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第42 卷第 7 期2023 年7 月Vol.42 No.7833~840分析测试学报FENXI CESHI XUEBAO（Journal of Instrumental Analysis）超高效液相色谱－串联质谱法同时测定水产品中10种镇静剂及其代谢物残留王旭峰，王强，张英侠，黄珂*（农业农村部渔业环境及水产品质量监督检验测试中心（广州），中国水产科学研究院南海水产研究所，广东广州510300）摘要：建立了测定水产品中10种镇静剂及其代谢物的通过式固相萃取（SPE）/超高效液相色谱－串联质谱（UPLC－MS/MS）多残留分析方法。
样品经1%氨水－乙酸乙酯提取，KNORTH m-PFC SPE小柱一步式净化。
洗脱液经氮气吹干浓缩，0.5 mL乙腈溶解残渣，采用UPLC－MS/MS测定。
目标物采用JADE－PAK KP－C18（100 mm × 2.1 mm，1.7 μm）色谱柱分离，以0.1%甲酸－乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱。
电喷雾电离正离子（ESI+）扫描，多反应监测（MRM）模式下检测，以保留时间和离子丰度比定性，内标法定量。
10种目标物在对应质量浓度范围内呈良好的线性关系，相关系数（r2）大于0.999，检出限和定量下限分别为0.1 ~ 0.15 μg/kg和0.3 ~ 0.5 μg/kg。
在4种水产品基质中进行3个浓度水平的加标实验，平均加标回收率为82.6% ~ 117%，相对标准偏差（RSD，n = 6）为1.5% ~ 9.3%。
该方法灵敏度高、适用性强，适用于不同水产品基质中镇静剂及其代谢物残留的分析。
关键词：镇静剂；代谢物；通过式固相萃取；超高效液相色谱－串联质谱；水产品中图分类号：O657.7；TS207.3文献标识码：A 文章编号：1004-4957（2023）07-0833-08Simultaneous Determination of Ten Tranquilizers and Their Metabo⁃lites in Aquatic Products by Ultra-performance LiquidChromatography－Tandem Mass SpectrometryWANG Xu-feng，WANG Qiang，ZHANG Ying-xia，HUANG Ke*（South China Sea Fisheries Research Institute，Chinese Academy of Fishery Sciences；Fishery Environment and Aquatic Products Quality Inspection & Testing Center of the Ministry of Agriculture andRural Affaires（Guangzhou），Guangzhou 510300，China）Abstract：A multi-residue analytical method was established for the simultaneous determination of ten tranquilizers and their metabolites in aquatic products by pass-through solid phase extraction（SPE）in combination with ultra-performance liquid chromatography－tandem mass spectrometry（UPLC－MS/ MS）．Samples were extracted with 1% ammonium hydroxide－ethyl acetate，followed by one-step clean⁃up based on KNORTH m-PFC SPE cartridge．The purified extractions were blew to dryness under nitro⁃gen gas．The dried residues were dissolved with 0.5 mL acetonitrile and then injected into UPLC－MS/ MS．The chromatographic separation of ten target analytes were conducted on a JADE－PAK KP－C18 column（100 mm × 2.1 mm，1.7 μm） by gradient elution，utilizing 0.1% formic acid－acetonitrile and 0.1% formic acid solution as mobile phases．The targeted analytes were analyzed with positive electro⁃spray ionization under multiple reaction monitoring（MRM） mode，confirmed using ion ratio and retention time，and quantitated by internal standard method．Excellent linearities for ten target analytes were ob⁃tained in the corresponding mass concentration ranges，with correlation coefficients（r2）larger than 0.999．