气相色谱-质谱法测定肝脏组织中盐酸克伦特罗和盐酸菜克多巴胺

建立了同时测定动物肝组织中盐酸克伦特罗和盐酸莱克多巴胺残留量的固相萃取-气相色谱-质谱分析方法。动物肝组织样品在碱化的条件下用乙酸乙酯和异丙醇混合溶剂提取，提取液浓缩后用乙酸乙酯溶解，然后再用稀盐酸反萃取去除脂肪，调pH值后经SCX固相萃取（SPE）柱净化，洗脱液经氮气吹干后经双三甲基硅基三氟乙酰氨（BSTFA）衍生，采用选择离子模式（盐酸克伦特罗：86、212、262、277，盐酸莱克多巴胺：163、192、234、250）进行测定，外标法定量。盐酸克伦特罗和盐酸莱克多巴胺的检出限分别为0．30和1．00μg／kg。盐酸克伦特罗添加浓度在1．0～5．0μg／kg范围内，添加回收率为77．4％～88．3％；相对标准偏差（RSD）为3．1％～5．1％；盐酸莱克多巴胺添加浓度在4．0～20．0μg／kg，添加回收率为69．8％～82．1％；相对标准偏差（RSD）为3．5％～4．9％；衍生物的峰面积与被测物浓度分别在0．003～1．00mg／L和0．012～4．00mg／L范围内呈良好的线性关系，线性回归系数均大于0．999。     

稻米中13种苯氧羧酸类除草剂多残留的高效液相色谱-质谱测定

建立了高效液相色谱-质谱联用（HPLC—MS）选择离子监测（SIM）同时测定稻米中13种苯氧羧酸类除草剂多残留的方法。样品经过乙腈提取,盐酸酸化,SCX阳离子交换吸附剂分散固相萃取净化后,采用HPLC—MS测定。对13种苯氧羧酸类除草剂的液相色谱分离、样品前处理条件进行了详细的研究和优化,13种苯氧羧酸类除草剂在0．02～1．0mg／L范围内线性良好,相关系数为0．9954～0．9998。在0．05～1．0mg／kg范围内,平均添加回收率为77％～99％,相对标准偏差为0．9％～14．9％。     

猪肝脏和肌肉组织中β-兴奋剂克伦特罗的高效液相色谱电喷雾质谱分析研究

建立了猪肉和肝组织中克伦特罗的高效液相色谱电喷雾质谱(HPLC—ESI／MS)分析方法。在最佳色谱条件下克伦特罗的保留时间为16min,样品空白无干扰。定量分析的线性范围为2—100mg／L;最低检出限为0．75mg／L;方法回收率为95％-98％;RSD小于2．0％。利用ESI／MS／MS对β-兴奋剂克伦特罗进行了质谱解析,选择特征离子峰m／z277、259和203作为准确定性的依据。对实际生物样品猪瘦肉和肝进行检测结果表明,当样品中克伦特罗残留含量较高时,可以利用紫外检测数据对其进行准确定量。当残留含量低于最低检出限时,可以根据HPLC／ESI／MS结果中有无特征峰出现,给出较准确的定性结果。     

气相色谱-质谱法测定肝脏组织中盐酸克伦特罗和盐酸莱克多巴胺

建立了同时测定动物肝组织中盐酸克伦特罗和盐酸莱克多巴胺残留量的固相萃取-气相色谱-质谱分析方法。动物肝组织样品在碱化的条件下用乙酸乙酯和异丙醇混合溶剂提取,提取液浓缩后用乙酸乙酯溶解,然后再用稀盐酸反萃取去除脂肪,调pH值后经SCX固相萃取(SPE)柱净化,洗脱液经氮气吹干后经双三甲基硅基三氟乙酰氨(BSTFA)衍生,采用选择离子模式(盐酸克伦特罗:86、212、262、277,盐酸莱克多巴胺:163、192、234、250)进行测定,外标法定量。盐酸克伦特罗和盐酸莱克多巴胺的检出限分别为0.30和1.00μg/kg。盐酸克伦特罗添加浓度在1.0~5.0μg/kg范围内,添加回收率为77.4%~88.3%;相对标准偏差(RSD)为3.1%~5.1%;盐酸莱克多巴胺添加浓度在4.0~20.0μg/kg,添加回收率为69.8%~82.1%;相对标准偏差(RSD)为3.5%~4.9%;衍生物的峰面积与被测物浓度分别在0.003~1.00 mg/L和0.012~4.00 mg/L范围内呈良好的线性关系,线性回归系数均大于0.999。     

