动物可食性组织中兽药多残留检测关键技术研究
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摘要
为确保动物性食品的安全,开展兽药残留分析具有非常重要的意义。目前关于药物的残留分析方法较多,但研究重点主要是检测方法的改进,且研究对象禁锢于单一基质或单组分,所采用的样品前处理方法都是传统的液液萃取。样品前处理是残留分析的保障,其好坏直接影响到分析的各项指标、成本和效率。
快速溶剂萃取作为一种新的样品前处理方法,是在一定的压力和温度下用溶剂对固体或者半固体样品进行提取的方法。使用常规的溶剂、通过提高温度和增加压力来提高萃取的效率,其结果大大缩短了萃取的时间并明显降低萃取溶剂的使用量。
本课题深入探索并建立了动物性食品中多种四环素类、磺胺类、氟喹诺酮类、环丙氨嗪及其相关化合物,双甲脒的药物残留分析方法,使用快速溶剂萃取法,节省样品前处理时间,提高食品安全检测的效率,为5类药物的残留监控提供技术支持和理论依据,对动物源食品安全评价具有指导意义和参考价值。
1.动物可食性组织中四环素类药物分析方法研究
建立了动物性食品中7种四环素类残留检测的高效液相色谱定量方法和液相色谱串联质谱确证方法。动物组织样品采用三氯乙酸和甲醇溶液提取,萃取的温度60℃,压力120 bar时回收率最佳。提取液经HLB固相萃取小柱净化,氮气流吹干浓缩,流动相溶解残渣,高效液相色谱和液相色谱串联质谱检测。定量方法中,动物源食品中的7种四环素类药物定量限均低于20μg/kg,组织添加回收率为75.0%-104.9%,相对标准偏差小于10%；确证方法中,各种动物组织以及牛奶,鸡蛋和蜂蜜中的检测限为0.2μg/kg,定量限为0.5μg/kg。7种四环素类药物在组织中添加浓度为0.5-200μg/kg,回收率为78.8-105.2%,相对标准偏差小于11%。该方法的建立,解决了四环素类分析方法中存在的回收率低,样品前处理繁琐的问题。
2.动物可食性组织中磺胺类药物同时分析方法研究
建立了动物性食品中18种磺胺类药物的高效液相色谱定量方法和20种磺胺类药物液相色谱串联质谱确证方法。当萃取温度为60℃,压力65 bar,萃取溶剂为乙腈时,提取回收率最高。提取液经减压旋转蒸干后,残渣加入2%的乙酸10mL溶解混匀,过SPE柱净化,流动相定容,待检测。定量方法中,组织中的检测限为5μg/kg,定量限为10μg/kg,在组织中添加回收率为71.1%-118.3%,变异系数小于12%。确证方法中,动物性食品中的检测限为0.5μg/kg,定量限为1μg/kg,在组织中添加回收率为70.5%-117.5%,变异系数小于13%。本研究应用快速溶剂萃取技术提取了动物可食性组织中20种磺胺类药物,为磺胺类药物多残留快速分析提供了参考。
3.动物可食性组织中氟喹诺酮类药物分析方法研究
建立了动物性食品中15种氟喹诺酮类药物的高效液相色谱定量方法和20种氟喹诺酮类药物残留的液相色谱串联质谱确证分析方法。优化了快速溶剂萃取参数,萃取池温度65℃,压力100 bar,萃取溶剂为甲醇时,提取效率最佳。提取合并提取液,40℃减压旋转蒸干,残渣加入磷酸盐缓冲液10 mL溶解混匀,过SPE柱净化后供测定。定量方法中,动物性食品中的检测限为5μg/kg,定量限为1 0μg/kg,在组织中添加回收率为70.6%-111.1%,变异系数小于13%。确证方法中,动物性食品中的检测限为0.5μg/kg,定量限为1μg/kg,在组织中添加回收率为73.7%-111.2%,变异系数小于15%。该方法应用快速溶剂萃取技术提取了动物可食性组织中20种磺胺类药物。
4.动物可食性组织中环丙氨嗪,三聚氰胺及其代谢物分析方法研究
建立了动物性食品中环丙氨嗪,三聚氰胺及其代谢物残留的高效液相色谱定量方法和液相色谱串联质谱确证分析方法。优化了快速溶剂萃取参数,萃取溶剂为甲醇/水(90/10,v/v),萃取池温度为70℃,压力90 bar时,提取效率最佳。提取合并提取液,40℃减压旋转蒸干,过膜测定。液相色谱条件中色谱柱为APS-2分析柱,检测波长230 nm。质谱在正离子模式下,应用选择反应监控。定量方法中,动物性食品中的5种化合物的检测限为10μg/kg,定量限为40μg/kg,在组织中添加回收率为72.2%-115.4%,变异系数小于12%。确证方法中,动物性食品中的检测限为5μg/kg,定量限为10μg/kg,在组织中添加回收率为70.2%-118.4%,变异系数小于15%。该方法已成功的用于动物性食品中这5种化合物的残留检测。
5.动物可食性组织中双甲脒药物分析方法研究