The limits of detection and the limits of quantitation for aquatic product samples were in the range of 0.1－0.15 μg/kg and 0.3－0.5 μg/kg，respectively．The average recoveries for four negative aquat⁃ic product matrixes at three spiked levels ranged from 82.6% to 117%，with relative standard deviations （RSDs，n = 6） of 1.5%－9.3%．The proposed method is sensitive and versatile，and it can be applieddoi：10.19969/j.fxcsxb.23040604收稿日期：2023－04－06；修回日期：2023－05－09基金项目：中国水产科学研究院南海水产研究所中央级公益性科研院所基本科研业务费专项资金（2021SD20）；农业国家标准和行业标准制修订项目（NYB-23110）；广东省现代农业产业技术体系创新团队建设专项资金（2023KJ151）∗通讯作者：黄珂，副研究员，研究方向：水产品质量安全检测与风险评估，E-mail：xiamike@834分析测试学报第 42 卷to the multi-residue analysis of ten tranquilizers and their metabolites in various aquatic product matrixes.Key words：tranquilizers；metabolite；pass-through solid phase extraction；ultra-performance liq⁃uid chromatography－mass spectrometry；aquatic product镇静剂是一类具有镇定和安眠作用的药物，通过直接抑制中枢神经系统多巴胺活性，从而使动物机能恢复安定，防止狂躁，也能降低动物运输途中死亡率［1］。
史上最详细的“毒死蜱”产品说明书英文通用名称chlorpyrifos其他名称乐斯本化学名称：O,O-二乙基-O-3、5、6-三氯-2-吡啶基硫逐磷酸酯* 实验式：C9H11C13NO3PS分子量：二、理化性质白色结晶固体，溶点-43℃，25℃时饱和蒸汽压，25℃时水中的溶解度为2mg/L，丙醇中为650g/L，苯中为190g/L，二甲苯中为400mg/L，甲醇中为45g/L。
工业品具有似煤油或松节油味。
不溶于水，易溶于苯、乙醚。
毒性急性口服LD50，雄大鼠163mg/kg；雌大鼠135mg/kg。
对免的急性皮LD50约为2000mg/kg；毒死蜱属中等杀虫剂。
对眼睛有轻度刺激，对皮肤有明显刺激，长时间接触会产生灼伤。
在试验剂量下未见致畸、致突变、致癌作用。
在动物体内能很快解毒，对鱼和水生动物毒性较高，对蜜蜂有毒。
剂型２％神农灭蟑螂胶饵，乐斯本%乳油，杀死虫蓝珠14%颗粒剂。
特点毒死蜱具有触杀、胃毒和熏蒸作用。
在叶片上残留期不长，但在土壤中残留期较长，因此对地下害虫防治效果较好，对烟草有药害。
适用范围适用于水稻、小麦、棉花、果树、蔬菜、茶树上多种咀嚼式和刺吸式口器害虫，也可用于防治城市卫生害虫，如１％神农灭蟑螂饵剂。
使用方法11．水稻害虫的防治稻纵卷叶螟、稻蓟马、稻瘿蚊、稻飞虱、稻叶蝉每亩用%乳油60-120毫升对水喷雾。
?2．小麦害虫的防治粘虫、蚜虫每亩用%乳油50-75毫升，对水40-50千克喷雾。
3．棉花害虫的防治棉蚜每亩用%乐斯本乳油50毫升，对水40千克喷雾。
棉叶螨每亩用%乐斯本乳油70--100毫升，对水40千克喷雾。
棉铃虫、红铃虫每亩用100--169毫升，对水喷雾。
4．蔬菜害虫的防治菜青虫、小菜蛾、豆野螟每亩用%乐斯本乳油100-150毫升对水喷雾。
5．大豆害虫的防治大豆食心虫、斜纹夜蛾每亩用%乳油75--100毫升对水喷雾。
6．果树害虫的防治柑橘潜叶蛾、红蜘蛛用%乳油1000-2000倍液喷雾。
超高效液相色谱-串联质谱法测定人尿中硫酸吲哚酚和硫酸对甲酚的含量肖永华; 许开冰; 王胜; 毛翔; 卢圆圆【期刊名称】《《理化检验-化学分册》》【年(卷),期】2019(055)010【总页数】6页(P1151-1156)【关键词】超高效液相色谱-串联质谱法; 硫酸吲哚酚; 硫酸对甲酚; 人尿【作者】肖永华; 许开冰; 王胜; 毛翔; 卢圆圆【作者单位】武汉市疾病预防控制中心武汉 430022; 华中科技大学同济医学院附属同济医院武汉 430030【正文语种】中文【中图分类】O657.63硫酸吲哚酚和硫酸对甲酚分别为色氨酸和酪氨酸在肠道细菌作用下的代谢产物。
食物中的色氨酸经大肠埃希菌分解产生吲哚,吲哚经过门静脉进入肝脏经羟化、硫酸化过程,最终生成硫酸吲哚酚[1-2];肠道厌氧菌将食物中的酪氨酸转变为4-羟基苯乙酸,4-羟基苯乙酸脱羧成为对甲酚,大部分对甲酚经肠道黏膜吸收,在肠道上皮细胞磺基转移酶的作用下转化为硫酸对甲酚。
有研究表明,硫酸吲哚酚和硫酸对甲酚具有肾脏毒性和心血管毒性,能促进心肌细胞凋亡,加重动脉钙化使动脉壁变厚以及心室肥大[3-7],同时,心血管疾病是慢性肾病患者最主要的影响因素之一[8]。
硫酸吲哚酚和硫酸对甲酚还能促进肾间质细胞向成纤维细胞转化,引起肾脏的纤维化,属于尿毒症毒素[9-11]。
当人体肾功能出现障碍时,硫酸对甲酚和硫酸吲哚酚不能有效排除体外,导致在人体内蓄积,从而对人体带来毒副作用。
我国慢性肾病的发病率高达11%,发病率和血液透析人数呈逐年上升趋势[12],在慢性肾病患者的队列研究中,发现游离的硫酸对甲酚是慢性肾病患者的一个重要的死亡率预测因子[13]。