应用表面增强拉曼光谱技术快速检测尿样中的β-兴奋剂

应用表面增强拉曼光谱技术与化学计量法相结合分析克伦特罗、沙丁胺醇和莱克多巴胺3种β-兴奋剂的标准溶液.在取自10头猪的尿样中,分别添加5个不同浓度的莱克多巴胺(1～20 mg/L),采用快速的液液萃取法对样品进行前处理,再进行表面增强拉曼测试.结果表明,克伦特罗和沙丁胺醇标准溶液的最低检测浓度为2 μg/L,莱克多巴胺标准溶液的最低检测浓度为0.1 mg/L;通过偏最小二乘法建立模型进行定量分析,3种药物的实际值与预测值的相关系数(R2)为0.9134～0.9368;本方法可检测尿样中1 mg/L莱克多巴胺,经外部验证后模型的实际值与预测值的相关系数(R2)为0 881,相对分析误差(RPD)为2.83;分析尿液中的莱克多巴胺含量所需时间小于30 min,为快速检测莱克多巴胺提供新途径.     

Determination of Four β2-Agonists Residues in Sausage by Matrix Solid-phase Dispersion and High Performance Liquid Chromatography- Tandem Mass Spectrometry

利用同位素稀释技术,建立了肉肠中4种β2-受体激动剂克伦特罗、莱克多巴胺、沙丁胺醇和特布他林的基质固相分散/高效液相色谱-串联质谱( MSPD/HPLC - MS/MS)分析方法.样品经C1s填料研磨,甲醇洗脱,提取物经酶解后,用MCX小柱净化,经高效液相色谱分离,在正离子多反应监测(MRM)模式下用电喷雾电离串联质谱测定,内标法定量.4种β2-受体激动剂在0.2～20.0 μg/L质量浓度范围内呈良好的线性关系,相关系数(r2)均大于0.990;沙丁胺醇和克伦特罗的检出限为0.10 μg/kg;莱克多巴胺和特布他林的检出限为0.15 μg/kg;方法的回收率为80％～ 109％,相对标准偏差小于10％.该方法简便快捷、灵敏度高,样品和溶剂用量少,可满足肉肠中4种β2-受体激动剂残留的快速检测.     

离子阱GC-MS-MS检测鼠药中的毒鼠强

建立了离子阱气相色谱-串级质谱（MS—MS）检测鼠药中毒鼠强的方法。测定毒鼠强的线性范围为0．2～5．0mg／L,线性相关系数为0．9984,检出限为0．0013mg／kg,回收率为76．1％～116．7％,测定结果的相对标准偏差为6．1％（n=6）。同时利用二级质谱分析了毒鼠强裂解规律,该法对毒鼠强具有良好的确证性。     

林蛙油中农药残留的GC-MS/MS检测方法

首次建立了林蛙油中15种农药（p，p′DDE，O，p′-DDD，o p′-DDT，p，p′-DDT，BHC（α、β、γ、δ），异丙威，甲拌磷，六氯苯，百菌清，皮蝇磷，倍硫磷，甲氰菊酯）的GC—MS／MS残留检测方法。样品用乙酸乙酯提取、Florisil层析柱净化后，经GC—MS／MS检测，用外标法定量。15种农药在0．050～10．0mg／L范围内，线性关系良好，相关系数r≥0．996。当添加量在0．050—2．00mg／kg间，平均加标回收率为81％～117％，RSD为2．4％-18．2％，方法的检出限为0．050mg／kg。该方法准确、灵敏，适用于农药残留的分析。     

