媛, 金静, 郭崔崔, 陈吉平, 胡春. 同位素稀释气相色谱-三重四极杆质谱法测定环境空气中的多氯萘[J]. 色谱, 2022, 40(7): 644-652.
[6]	荣杰峰, 许美珠, 张志勇, 邹强, 徐敦明, 钟坚海, 张松艳, 乐有东, 佘紫文. 气相色谱-三重四极杆质谱法测定植物源性食品中棉隆及其代谢物异硫氰酸甲酯残留[J]. 色谱, 2022, 40(7): 661-668.
[7]	张权, 毕珊, 吴玉田, 李磊, 周贻兵, 刘利亚, 刘文政, 陈庆园, 周雪, 郭华. Sin-QuEChERS Nano净化柱结合气相色谱-串联质谱法快速筛查石斛中84种农药残留[J]. 色谱, 2022, 40(6): 565-575.
[8]	徐红斌, 张申平, 杜茹芸, 周静, 翁史昱. 超高效液相色谱-Orbitrap高分辨质谱用于减肥和壮阳类保健食品中32种非法添加药物的快速筛查和确证[J]. 色谱, 2022, 40(6): 531-540.
[9]	柯庆青, 李诗言, 王鼎南, 周钦, 周凡, 贝亦江, 陈小明, 王扬. 超高效液相色谱-四极杆-飞行时间质谱法快速筛查和确证渔药中86种非法添加化学品[J]. 色谱, 2022, 40(6): 520-530.
[10]	张秀尧, 蔡欣欣, 张晓艺, 李瑞芬, 赵云峰. 免疫亲和柱净化-超高效液相色谱-三重四极杆质谱法高灵敏测定尿液和血浆中3种鹅膏毒肽[J]. 色谱, 2022, 40(5): 443-451.
[11]	孙慧婧, 李佩纹, 张蓓蓓, 陈慧敏. 大体积直接进样-超高效液相色谱-三重四极杆质谱法测定水中7大类42种抗生素残留[J]. 色谱, 2022, 40(4): 333-342.
[12]	薛高旭, 王沁怡, 曹玲, 孙晶, 杨功俊, 冯有龙, 方方. 固相萃取-离子迁移谱法快速筛查祛痘类化妆品中14种抗菌药物[J]. 色谱, 2022, 40(12): 1119-1127.
[13]	陈永艳, 吕佳, 张岚, 叶必雄, 金宁. 在线固相萃取-超高效液相色谱-三重四极杆质谱法测定水源水和饮用水中107种典型农药及代谢产物[J]. 色谱, 2022, 40(12): 1064-1075.
[14]	钱冲, 张梅, 刘珊珊, 勾新磊, 王尉, 胡光辉. 衍生化-气相色谱-三重四极杆质谱法测定泼尼松龙中联氨[J]. 色谱, 2021, 39(7): 750-757.
[15]	詹未, 韩志宇, 李勇, 刘非, 张永. 吹扫捕集-气相色谱-三重四极杆质谱法同时测定饮用出厂水中6种卤乙腈[J]. 色谱, 2021, 39(7): 758-763.