目前,研究硫酸吲哚酚和硫酸对甲酚的生物样本主要为血清和血浆[14-15],对尿液中硫酸吲哚酚和硫酸对甲酚的研究较少。
同时,研究对象主要为肾功能异常的患者,对正常人群研究较少,在国内仅有初启江等[16]研究了正常人血清及尿样中硫酸吲哚酚的含量的分析方法,但是对儿童和孕妇尿样中硫酸吲哚酚和硫酸对甲酚的研究还未见报道。
Vol. 13 ,No.2March 2021第13卷第2期2021年3月环境监控与预警Environmental Monitoring and Forewarning !监测技术！DOI : 10. 3969/j. issn. 167^6732. 2021.02. 005超高效液相色谱-串联质谱法测定水中拟除虫菊酯 和有机磷农药残留杨敏娜，秦兴秀，王来梁（江苏省地质调查研究院自然资源部国土（耕地）生态监测与修复工程技术创新中心，江苏 南京210018 %摘 要：采用直接进样法和萃取浓缩法2种前处理方式，通过超高效液相色谱-串联质谱法对水中20种拟除虫菊酯类和 有机磷类农药进行了测定，并对仪器条件的选择和前处理条件的优化进行了探讨$结果表明,20种农药的线性关系良好,相关系数均〉0.999，直接进样法检出限为0.21 -2.47 'g/L ,回收率为81.0% -119%，相对标准偏差＜10% $萃取浓缩法检出限为0.002 2 -0.004 3 'g/L ,回收率为71.5% -115%，相对标准偏差＜15% $该方法简便、快捷，精密度和准确度较高，可满足水中拟除虫菊酯类和有机磷类农药的检测要求$关键词：超高效液相色谱-串联质谱法；拟除虫菊酯类农药；有机磷类农药中图分类号：X832 ；O657.63文献标志码:B文章编号：1674 -6732 （2021） 02 -0024 -05Determination of Pyrethriod Pesticide and Organic Phosphorus Pesticide Residues in Water by Ultra Performance Liquid Chromatography 一 Tandem Mass SpectrometryYANG Min-na , QIN Xing-xiu , WANG Lai-liang% Cultivated Land Ecological Monitoring and Restoration Engineering Technology Innovation Center of Ministry ofNatural Resourcet , Geological Survey of Jiangsu Provinco , Nanjing , Jiangsu 210018 , China )Abstract : A method for determination of 20 organic phosphorus and pyrethriod pesticides in wateo was established by using ultroperformance liquid chromatography - tandem mass spectrometiy after direci injection or after extraction and concentrated. Theinstrumeni ccnditions and pretreetment ccnditions were optimized. The regression equation of 20 kinds of pesticides showed goodlinear relationship , the ccrrelation coefficients were all greater than 0. 999. The detection limitr were in the range from 0. 21 te2.47 'g/L foe direct injection, and the average reccvvries ranged from 81. 0% to 119% with the relativv standard deviations lessthan 10% . For extraction and ccnccntration method , the method detection limitr of the target ccmpounds were in the range from 0.002 2 to 0.004 3 'g/L, and the average recoveries ranged from 71.5% to 115% with the relative standard deviations less than15% . This method is simple and fast, and itr precision and accuracy can meet the demands of determination of pyrethriod prsticideand oraanic phosphorus pesticide in water.Key words : UPLC-MS/MS ； Pyrethriod pesticide ； Oraanic phosphorous pesticide农药在现代化农业中必不可少,有机磷、拟除 虫菊酯和氨基甲酸酯类农药是目前使用量最大的 3类农药，它们普遍具有高效、广谱、低毒、低残留等特点'1（,在农业生产中被广泛应用'_3（。