蛋白芯片法同时检测食品中克伦特罗与莱克多巴胺的残留量

建立了食品中克伦特罗和莱克多巴胺残留含量同时检测的微阵列蛋白芯片法。结果显示:克伦特罗的线性范围为0.07～1.2 ng/g;莱克多巴胺的线性范围为0.05～0.8 ng/g。猪肉、猪肝中上述两种物质的加标回收率为74%～132%,相对标准偏差均小于10%。将所建立的方法与HPLC-MS方法进行对比,两者检测结果一致。该方法简单、快速、通量高,可用于实际样品中克伦特罗和莱克多巴胺残留量的检测。     

固相萃取-气相色谱法测定动物组织中盐酸克伦特罗残留量

建立了固相萃取-气相色谱分析动物组织中盐酸克伦特罗残留量的方法．采用固相萃取,分离富集动物组织中的盐酸克伦特罗．肉样的加标回收率在70％～80％;最低检出限为1μg／kg．盐酸克伦特罗的硅烷化衍生产物,采用气相色谱(ECD检测器)检测,其衍生物的峰面积与样品浓度在0．005～1．0μg／mL范围内呈良好的线性关系,线性回归系数大于0．999．     

基质固相分散/高效液相色谱-串联质谱法分析肉肠中4种β-2-受体激动剂残留

利用同位素稀释技术,建立了肉肠中4种β2-受体激动剂克伦特罗、莱克多巴胺、沙丁胺醇和特布他林的基质固相分散/高效液相色谱-串联质谱(MSPD/HPLC-MS/MS)分析方法。样品经C18填料研磨,甲醇洗脱,提取物经酶解后,用MCX小柱净化,经高效液相色谱分离,在正离子多反应监测(MRM)模式下用电喷雾电离串联质谱测定,内标法定量。4种β2-受体激动剂在0.2～20.0μg/L质量浓度范围内呈良好的线性关系,相关系数(r2)均大于0.990;沙丁胺醇和克伦特罗的检出限为0.10μg/kg;莱克多巴胺和特布他林的检出限为0.15μg/kg;方法的回收率为80%～109%,相对标准偏差小于10%。该方法简便快捷、灵敏度高,样品和溶剂用量少,可满足肉肠中4种β2-受体激动剂残留的快速检测。     

Simultaneous determination of 20 beta-agonists in pig muscle and liver by high-performance liquid chromatography/tandem mass spectrometry

A method was developed to determine 20 illegal residual beta-agonists in pork tissues, including muscle and liver simultaneously. The samples were hydrolyzed by beta-glucuronidase, purified by PCX SPE cartridges, and detected by HPLC coupled with electrospray ionization MS/MS operating in the positive ion mode. Matrix-fortified calibration was performed to compensate for the matrix effect and loss in sample preparation. Decision limit ranged from 0.05 to 0.23 microg/kg in muscle and 0.05 to 0.57 microg/kg in liver. Decision capacity ranged from 0.11 to 0.4 microg/kg in muscle and 0.16 to 0.79 microg/kg in liver. In Food Analysis Performance Assessment Scheme proficiency test 0287, a pig liver test material containing 13 beta-agonists was analyzed using the method developed, and clenbuterol and ractopamine were confirmed as being present. Z-scores for clenbuterol and ractopamine were 0.2 and 0.6, respectively.     

