水产品中水杨酸的液相色谱-串联质谱检测及其残留来源分析
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摘要
本研究建立了高效液相色谱-串联质谱快速测定水产品中水杨酸的分析方法。样品直接采用1%甲酸-乙腈溶液提取,乙腈饱和正己烷除油净化,提取液过膜后采用C18(1.7μm,2.1mm×50mm i.d)色谱柱进行分离,以乙腈-0.10%甲酸水溶液为流动相进行梯度洗脱,电喷雾电离,负离子多反应监测模式检测,外标法定量。结果表明:在所建立的方法条件下,水杨酸在0.5～50ng/mL范围内线性关系良好,相关系数为0.999;检出限为2.5μg/kg;不同水产品(黄鳝、财鱼、草鱼和龙虾)在高、中、低3个添加水平下的平均加标回收率在69.10%～97.30%之间,相对标准偏差在2.30%～13.40%之间(n=6)。本方法简便快速、灵敏度高,在日常检测方面存在一定的优势。采用所建立的方法对实际水产样品中的水杨酸残留进行检测,并对残留来源进行溯源分析,可为食品安全风险性评价提供参考依据。
In this study, a rapid method was developed for determination of salicylic acid in aquatic products by high performance liquid chromatography-tandem mass spectrometry. Samples were directly extracted with 1% formic acid acetonitrile and purified with acetonitrile saturated N-hexane, then separated on a C_(18)(1.7 μm, 2.1 mm×50 mm i.d) column and eluted with the mobile phase of acetonitrile -0.10% formic acid aqueous solution, and analyzed by mass spectrometry in negative ion multiple reaction monitoring mode and using external standards. The results showed that good linearity was obtained in the range of 0.5～50 ng/mL for salicylic acid under the established method, and the correlation coefficients was 0.999. The limits of detection(LOD) was 2.5 μg/kg. The average recoveries of the method was ranged from 69.10% to 97.20%with relative standard deviations ranged from 2.30% to 13.40% in aquatic products(Monopterus albus, Snakehead, grass carp and lobster) at three spiked levels(n=6). This proposed method was advantageous in routine detection of salicylic acid residues in aquatic products for its simplicity and high sensibility. The established method was used to detect salicylic acid residues in real aquatic products, and trace the source analysis of the residues, which can provide a useful guideline for risk assessment of the food safety.
In this study, a rapid method was developed for determination of salicylic acid in aquatic products by high performance liquid chromatography-tandem mass spectrometry. Samples were directly extracted with 1% formic acid acetonitrile and purified with acetonitrile saturated N-hexane, then separated on a C_(18)(1.7 μm, 2.1 mm×50 mm i.d) column and eluted with the mobile phase of acetonitrile -0.10% formic acid aqueous solution, and analyzed by mass spectrometry in negative ion multiple reaction monitoring mode and using external standards. The results showed that good linearity was obtained in the range of 0.5～50 ng/mL for salicylic acid under the established method, and the correlation coefficients was 0.999. The limits of detection(LOD) was 2.5 μg/kg. The average recoveries of the method was ranged from 69.10% to 97.20%with relative standard deviations ranged from 2.30% to 13.40% in aquatic products(Monopterus albus, Snakehead, grass carp and lobster) at three spiked levels(n=6). This proposed method was advantageous in routine detection of salicylic acid residues in aquatic products for its simplicity and high sensibility. The established method was used to detect salicylic acid residues in real aquatic products, and trace the source analysis of the residues, which can provide a useful guideline for risk assessment of the food safety.