农药研究Pesticide Science and Administration2021,42(2)超高效液相色谱-串联质谱法测定水中双酰胺类杀虫剂的残留量韩帅兵，张耀中，于淼，薛雯，李向阳，吴亚玉，周力*(山东省农药检定所，山东济南250100)Determination of Diamide Insecticides Residues in Water by High Performance Liquid Chromatography-Tandem Mas s Spectrometry3an Shuaibing,Zhang Yaozhong,Yu Mao,Xue Wen,Li Xiangyang,Wu Yayg,Zhoo Li(Shandong Institute of the Control of Agrochemicals,Jinan Shandong250100,China)Abstract:A method fXr the determination of5diamide insecticides residues in water by ultra per-formoice liquid chromatoaraphy-tandem mass spectrometa(UPLC-MS/MS)was established.Firstly,residues in water were eneded and puriWed by SPE caeridges.Then,the SPE caeridgeswere eluted with oraanic solvenO Fingly,the samples were concentrated and determined.The results demonstrated that the concentrations of3pesticides including chlorantraniliprole had a goodlinear relationshin with the corresponding peak area in the range of0.004〜0.4mg/L and the coxelation coefficients were all above0.99-The average recavvees ranged from85-1%to104-8%,with RSDs from 1.7%to8.5%in the range of0.1〜5.0"g/L.The limit of quantification was0.1"g/L.The concentrations of the other2pesticides including cyantraniliprole had a good linearrelationshin with the cocesponding peak area in the range of0.01〜0.4mg/L and the cecelationcoefficients were all above0.99-The average recaveees ranged from76.4%to107.9%,with RSDs from 1.8%to10.7%in the range of0.5〜5.0"g/L.The Omit of quantification was0.5"gL.The method showed good chamcme sties of simplicity,accurace and time-saving.Key words：diamide insecticides；water；residues；UPLC-MS/MS摘要：建立了使用超高效液相色谱一串联质谱法(UPLC-MS/MS)测定水中5种双酰胺收稿日期：2020-12-22作者简介：韩帅兵，男，博士研究生，高级农艺师，主要从事农药残留检测工作。
QuEChERS－超高效液相色谱－串联质谱法测定蜂蜜中１９种喹诺酮类抗生素倪杨 杨军军 石磊 张莹莹 熊融（北京市农林科学院林业果树研究所，北京市落叶果树工程技术研究中心，农业农村部果品及苗木质量监督检验测试中心（北京），北京 100093）摘要：建立超高效液相色谱-串联质谱法（ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS）同时测定蜂蜜中19种喹诺酮类药物含量的分析方法。
实验对样品前处理过程及色谱质谱仪器条件进行优化。
蜂蜜样品与超纯水1∶1混合后涡旋振荡溶解，经乙腈溶液超声提取，再加入氯化钠盐析分层，离心后上清液采用C18吸附剂进行净化处理，以ACQUITY BEH C18色谱柱分离。
在电喷雾离子（electrospray ionization, ESI）源正离子扫描模式下，采用多反应监测（multiple reaction monitoring, MRM）模式进行检测，外标法进行定量。
结果表明，19种喹诺酮类药物在3 min内完成色谱分离分析，在0.2~50 μg/L质量浓度范围内呈现良好线性关系，相关系数（R2）均大于0.995，检出限（limit of detection, LOD）为0.25~0.50 μg/kg，定量限（limit of quantification, LOQ）为0.80~1.50 μg/kg。
在低、中、高3个添加浓度水平下，蜂蜜中19种喹诺酮类药物的加标回收率为78.9%~96.5%，相对标准偏差（relative standard deviations, RSDs）为1.8%~4.9%（n=6）。
该方法稳定、准确、灵敏、快速，适用于蜂蜜中喹诺酮类抗生素的快速检测和分析确证。