高效液相色谱-串联质谱法测定加工肉制品中莱克多巴胺及克伦特罗的含量

建立了高效液相色谱串联质谱测定加工肉制品中莱克多巴胺和克伦特罗的方法。采用阳离子交换色谱柱(SCX)分离目标化合物,改进了前处理方法,采用PXC固相萃取柱净化,并对洗脱溶液和高效液相色谱串联质谱的各参数进行优化。高效液相色谱流动相流速为0.4 mL/min,进样量为10μL,柱温为40℃。样品均质后加入30μLβ-盐酸葡萄糖醛苷酶-芳基硫酸酯酶,并经0.02 mol/L乙酸铵溶液(pH 5.2)提取,离心,过固相萃取柱净化。两种目标化合物在0.1～100μg/L范围内线性关系良好,检出限和定量下限分别不超过0.04μg/kg和0.15μg/kg。样品平均加标回收率为72%～98%,RSD低于8.5%。结果表明,此方法适于加工肉制品中莱克多巴胺和克伦特罗的测定。     

急性瘦肉精中毒检材的QuEChERS净化-液质联用快速确证方法

目前液相色谱串联质谱法测定动物源性食品中瘦肉精普遍采用酶水解提取、固相萃取净化的方式处理样品,该方法耗时长、分析成本高。 本研究采用酸水解和酶水解两种提取方式结合QuEChERS(Quick,Easy,Cheap,Effective,Rugged,Safe)净化和高效液相色谱串联质谱建立了动物性食品中特布他林、沙丁胺醇、莱克多巴胺和克伦特罗4种β2受体激动剂的快速定性确证和定量检测方法。 采用酶水解提取-QuEChERS净化处理样品,在电喷雾离子源正离子扫描(ESI+)和多反应监测(MRM)模式下,4种瘦肉精在1.0~20.0 μg/L浓度之间呈线性,线性相关系数均大于0.999,检出限和定量限分别为0.1和0.3 μg/kg,猪肉和牛肉样品中4种化合物的回收率为78.5%~112%,相对标准偏差RSD为2.8%~8.9%。 采用酸水解法代替酶水解提取时,尽管对于样品中莱克多巴胺测定结果稍偏低,但样品前处理时间大大缩短。 两种提取方法结合使用对于提高瘦肉精引起的食物中毒应急处置效率具有重要意义。     

Evaluation of matrix solid‐phase dispersion extraction for 11 β‐agonists in swine feed by liquid chromatography with electrospray ionization tandem mass spectrometry

A sensitive liquid chromatography with tandem mass spectrometry method was developed for the determination of 11 β‐agonists (clenbuterol, salbutamol, ractopamine, terbutaline, fenoterol, cimaterol, isoxsuprine, mabuterol, mapenterol, clenproperol, and tulobuterol) in swine feed. This rapid, simple, and effective extraction method was based on matrix solid‐phase dispersion. The limit of quantification of clenbuterol, cimaterol, mabuterol, salbutamol, terbutaline, mapenterol, clenproperol, and tulobuterol was 1 μg/kg and that of ractopamine, fenoterol, and isoxsuprine was 2 μg/kg. The recoveries of β‐agonists spiked in swine feeds at a concentration range of 1–8 μg/kg were >83.1% with relative standard deviations <9.3%. This rapid and reliable method can be used to efficiently separate, characterize, and quantify the residues of 11 β‐agonists in swine feeds with advantages of simple pretreatment and environmental friendliness.     

Simultaneous determination of clenbuterol, salbutamol and ractopamine in milk by reversed-phase liquid chromatography tandem mass spectrometry with isotope dilution