引文
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[5]韩晓光,周迎春.解热镇痛药阿司匹林的制备研究[J].安徽化工,2017,43(6):54-55HAN Xiao-guang,ZHOU Ying-chun.Study on the preparation of antipyretic analgesic Aspirin[J].Anhui Chemical Industry,2017,43(6):54-55
[6]祝志凌,刘志平,林君妹,等.胆酸-水杨酸酯缀合物的合成与表征[J].广西师范学院学报(自然科学版),2018,35:59-62ZHU Zhi-ling,LIU Zhi-ping,LIN Jun-mei,et al.Synthesis and characterization of cholic acid and salicylate conjugate compounds[J].Journal of Guangxi Teachers Education University(Natural Science Edition),2018,35:59-62
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[8]Wang G,Liu G G,Liu H J,et al.Photodegradation of salicylic acid in aquatic environment:Effect of different forms of nitrogen[J].Science of the Total Environment,2012,435-436(7):573-577
[9]钟冬莲,任传义,李祖光,等.HPLC-MS/MS法同时测定马尾松松针中水杨酸和茉莉酸[J].分析试验室,2017,36(2):164-167ZHONG Dong-lian,REN Chuan-yi,LI Zu-guang,et al.Simultaneous determination of salicylic acid and jasmonic acid in Pinus massoninan by high performance liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Analysis Laboratory,2017,36(2):164-167
[10]Sun L J,Feng Q M,Yan Y F,et al.Paper-based electroanalytical devices for in situ determination of salicylic acid in living tomato leaves[J].Biosensors and Bioelectronics,2014,60(11):154-160
[11]杨国慧,范婷婷,陈效杰,等.树莓叶果中水杨酸含量测定及其抑菌性分析[J].江苏农业科学,2017,45(23):181-183YANG Guo-hui,FAN Ting-ting,CHEN Xiao-jie,et al.Determination of salicylic acid content in Yeguo and its antibacterial properties[J].Jiangsu Agricultural Sciences,2017,45(23):181-183
[12]Elisa S,Marta R,Gabriele C.Simultaneous determination of shikimic acid,salicylic acid and jasmonic acid in wild and transgenic Nicotiana langsdorffii plants exposed to abiotic stresses[J].Plant Physiology and Biochemistry,2016,103:53-60
[13]张瑞,陆舍铭,丁丽婷,等.超高效液相色谱-串联质谱法快速测定化妆品中水杨酸[J].理化检验-化学分册,2011,47(1):65-67ZHANG Rui,LU She-ming,DING Li-ting,et al.Rapid determination of salicylic acid in cosmetics by UPLC-MS/MS[J].Physical Testing and Chemical Analysis,2011,47(1):65-67
[14]杨孝容,向清祥,向茜新,等.HPLC同时测定阿司匹林类药物中阿司匹林的含量和游离水杨酸的限量[J].华西药学杂志,2017,32(1):84-86YANG Xiao-rong,XIANG Qing-xiang,XIANG Qian-xin,et al.Simultaneous determination of the content of aspirin and the limit of free salicylic acid in Aspirin type drugs by HPLC[J].West China Journal of Pharmaceutical Sciences,2017,32(1):84-86
[15]魏永锋,李小花,马冬梅.同步扫描荧光光谱法同时测定阿司匹林和水杨酸[J].光谱学与光谱分析,2005,25(4):588-590WEI Yong-feng,LI Xiao-hua,MA Dong-mei.Simultaneous determination of aspirin and salicyclic acid by synchronous fluorescence spectrometry[J].Spectroscopy and Spectral Analysis,2005,25(4):588-590
[16]Murillo P J,Ala?ón M A,Fernández L P,et al.Direct determination of closely overlapping drug mixtures of diflunisal and salicylic acid in serum by means of derivative matrix isopotential synchronous fluorescence spectrometry[J].Analytica Chimica Acta,2007,583(1):55-62
[17]李秀敏,赵颖,杨宁,等.海勒氏液中苯甲酸、水杨酸的含量测定[J].药物分析杂志,2015,35(11):2032-2035LI Xiu-min,ZHAO Ying,YANG Ning,et al.Determination of benzoic acid and salicylic acid in Haileshi Ye[J].Chinese Journal of Pharmaceutical Analysis,2015,35(11):2032-2035