关键词：QuEChERS；超高效液相色谱-串联质谱；喹诺酮类抗生素；蜂蜜Simultaneous determination of 19 quinolone antibiotics in honey byQuEChERS-UPLC-MS/MSNi Y ang, Y ang Junjun, Shi Lei, Zhang Yingying, Xiong Rong(Institute of Forestry and Pomology, Beijing Academy of Agriculture and Forestry Sciences, Beijing Engineering Research Center for Deciduous Fruit Trees, Inspection and Testing Laboratory of Fruits and Nursery Stocks (Beijing) Ministry ofAgriculture and Rural Affairs, Beijing 100093, China)Abstract: To establish a method for simultaneous determination of 19 quinolone antibiotics in honey by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) combined with QuEChERS extraction. The pretreatment process and instrument conditions were optimized. Samples were mixed with ultrapure water at a ratio of 1:1, ultrasonic extracted with acetonitrile solution and salted out by adding NaCl. After centrifugation, the supernatant was cleaned up by C18 sorbent and separated on an ACQUITY BEH C18 column. In the electrospray ionization (ESI) positive ion scanning mode, the samples were analyzed by multiple reaction monitoring (MRM) and quantifi ed by external standard method. Result showed that all the 19 quinolone antibiotics were well separated in 3 min and the calibration curves in the range of 0.2-50 μg/L for all compounds were linear with correlation coeffi cients(R2)were more than 0.995. The limits of detection (LODs) and limits of quantifi cation (LOQs) in honey were 0.25-0.50 μg/kg and 0.80-1.50 μg/kg, respectively. The average recoveries of 19 quinolone antibiotics in different matrices at low, medium and high spiked levels were ranged from 78.9%-96.5%, with relative standard deviations (RSDs) in the range of 1.8%-4.9% (n=6). The method is proved to be stable, accurate, sensitive and rapid, and can meet requirements for the rapid and accurate determination of quinolone antibiotics in honey sample.Key words: QuEChERS; UPLC-MS/MS; quinolone antibiotics; honey基金项目：北京市科技计划项目（Z201100008920007），北京市农林科学院科技创新能力建设专项（KJCX20200302）作者简介：倪杨（1985-），女，博士，高级农艺师，研究方向农产品质量安全，E-mail:***************通信作者：熊融（1977-），女，硕士，高级工程师，研究方向植物资源评价与检测技术研究，E-mail:**********************中国蜂业APICULTURE OF CHINA和除杂富集效果有待提高，因其操作复杂、过柱时间长且成本较高，不适合大批量快速检测。
第42 卷第 10 期2023 年10 月Vol.42 No.101343~1350分析测试学报FENXI CESHI XUEBAO（Journal of Instrumental Analysis）超高效液相色谱-串联质谱筛查确证尿液中磺胺、喹诺酮与四环素抗生素张楠1，唐增煦2，王莉莉1，孙开奇1，赵榕1*，范赛1*（1．北京市疾病预防控制中心，北京市预防医学研究中心，北京100013；2．中国疾病预防控制中心营养与健康所，北京100050）摘要：建立了超高效液相色谱-串联质谱法（UPLC-MS/MS）同时测定尿液中磺胺类、四环素类、喹诺酮类共45种抗生素的检测方法。
尿液样品经提取后，采用HLB固相萃取柱（200 mg/6 mL）净化，使用ThermoAccu⁃core RP-MS（100 mm×2.1 mm，2.6 µm）色谱柱进行分离，以乙腈-0.02%甲酸溶液为流动相梯度洗脱。
在正离子扫描模式下（ESI+），以选择反应监测模式（SRM）检测，外标法定量。