A simple, sensitive and reliable analytical method was developed for the simultaneous determination of clenbuterol (CLB), salbutamol (SAL) and ractopamine (RAC) in milk by ultra high performance liquid chromatography–positive electrospray ionization tandem mass spectrometry (UHPLC–ESI-MS/MS) with isotope dilution. Samples were directly purified through HLB cartridge. Then the eluate was dried under nitrogen and residues were redissolved in mobile phase. Samples were analyzed by LC–MS/MS on an Acquity UPLC^® BEH C₁₈ column with gradient elution. The samples were quantified using clenbuterol-D₉, salbutamol-D₃ and ractopamine-D₆ as internal standards. The proposed method was validated according to the European Commission Decision 2002/657/EC determining specificity, decision limit (CCα), detection capability (CCβ), recovery, precision, linearity, robustness and stability. CCα values were 0.054, 0.006 and 0.008 μg/kg for CLB, SAL and RAC, respectively. CCβ values were 0.058, 0.007 and 0.009 μg/kg for CLB, SAL and RAC, respectively. The mean recoveries, repeatability (expressed as coefficient of variation, CV_r), and reproducibility (CV_R) varied from 95.8 to 106.2%, from 3.60 to 6.44% (CVr), and from 4.77 to 7.53% (CV_R), respectively. The method is demonstrated to be suitable for the determination of clenbuterol, salbutamol and ractopamine in milk. The total time required for the analysis of one sample, including sample preparation, was about 45 min.     

Determination of beta-agonists in liver and retina by liquid chromatography-tandem mass spectrometry

A liquid chromatography-tandem mass spectrometry (LC/MS/MS) method for the determination of bromobuterol, cimaterol, clenbuterol, clenpenterol, hydroxymethylclenbuterol, isoxsuprine, mabuterol, ractopamine, ritrodrine, salbutamol, terbutaline, and tulobuterol residues in bovine liver and retina is reported. This procedure uses enzymatic digestion, liquid-liquid extraction, and cleanup on Oasis HLB solid-phase extraction cartridges, followed by determination of the residues by LC-tandem quadrupole MS using atmospheric pressure chemical ionization in the positive ion mode. Overall average recoveries ranged from 23 to 76% for liver and 34 to 77% for retina. The mean values for samples fortified at levels between 0.5-2.0 microg/kg (liver) and 5-20 microg/kg (retina) agreed within 98-118% of the spiked levels, with coefficients of variation ranging from 6 to 20%. The decision limits, CCalpha, ranged from 0.1 to 0.3 microg/kg for liver, 1-3 microg/kg for retina, and detection capabilities, CCbeta, from 0.2-0.5 microg/kg for liver and 2-5 microg/kg for retina.     

GC-MS法测定白酒中邻苯二甲酸酯残留量

采用正己烷提取白酒中的16种邻苯二甲酸酯类增塑剂,建立了气相色谱-质谱联用法测定白酒中污染物邻苯二甲酸酯类增塑剂残留量的检测方法。该方法对白酒中16种邻苯二甲酸酯化合物的检测限为0.05 mg/kg,方法的检测浓度线性范围为0.5~5.0 mg/L,样品的加标回收率为80.0%~95.0%,测定结果的相对标准偏差为2.1%~7.0%(n=6)。该方法可以满足白酒中污染物邻苯二甲酸酯检测的需要。     

New sulfonate composite functionalized with multiwalled carbon nanotubes with cryogel solid‐phase extraction sorbent for the determination of β‐agonists in animal feeds

A new mixed‐mode cation‐exchange sulfonate composite functionalized with multiwalled carbon nanotubes with polyvinyl alcohol cryogel was fabricated and used for the first time as a solid‐phase extraction sorbent for the determination of β‐agonists in animal feeds. Feed samples were extracted with 0.20 M phosphoric acid and methanol (1:4, v/v) using ultrasonication, cleaned‐up using the developed sorbent to which the β‐agonists bound then finally eluted with 5.0% ammonia in methanol and analyzed by high‐performance liquid chromatography. Various parameters that affected the extraction efficiency were optimized. Under the optimal conditions, the developed sorbent strongly interacted with β‐agonists by cationic exchange and hydrophobic and hydrophilic interactions, that provided a high extraction efficiency in the range of 92.8 ± 3.7–104.4 ± 2.3% over a range of 0.04–2.0 mg/kg for salbutamol and ractopamine, and 0.40–8.0 mg/kg for clenbuterol. The relative standard deviations were less than 6.0%. The developed method was successfully applied for the determination of β‐agonists in various types of animal feed and effectively reduced any matrix interference.