建立了动物性食品中双甲脒和2,4-二甲基苯胺残留的气相色谱的定量方法和气相色谱质谱确证分析方法。优化了ASE萃取参数,萃取池温度60℃,压力120 bar,提取溶剂为正己烷和甲醇时,提取效率最高。提取液浓缩后过固相萃取小柱净化,气相色谱质谱分析,对于气相色谱分析,样品需要加入HFBA进行衍生。定量方法中,猪、牛、羊的脂肪、肝脏和肾脏的检测限为5μg/kg,定量限为10μg/kg,在猪、牛、羊的组织中添加回收率为72.4%-101.3%,变异系数小于11.5%。确证方法中,猪、牛、羊的脂肪、肝脏和肾脏的检测限为2μg/kg,定量限为5μg/kg,在组织中添加回收率77.4%-107.1%,变异系数小于11.6%。该方法将快速溶剂萃取成功地应用到动物可食性组织中双甲脒的残留分析。
本论文开展了动物性食品中5类兽药残留的定量确证方法研究。应用快速溶剂萃取技术,针对药物的化学特性和组织基质的特点,优化了各项提取参数,获得了满意的效果。这些研究为5类药物残留监控提供了先进的检测方法和强有力的理论依据,对动物性食品安全评价和药物的再评估有重要参考价值。
To ensure confidence and to limit the residues of these drugs in animal products, accurate detection and quantitative determination of these molecules in food of animal origin are of paramount importance. However, prior studies mostly focused on the improvement of detection, the main method for sample pretreatment is liquid to liquid extraction, only a very few paid attention to sample preparation techniques, additionally, most of the methods in the previous literatures only allow the determination of one or two analytes, or only focus on one matrix.
Accelerated solvent extraction (ASE) is a recent advance in sample preparation for trace analyte and this technique uses conventional solvents at elevated pressures and temperatures to extract solid samples quickly. The process takes advantage of the increasing solubility of analyte at temperatures and pressures well above the common, raising the diffusion rate and decreasing the viscosity and surface tension, so the kinetic processes for analytes desorbing from the matrix are accelerated.
Based on this aspect, this study aims to explore analysis methods for determination of tetracycline. sulfanilamide, fluoquinolones, cyromazine and its related metabolites and amitraz in foods of animal origin, and investigate various kinds of parameters deeply. Pressurized liquid extraction will be firstly combined with HPLC and LC-MS/MS. The optimized PLE method reduces the use of solvents and extraction time compared to traditional liquid-liquid extractions. It generates less hazardous waste and was more benign to the environment. Our study will provide technical support for monitoring, and it also has a great value for evaluation on animal food safety.