[18]Fang X A,Chen G S,Qiu J L,et al.Determination of four salicylic acids in aloe by in vivo solid phase microextraction coupling with liquid chromatography-photodiode array detection[J].Talanta,2018,184:520-526
[19]Antonella A,CarloZ.Simultaneous determination of salicylic,3-methyl salicylic,4-methyl salicylic,acetylsalicylic and benzoic acids in fruit,vegetables and derived beverages by SPME-LC-UV/DAD[J].Journal of Pharmaceutical and Biomedical Analysis,2016,121:63-68
[20]宋圆圆,徐建峰,梁笑婷,等.利用气相色谱法同时测定番茄叶片中的信号物质水杨酸和茉莉酸[J].江西农业大学学报,2010,32(5):1056-1060SONG Yuan-yuan,XU Jian-feng,LIANG Xiao-ting,et al.Simultaneous quantification of jasmonic and salicylic acids in tomato plants by gas chromatography[J].Acta Agriculturae Universitatis Jiangxiensis,2010,32(5):1056-1060
[21]Michael J S,Dominic P T,Roberts L A,et al.Free salicylic acid and acetyl salicylic acid content of foods using gas chromatography-mass spectrometry[J].Food Chemistry,2007,105(1):273-279
[22]Anja J,Peet J V R,Stephan L,et al.Stable isotope dilution analysis of salicylic acid and hydroquinone in human skin samples by gas chromatography with mass spectrometric detection[J].Journal of Chromatography B,2007,852(1-2):300-307
[23]李腾飞,赵风年,张超,等.高效液相色谱-三重四极杆质谱法同时测定番茄中水杨酸和赤霉酸[J].食品科学,2016,37(8):182-186LI Teng-fei,ZHAO Feng-nian,ZHANG Chao,et al.Simultaneous determination of salicylic acid and gibberellic acid in tomato by high performance liquid chromatography tandem mass spectrometry[J].Food Science,2016,37(8):182-186
[24]Dávid S,Márat P,Gábor S,et al.Robust and sensitive LC/MS-MS method for simultaneous detection of acetylsalicylic acid and salicylic acid in human plasma[J].Microchemical Journal,2018,136:200-208
[25]GB/T 27404-2008,实验室质量控制规范食品理化检验[S]GB/T 27404-2008,Criterion on quality control of laboratories-chemical testing of food[S]
[26]王立琦,贺利民,曾振灵,等.液相色谱-串联质谱检测兽药残留中的基质效应研究进展[J].质谱学报,2011,32(6):321-332WANG Li-qi,HE Li-min,ZENG Zhen-ling,et al.Progress in matrix effect of veterinary drug residues analysis by high-performance liquid chromatography tandem mass spectrometry[J].Journal of Chinese Mass Spectrometry Society,2011,32(6):321-332
[27]朱晓玲,张莉,韩智,等.湖北省水产养殖环节安全现状及所存在的问题-基于对湖北咸宁、仙桃和潜江三地的实地调研[J].食品安全质量检测学报,2018,9(8):1906-1910ZHU Xiao-ling,ZHANG Li,HAN Zhi,et al.Present status and existing problems of aquaculture safety in Hubei province-Based on the field investigation of Xianning,Xiantao and Qianjiang in Hubei[J].Journal of Food Safety and Quality,2018,9(8):1906-1910
[2]季丹丹,刘艳红,祝钧.化妆品用水杨酸酯类衍生物的制备及应用进展[J].日用化学工业,2015,45(11):648-652JI Dan-dan,LIU Yan-hong,ZHU Jun.Preparation and applications of salicylic acid esters used in cosmetics[J].China Surfactant Detergent&Cosmetics,2015,45(11):648-652
[3]薛峰,林毅侃,马跃龙,等.食品中水杨酸含量测定方法的研究进展[J].食品工业科技,2012,33(14):429-431XUE Feng,LIN Yi-kan,MA Yue-long,et al.Research progress in method of determination of salicylic acid in food[J].Science and Technology of Food Industry,2012,33(14):429-431