45种目标化合物在3个加标水平（2.0、5.0、10.0 µg/L）下的回收率为78.6%~114%，相对标准偏差为0.60%~18%；方法的检出限为0.1~0.5 µg/L，定量下限为0.3~1 µg/L。
将所建方法用于280个尿液样品中抗生素的检测，均未检测到抗生素残留。
所建方法的精密度和准确度高，操作简单便捷，为尿液中抗生素残留的筛查提供了方法支持。
关键词：抗生素；尿液；超高效液相色谱-串联质谱法；磺胺；喹诺酮；四环素中图分类号：O657.7；S816.73文献标识码：A 文章编号：1004-4957（2023）10-1343-08Study on the Method for the Identification of Sulfanilamide，Quino⁃lone and Tetracycline in Urine by Ultra-high Performance LiquidChromatography-Tandem Mass SpectrometryZHANG Nan1，TANG Zeng-xu2，WANG Li-li1，SUN Kai-qi1，ZHAO Rong1*，FAN Sai1*（1．Beijing Center for Disease Control and Prevention，Beijing Center for Preventive Medicine Research，Beijing 100013，China；2．Institute of Nutrition and Health，Chinese Center for Disease Control and Prevention，Beijing 100050，China）Abstract：A confirmatory test for the simultaneous determination of sulfonamides，tetracyclines，and quinolones in urine totalling 45 antibiotics by ultra-high performance liquid chromatography-tan⁃dem mass spectrometry（UPLC-MS/MS） was developed. The urine samples were extracted and then cleaned up by an HLB solid phase extraction column（200 mg/6 mL），and the separation of the target was performed on a ThermoAccucore RP-MS column（100 mm×2.1 mm，2.6 µm）using acetoni⁃trile-0.02%formic acid aqueous solution with gradient separation elution，detected in positive ion scanning mode（ESI+） in multiple selected reaction monitoring（SRM） and quantified by external stan⁃dard method. The recoveries of a total of 45 target compounds from three classes of antibiotics at three spiked levels（2.0，5.0 and 10.0 µg/L） were in the range of 78.6 %-114% with the RSDs in the range of 0.60%-18%，and the limits of detection（LODs） and the limits of quantification（LOQs） of the method were in the range of 0.1-0.5 µg/L and 0.3-1 µg/L，respectively. The developed meth⁃od was applied to 280 urine samples for the detection of antibiotics，none of which detected antibiot⁃ics residues in excess of limit. The results showed that the established method was highly precise and accurate，simple and convenient，and included commonly used antibiotic species，which can sup⁃port the screening antibiotic residues in urine.Key words：antibiotic；urine；ultra-high performance liquid chromatography-tandem mass spec⁃trometry；sulfonamides；quinolones；tetracyclines四环素类、磺胺类和喹诺酮类广谱抗生素是常见的既可治疗人类疾病，又可作为生长促进剂促进doi：10.19969/j.fxcsxb.23061602收稿日期：2023－06－16；修回日期：2023－07－22基金项目：国家重点研发计划（2017YFC160050002）∗通讯作者：赵 榕，主任技师，研究方向：食品安全，E-mail：lxyue@范 赛，博士，研究员，研究方向：食品安全，E-mail：fansai@第 42 卷分析测试学报动物生长的化学物质［1］，因此在医药卫生及动物养殖行业得到了广泛使用。