1. Development of a method for simultaneous quantification and confirmation of tetracyclines in the foods of animal origin
A simple and especially rapid method-using accelerated solvent extraction (ASE) and HPLC has been developed for the quantitative determination of seven tetracyclines in muscle and liver of porcine, chicken and bovine. The procedure consisted of a TCA/methanol extraction conducted at elevated temperature (60℃) and pressure (65 bar), after further clean-up, the extraction solution was concentrated and finally for liquid chromatography tandem mass spectrometry analysis. For HPLC, the limits of quantitation (LOQ) was lower than 20μg/kg, recoveries of 7 tetracyclines in spiked tissues were from 75.6-103.5%. For LC-MS/MS, LOQs were 0.5μg/kg for 7 tetracyclines in muscle, liver and kidney. The limits of detection (LOD) were 0.2μg/kg. Recoveries of 7 tetracyclines in tissues spiked from 0.5 to 2.0μg/kg were in the range of 78.8%～105.2%. Coefficients of variation were in the range of 5.7%～10.8%. The simple method reduced the time for sample pretreatment, and met the requirement for tetracycline residue analysis.
2. Development of a method for simultaneous quantification and confirmation of sulfonamides in the foods of animal origin
A rapid method-using accelerated solvent extraction (ASE) and HPLC has been developed for the quantitative determination of 18 sulfonamides in muscle and liver of porcine, chicken and bovine. The procedure consisted of an acetonitrile extraction conducted at elevated temperature (60℃) and pressure (65 bar), after further clean-up, the extraction solution was concentrated and finally for HPLC and LC-MS/MS analysis. For HPLC, the LOD was 5μg/kg and LOQ were 10 [ig/kg for 18 sulfonamides in foods of animal origin, recoveries of 20 drugs in spiked tissues were from 71.1%～118.3%. For LC-MS/MS, the LOD was 0.5μg/kg and LOQ was 1μg/kg, respectively. Recoveries of 20 drugs in spiked tissues were in the range of 70.5%-117.5%. Coefficients of variation were less than 13%. The simple method reduced the time for sample pretreatment, and met the requirement for sulfonamides residue analysis.
3. Development of a method for simultaneous quantification and confirmation of fluoroquinolones in the foods of animal origin
A rapid method-using accelerated solvent extraction (ASE) and HPLC has been developed for the quantitative determination of 15 fluoroquinolones in muscle and liver of porcine, chicken and bovine. The procedure consisted of an acetonitrile extraction conducted at elevated temperature (65℃) and pressure (85 bar), after further clean-up, the extraction solution was concentrated and finally for HPLC and LC-MS/MS analysis. For HPLC, the LOD was 5μg/kg and LOQ were 10μg/kg for 15 fluoroquinolones in foods of animal origin, recoveries of 15 drugs in spiked tissues were in the range of 70.6%～111.1%, with RSD less than 15%. For LC-MS/MS, the LOD was 0.5μg/kg and LOQ was 1μg/kg. recoveries of 20 drugs in spiked tissues were in the range of 73.7%～111.2%, with RSD less than 15%. The simple method reduced the time for sample pretreatment, and met the requirement for fluoquinolones residue analysis.
4. Development of a method for simultaneous quantification and confirmation of cyromazine, melamine and its related metabolites in the foods of animal origin
Simple and sensitive methods have been developed for simultaneous detection of cyromazine, melamine and their metabolites (ammeline, ammelide and cyanuric acid) in samples of animal origins. These include a high performance liquid chromatography (HPLC) method and a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method and are useful in regular monitoring and in toxicity studies of these molecules. Representative samples used in this study include muscles and livers of swine, bovine, sheep and chicken, kidneys of swine, bovine and sheep, and milk powder. A new sample preparation procedure with pressurized liquid extraction (PLE) at 90 bar and 70℃was investigated. Quantification of these five compounds by HPLC was achieved using an APS-2 column with UV detection at 230 nm. Limit of detection (LOD) was at 20μg/kg, and limit of quantification (LOQ) was at 40 p.g/kg. Recoveries of the five analytes in spiked samples ranged from 72.2% to 115.4% with RSD less than 12%. Confirmatory analysis of the analytes was performed using LC-MS/MS in Selected Reaction Monitoring (SRM) mode. The LOD and LOQ were 5μg/kg and 10μg/kg, respectively.