[4]Labib R,Bury D,Boisleve F,et al.A kinetic-based safety assessment of consumer exposure to salicylic acid from cosmetic products demonstrates no evidence of a health risk from developmental toxicity[J].Regulatory Toxicology and Pharmacology,2018,94:245-251
[5]韩晓光,周迎春.解热镇痛药阿司匹林的制备研究[J].安徽化工,2017,43(6):54-55HAN Xiao-guang,ZHOU Ying-chun.Study on the preparation of antipyretic analgesic Aspirin[J].Anhui Chemical Industry,2017,43(6):54-55
[6]祝志凌,刘志平,林君妹,等.胆酸-水杨酸酯缀合物的合成与表征[J].广西师范学院学报(自然科学版),2018,35:59-62ZHU Zhi-ling,LIU Zhi-ping,LIN Jun-mei,et al.Synthesis and characterization of cholic acid and salicylate conjugate compounds[J].Journal of Guangxi Teachers Education University(Natural Science Edition),2018,35:59-62
[7]中华人民共和国农业部公告第235号,动物性食品中兽药最高残留限量.[EB/OL].http://jiuban.moa.gov.cn/zwllm/nybz/200803/t20080304_1028649.htm Ministry of Agriculture of the People's Republic of China Notice No.235,Maximum residue limit of Veterinary Medicine in animal foods[EB/OL].http://jiuban.moa.gov.cn/zwllm/nybz/200803/t20080304_1028649.htm
[8]Wang G,Liu G G,Liu H J,et al.Photodegradation of salicylic acid in aquatic environment:Effect of different forms of nitrogen[J].Science of the Total Environment,2012,435-436(7):573-577
[9]钟冬莲,任传义,李祖光,等.HPLC-MS/MS法同时测定马尾松松针中水杨酸和茉莉酸[J].分析试验室,2017,36(2):164-167ZHONG Dong-lian,REN Chuan-yi,LI Zu-guang,et al.Simultaneous determination of salicylic acid and jasmonic acid in Pinus massoninan by high performance liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Analysis Laboratory,2017,36(2):164-167
[10]Sun L J,Feng Q M,Yan Y F,et al.Paper-based electroanalytical devices for in situ determination of salicylic acid in living tomato leaves[J].Biosensors and Bioelectronics,2014,60(11):154-160
[11]杨国慧,范婷婷,陈效杰,等.树莓叶果中水杨酸含量测定及其抑菌性分析[J].江苏农业科学,2017,45(23):181-183YANG Guo-hui,FAN Ting-ting,CHEN Xiao-jie,et al.Determination of salicylic acid content in Yeguo and its antibacterial properties[J].Jiangsu Agricultural Sciences,2017,45(23):181-183
[12]Elisa S,Marta R,Gabriele C.Simultaneous determination of shikimic acid,salicylic acid and jasmonic acid in wild and transgenic Nicotiana langsdorffii plants exposed to abiotic stresses[J].Plant Physiology and Biochemistry,2016,103:53-60
[13]张瑞,陆舍铭,丁丽婷,等.超高效液相色谱-串联质谱法快速测定化妆品中水杨酸[J].理化检验-化学分册,2011,47(1):65-67ZHANG Rui,LU She-ming,DING Li-ting,et al.Rapid determination of salicylic acid in cosmetics by UPLC-MS/MS[J].Physical Testing and Chemical Analysis,2011,47(1):65-67
[14]杨孝容,向清祥,向茜新,等.HPLC同时测定阿司匹林类药物中阿司匹林的含量和游离水杨酸的限量[J].华西药学杂志,2017,32(1):84-86YANG Xiao-rong,XIANG Qing-xiang,XIANG Qian-xin,et al.Simultaneous determination of the content of aspirin and the limit of free salicylic acid in Aspirin type drugs by HPLC[J].West China Journal of Pharmaceutical Sciences,2017,32(1):84-86
[15]魏永锋,李小花,马冬梅.同步扫描荧光光谱法同时测定阿司匹林和水杨酸[J].光谱学与光谱分析,2005,25(4):588-590WEI Yong-feng,LI Xiao-hua,MA Dong-mei.Simultaneous determination of aspirin and salicyclic acid by synchronous fluorescence spectrometry[J].Spectroscopy and Spectral Analysis,2005,25(4):588-590
