基质辅助激光解吸电离-飞行时间质谱法快速筛查食品中10种非法壮阳抗疲劳类药物  

Fast Screening of 10 Kinds of Illegal Aphrodisiac Drugs in Foods by Matrix-assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry

作　　者：曾羲 王宇 陈迎丽 赵甜甜 徐振林[2] 周恒鑫 ZENG Xi;WANG Yu;CHEN Ying-Li;ZHAO Tian-Tian;XU Zhen-Lin;ZHOU Heng-Xin(Guangzhou Institute for Food Control,Guangzhou 511400,China;Guangdong Provincial Key Laboratory of Food Quality and Safety,College of Food Science,South China Agricultural University,Guangzhou 510642,China;Guizhou Provincial Detection Technology Research and Application Center,Guiyang 550016,China;Guangdong Key Laboratory of Agricultural Products Processing,Key Laboratory of Functional Foods,Ministry of Agriculture and Rural Affairs,Sericulture&Agri-food Research Institute,Guangdong Academy of Agricultural Sciences,Guangzhou 510610,China)

机构地区：[1]广州市食品检验所,广州511400 [2]华南农业大学食品学院,广东省食品质量安全重点实验室,广州510642 [3]贵州省检测技术研究应用中心,贵阳550016 [4]广东省农业科学院蚕业与农产品加工研究所,农业农村部功能食品重点实验室,广东省农产品加工重点实验室,广州510610

出　　处：《分析化学》2025年第3期441-450,共10页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.32061160473);广东省自然科学基金项目(No.2023A1515012605);广东省食品质量安全重点实验室开放基金项目(No.2024KF01);广东省市场监督管理局科技项目(No.2023CS01);贵州省科学院项目(No.黔科院J字(2023)23号)资助。

摘　　要：建立了基质辅助激光解吸电离-飞行时间质谱(MALDI-TOF MS)分析食品中西地那非、红地那非、那红地那非、豪莫西地那非、罗地那非碳酸酯、西地那非二聚体杂质、伐地那非二聚、羟基红地那非、N-去甲基西地那非和乌地那非10种非法添加壮阳抗疲劳药物的方法。考察了基质种类、基质溶剂和用量、激光强度和点样方式对各目标物的质谱信号强度和信噪比(S/N)的影响,并进行了方法学验证和实际样品检测。结果表明,选择以介子酸(SA)为基质,将其均匀分散在甲醇-水(50∶50,V/V)中,采用先点基质再点样品的点样方式,在反射线性正离子模式下选择激光强度为60%进行MALDI-TOF MS筛查时,质谱信号稳定、强度高、响应重复性好。方法学验证结果表明,10种非法壮阳抗疲劳药物浓度在10~100 ng/mL范围内与质谱叠加峰面积呈良好的线性关系,相关系数(r)>0.985,检出限(LOD)为0.1~1.0 ng/mL。保健酒、软胶囊和速溶咖啡3种食品基质中的加标回收率为72.9%~109.9%,相对标准偏差(RSDs)为0.7%~11.3%(n=3)。本方法分析速度快、准确性高、灵敏度好、抗干扰能力强、无样品基质效应,基于已有质谱信息可无需使用标准品,仅通过点靶上机测定即可实现对食品基质中10种非法壮阳抗疲劳药物的非靶向筛查。A matrix-assisted laser desorption ionization time-of-flight mass spectrometry(MALDI-TOF MS)method was developed for simultaneous analysis of 10 kinds of aphrodisiac drugs,including sildenafil,acetildenafil,nor-acetildenafil,homosildenafil,lodenafil carbonate,sildlenafil dimer impurity,vardenafil dimer,hydroxyacetildenafil,N-desmethylsildenafil and udenafil.By using different matrices(α-cyano-4-hydroxycinnamic acid(HCCA)and sinapic acid(SA)),the effects of solvents,amount of matrices,laser intensity and spotting methods on the peak strength and signal intensity of MALDI-TOF MS for the aphrodisiac drugs were investigated.As a result,SA was chosen as the matrix,and then dispersed in methanol-water(50∶50,V/V),and spotted by matrix firstly and sample secondly approach with the reflect linear positive mode and laser power of 60%.Under optimal conditions,the proposed MALDI-TOF MS method could obtain stable signal,high intensity and well-repeated mass spectrometric results.The results of method validation showed a linear range from 10 to 100 ng/mL,and the regression coefficients(r)were all above 0.985.The limits of detection(LOD)were 0.1-1.0 ng/mL,and the recoveries were in the range of 72.9%-109.9% for health wine,soft capsule and instant coffee samples,while the relative standard deviations(RSDs)ranged from 0.7% to 11.3%(n=3).The test results of 10 kinds of aphrodisiac drugs by MALDI-TOF MS were in accordance with the results of high-performance liquid chromatography-tandem mass spectrometry.This method exhibited high sensitivity,high accuracy,good anti-interference ability,low chemical solvents consumption and environmentally friendliness,and could be used to detect drugs without standards.The developed MALDI-TOF MS method could realize the non-target screening and detection of 10 kinds of illegally added aphrodisiac drugs in foods.

关 键 词：基质辅助激光解吸电离-飞行时间质谱 壮阳抗疲劳类药物 非法添加 α-氰基-4-羟基肉桂酸 介子酸 

分 类 号：O657.63[理学—分析化学]