5. Development of a method for simultaneous quantification and confirmation of amitraz and 2,4- dimethylaniline in the foods of animal origin
A method has been developed for determination and confirmation of amitraz and its main metabolite,2,4-dimethylaniline, in food animal tissues by using gas chromatography electron capture detector (GC-ECD) and gas chromatography mass spectrometry detector (GC-MS). This method is based on a new extraction procedure using accelerated solvent extraction (ASE). It consists of an n-hexane/methanol extraction step, a cleaning-up step by BakerBond octadecyl C18 silica bonded cartridge, hydrolysis and derivatization to 2,4- dimethyl-7-F-butyramide for GC-ECD analysis. For confirmation using GC-MS, hydrolysis and derivatization were not needed. Parameters for extraction pressure, temperature and cycle of ASE, clean-up, derivatization and analysis procedure have been optimized. Spike recoveries from 50 to 300μg/kg levels were found to be between 72.4% and 101.3% with relative standard deviation less than 11.5% in GC-ECD, from 5 to 20μg/kg levels were found to be between 77.4% and 107.1 % with relative standard deviation less than 11.6% in GC-MS. The LOD and LOQ are 5p.g/kg and 10μg/kg, respectively, for these two analytes using GC-ECD. For GC-MS, LOD and LOQ were 2 and 5μg/kg, respectively.
From above, analysis methods for determination of five classes of veterinary drugs in the foods of animal origin were studied in this dissertation. Accerated solvent extraction was used, and various parameters were optimized according to characters of drugs and matrix. All results from the study can provide advanced technologies and reasonable evidence for monitoring or surveillance for these kinds of veterinary drugs residue. And all of them have great values for food safety and drug safety re-evaluation.
快速溶剂萃取作为一种新的样品前处理方法,是在一定的压力和温度下用溶剂对固体或者半固体样品进行提取的方法。使用常规的溶剂、通过提高温度和增加压力来提高萃取的效率,其结果大大缩短了萃取的时间并明显降低萃取溶剂的使用量。
本课题深入探索并建立了动物性食品中多种四环素类、磺胺类、氟喹诺酮类、环丙氨嗪及其相关化合物,双甲脒的药物残留分析方法,使用快速溶剂萃取法,节省样品前处理时间,提高食品安全检测的效率,为5类药物的残留监控提供技术支持和理论依据,对动物源食品安全评价具有指导意义和参考价值。
1.动物可食性组织中四环素类药物分析方法研究
建立了动物性食品中7种四环素类残留检测的高效液相色谱定量方法和液相色谱串联质谱确证方法。动物组织样品采用三氯乙酸和甲醇溶液提取,萃取的温度60℃,压力120 bar时回收率最佳。提取液经HLB固相萃取小柱净化,氮气流吹干浓缩,流动相溶解残渣,高效液相色谱和液相色谱串联质谱检测。定量方法中,动物源食品中的7种四环素类药物定量限均低于20μg/kg,组织添加回收率为75.0%-104.9%,相对标准偏差小于10%；确证方法中,各种动物组织以及牛奶,鸡蛋和蜂蜜中的检测限为0.2μg/kg,定量限为0.5μg/kg。7种四环素类药物在组织中添加浓度为0.5-200μg/kg,回收率为78.8-105.2%,相对标准偏差小于11%。该方法的建立,解决了四环素类分析方法中存在的回收率低,样品前处理繁琐的问题。