[16]Murillo P J,Ala?ón M A,Fernández L P,et al.Direct determination of closely overlapping drug mixtures of diflunisal and salicylic acid in serum by means of derivative matrix isopotential synchronous fluorescence spectrometry[J].Analytica Chimica Acta,2007,583(1):55-62
[17]李秀敏,赵颖,杨宁,等.海勒氏液中苯甲酸、水杨酸的含量测定[J].药物分析杂志,2015,35(11):2032-2035LI Xiu-min,ZHAO Ying,YANG Ning,et al.Determination of benzoic acid and salicylic acid in Haileshi Ye[J].Chinese Journal of Pharmaceutical Analysis,2015,35(11):2032-2035
[18]Fang X A,Chen G S,Qiu J L,et al.Determination of four salicylic acids in aloe by in vivo solid phase microextraction coupling with liquid chromatography-photodiode array detection[J].Talanta,2018,184:520-526
[19]Antonella A,CarloZ.Simultaneous determination of salicylic,3-methyl salicylic,4-methyl salicylic,acetylsalicylic and benzoic acids in fruit,vegetables and derived beverages by SPME-LC-UV/DAD[J].Journal of Pharmaceutical and Biomedical Analysis,2016,121:63-68
[20]宋圆圆,徐建峰,梁笑婷,等.利用气相色谱法同时测定番茄叶片中的信号物质水杨酸和茉莉酸[J].江西农业大学学报,2010,32(5):1056-1060SONG Yuan-yuan,XU Jian-feng,LIANG Xiao-ting,et al.Simultaneous quantification of jasmonic and salicylic acids in tomato plants by gas chromatography[J].Acta Agriculturae Universitatis Jiangxiensis,2010,32(5):1056-1060
[21]Michael J S,Dominic P T,Roberts L A,et al.Free salicylic acid and acetyl salicylic acid content of foods using gas chromatography-mass spectrometry[J].Food Chemistry,2007,105(1):273-279
[22]Anja J,Peet J V R,Stephan L,et al.Stable isotope dilution analysis of salicylic acid and hydroquinone in human skin samples by gas chromatography with mass spectrometric detection[J].Journal of Chromatography B,2007,852(1-2):300-307
[23]李腾飞,赵风年,张超,等.高效液相色谱-三重四极杆质谱法同时测定番茄中水杨酸和赤霉酸[J].食品科学,2016,37(8):182-186LI Teng-fei,ZHAO Feng-nian,ZHANG Chao,et al.Simultaneous determination of salicylic acid and gibberellic acid in tomato by high performance liquid chromatography tandem mass spectrometry[J].Food Science,2016,37(8):182-186
[24]Dávid S,Márat P,Gábor S,et al.Robust and sensitive LC/MS-MS method for simultaneous detection of acetylsalicylic acid and salicylic acid in human plasma[J].Microchemical Journal,2018,136:200-208
[25]GB/T 27404-2008,实验室质量控制规范食品理化检验[S]GB/T 27404-2008,Criterion on quality control of laboratories-chemical testing of food[S]
[26]王立琦,贺利民,曾振灵,等.液相色谱-串联质谱检测兽药残留中的基质效应研究进展[J].质谱学报,2011,32(6):321-332WANG Li-qi,HE Li-min,ZENG Zhen-ling,et al.Progress in matrix effect of veterinary drug residues analysis by high-performance liquid chromatography tandem mass spectrometry[J].Journal of Chinese Mass Spectrometry Society,2011,32(6):321-332
[27]朱晓玲,张莉,韩智,等.湖北省水产养殖环节安全现状及所存在的问题-基于对湖北咸宁、仙桃和潜江三地的实地调研[J].食品安全质量检测学报,2018,9(8):1906-1910ZHU Xiao-ling,ZHANG Li,HAN Zhi,et al.Present status and existing problems of aquaculture safety in Hubei province-Based on the field investigation of Xianning,Xiantao and Qianjiang in Hubei[J].Journal of Food Safety and Quality,2018,9(8):1906-1910