2.动物可食性组织中磺胺类药物同时分析方法研究
建立了动物性食品中18种磺胺类药物的高效液相色谱定量方法和20种磺胺类药物液相色谱串联质谱确证方法。当萃取温度为60℃,压力65 bar,萃取溶剂为乙腈时,提取回收率最高。提取液经减压旋转蒸干后,残渣加入2%的乙酸10mL溶解混匀,过SPE柱净化,流动相定容,待检测。定量方法中,组织中的检测限为5μg/kg,定量限为10μg/kg,在组织中添加回收率为71.1%-118.3%,变异系数小于12%。确证方法中,动物性食品中的检测限为0.5μg/kg,定量限为1μg/kg,在组织中添加回收率为70.5%-117.5%,变异系数小于13%。本研究应用快速溶剂萃取技术提取了动物可食性组织中20种磺胺类药物,为磺胺类药物多残留快速分析提供了参考。
3.动物可食性组织中氟喹诺酮类药物分析方法研究
建立了动物性食品中15种氟喹诺酮类药物的高效液相色谱定量方法和20种氟喹诺酮类药物残留的液相色谱串联质谱确证分析方法。优化了快速溶剂萃取参数,萃取池温度65℃,压力100 bar,萃取溶剂为甲醇时,提取效率最佳。提取合并提取液,40℃减压旋转蒸干,残渣加入磷酸盐缓冲液10 mL溶解混匀,过SPE柱净化后供测定。定量方法中,动物性食品中的检测限为5μg/kg,定量限为1 0μg/kg,在组织中添加回收率为70.6%-111.1%,变异系数小于13%。确证方法中,动物性食品中的检测限为0.5μg/kg,定量限为1μg/kg,在组织中添加回收率为73.7%-111.2%,变异系数小于15%。该方法应用快速溶剂萃取技术提取了动物可食性组织中20种磺胺类药物。
4.动物可食性组织中环丙氨嗪,三聚氰胺及其代谢物分析方法研究
建立了动物性食品中环丙氨嗪,三聚氰胺及其代谢物残留的高效液相色谱定量方法和液相色谱串联质谱确证分析方法。优化了快速溶剂萃取参数,萃取溶剂为甲醇/水(90/10,v/v),萃取池温度为70℃,压力90 bar时,提取效率最佳。提取合并提取液,40℃减压旋转蒸干,过膜测定。液相色谱条件中色谱柱为APS-2分析柱,检测波长230 nm。质谱在正离子模式下,应用选择反应监控。定量方法中,动物性食品中的5种化合物的检测限为10μg/kg,定量限为40μg/kg,在组织中添加回收率为72.2%-115.4%,变异系数小于12%。确证方法中,动物性食品中的检测限为5μg/kg,定量限为10μg/kg,在组织中添加回收率为70.2%-118.4%,变异系数小于15%。该方法已成功的用于动物性食品中这5种化合物的残留检测。
5.动物可食性组织中双甲脒药物分析方法研究
建立了动物性食品中双甲脒和2,4-二甲基苯胺残留的气相色谱的定量方法和气相色谱质谱确证分析方法。优化了ASE萃取参数,萃取池温度60℃,压力120 bar,提取溶剂为正己烷和甲醇时,提取效率最高。提取液浓缩后过固相萃取小柱净化,气相色谱质谱分析,对于气相色谱分析,样品需要加入HFBA进行衍生。定量方法中,猪、牛、羊的脂肪、肝脏和肾脏的检测限为5μg/kg,定量限为10μg/kg,在猪、牛、羊的组织中添加回收率为72.4%-101.3%,变异系数小于11.5%。确证方法中,猪、牛、羊的脂肪、肝脏和肾脏的检测限为2μg/kg,定量限为5μg/kg,在组织中添加回收率77.4%-107.1%,变异系数小于11.6%。该方法将快速溶剂萃取成功地应用到动物可食性组织中双甲脒的残留分析。
本论文开展了动物性食品中5类兽药残留的定量确证方法研究。应用快速溶剂萃取技术,针对药物的化学特性和组织基质的特点,优化了各项提取参数,获得了满意的效果。这些研究为5类药物残留监控提供了先进的检测方法和强有力的理论依据,对动物性食品安全评价和药物的再评估有重要参考价值。
To ensure confidence and to limit the residues of these drugs in animal products, accurate detection and quantitative determination of these molecules in food of animal origin are of paramount importance. However, prior studies mostly focused on the improvement of detection, the main method for sample pretreatment is liquid to liquid extraction, only a very few paid attention to sample preparation techniques, additionally, most of the methods in the previous literatures only allow the determination of one or two analytes, or only focus on one matrix.
Accelerated solvent extraction (ASE) is a recent advance in sample preparation for trace analyte and this technique uses conventional solvents at elevated pressures and temperatures to extract solid samples quickly. The process takes advantage of the increasing solubility of analyte at temperatures and pressures well above the common, raising the diffusion rate and decreasing the viscosity and surface tension, so the kinetic processes for analytes desorbing from the matrix are accelerated.
Based on this aspect, this study aims to explore analysis methods for determination of tetracycline. sulfanilamide, fluoquinolones, cyromazine and its related metabolites and amitraz in foods of animal origin, and investigate various kinds of parameters deeply. Pressurized liquid extraction will be firstly combined with HPLC and LC-MS/MS. The optimized PLE method reduces the use of solvents and extraction time compared to traditional liquid-liquid extractions. It generates less hazardous waste and was more benign to the environment. Our study will provide technical support for monitoring, and it also has a great value for evaluation on animal food safety.
1. Development of a method for simultaneous quantification and confirmation of tetracyclines in the foods of animal origin
A simple and especially rapid method-using accelerated solvent extraction (ASE) and HPLC has been developed for the quantitative determination of seven tetracyclines in muscle and liver of porcine, chicken and bovine. The procedure consisted of a TCA/methanol extraction conducted at elevated temperature (60℃) and pressure (65 bar), after further clean-up, the extraction solution was concentrated and finally for liquid chromatography tandem mass spectrometry analysis. For HPLC, the limits of quantitation (LOQ) was lower than 20μg/kg, recoveries of 7 tetracyclines in spiked tissues were from 75.6-103.5%. For LC-MS/MS, LOQs were 0.5μg/kg for 7 tetracyclines in muscle, liver and kidney. The limits of detection (LOD) were 0.2μg/kg. Recoveries of 7 tetracyclines in tissues spiked from 0.5 to 2.0μg/kg were in the range of 78.8%～105.2%. Coefficients of variation were in the range of 5.7%～10.8%. The simple method reduced the time for sample pretreatment, and met the requirement for tetracycline residue analysis.
2. Development of a method for simultaneous quantification and confirmation of sulfonamides in the foods of animal origin
A rapid method-using accelerated solvent extraction (ASE) and HPLC has been developed for the quantitative determination of 18 sulfonamides in muscle and liver of porcine, chicken and bovine. The procedure consisted of an acetonitrile extraction conducted at elevated temperature (60℃) and pressure (65 bar), after further clean-up, the extraction solution was concentrated and finally for HPLC and LC-MS/MS analysis. For HPLC, the LOD was 5μg/kg and LOQ were 10 [ig/kg for 18 sulfonamides in foods of animal origin, recoveries of 20 drugs in spiked tissues were from 71.1%～118.3%. For LC-MS/MS, the LOD was 0.5μg/kg and LOQ was 1μg/kg, respectively. Recoveries of 20 drugs in spiked tissues were in the range of 70.5%-117.5%. Coefficients of variation were less than 13%. The simple method reduced the time for sample pretreatment, and met the requirement for sulfonamides residue analysis.
3. Development of a method for simultaneous quantification and confirmation of fluoroquinolones in the foods of animal origin
A rapid method-using accelerated solvent extraction (ASE) and HPLC has been developed for the quantitative determination of 15 fluoroquinolones in muscle and liver of porcine, chicken and bovine. The procedure consisted of an acetonitrile extraction conducted at elevated temperature (65℃) and pressure (85 bar), after further clean-up, the extraction solution was concentrated and finally for HPLC and LC-MS/MS analysis. For HPLC, the LOD was 5μg/kg and LOQ were 10μg/kg for 15 fluoroquinolones in foods of animal origin, recoveries of 15 drugs in spiked tissues were in the range of 70.6%～111.1%, with RSD less than 15%. For LC-MS/MS, the LOD was 0.5μg/kg and LOQ was 1μg/kg. recoveries of 20 drugs in spiked tissues were in the range of 73.7%～111.2%, with RSD less than 15%. The simple method reduced the time for sample pretreatment, and met the requirement for fluoquinolones residue analysis.
4. Development of a method for simultaneous quantification and confirmation of cyromazine, melamine and its related metabolites in the foods of animal origin
Simple and sensitive methods have been developed for simultaneous detection of cyromazine, melamine and their metabolites (ammeline, ammelide and cyanuric acid) in samples of animal origins. These include a high performance liquid chromatography (HPLC) method and a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method and are useful in regular monitoring and in toxicity studies of these molecules. Representative samples used in this study include muscles and livers of swine, bovine, sheep and chicken, kidneys of swine, bovine and sheep, and milk powder. A new sample preparation procedure with pressurized liquid extraction (PLE) at 90 bar and 70℃was investigated. Quantification of these five compounds by HPLC was achieved using an APS-2 column with UV detection at 230 nm. Limit of detection (LOD) was at 20μg/kg, and limit of quantification (LOQ) was at 40 p.g/kg. Recoveries of the five analytes in spiked samples ranged from 72.2% to 115.4% with RSD less than 12%. Confirmatory analysis of the analytes was performed using LC-MS/MS in Selected Reaction Monitoring (SRM) mode. The LOD and LOQ were 5μg/kg and 10μg/kg, respectively.
5. Development of a method for simultaneous quantification and confirmation of amitraz and 2,4- dimethylaniline in the foods of animal origin
A method has been developed for determination and confirmation of amitraz and its main metabolite,2,4-dimethylaniline, in food animal tissues by using gas chromatography electron capture detector (GC-ECD) and gas chromatography mass spectrometry detector (GC-MS). This method is based on a new extraction procedure using accelerated solvent extraction (ASE). It consists of an n-hexane/methanol extraction step, a cleaning-up step by BakerBond octadecyl C18 silica bonded cartridge, hydrolysis and derivatization to 2,4- dimethyl-7-F-butyramide for GC-ECD analysis. For confirmation using GC-MS, hydrolysis and derivatization were not needed. Parameters for extraction pressure, temperature and cycle of ASE, clean-up, derivatization and analysis procedure have been optimized. Spike recoveries from 50 to 300μg/kg levels were found to be between 72.4% and 101.3% with relative standard deviation less than 11.5% in GC-ECD, from 5 to 20μg/kg levels were found to be between 77.4% and 107.1 % with relative standard deviation less than 11.6% in GC-MS. The LOD and LOQ are 5p.g/kg and 10μg/kg, respectively, for these two analytes using GC-ECD. For GC-MS, LOD and LOQ were 2 and 5μg/kg, respectively.
From above, analysis methods for determination of five classes of veterinary drugs in the foods of animal origin were studied in this dissertation. Accerated solvent extraction was used, and various parameters were optimized according to characters of drugs and matrix. All results from the study can provide advanced technologies and reasonable evidence for monitoring or surveillance for these kinds of veterinary drugs residue. And all of them have great values for food safety and drug safety re-evaluation.
引文
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