【目的】玉米发酵生产燃料乙醇的副产物酒糟蛋白饲料(DDGS)常作为蛋白质替代饲料广泛用于动物生产中。随着DDGS产业链的扩大,其生产过程中所带来的抗生素的残留问题应该得到重视,但目前关于DDGS中抗生素的残留研究报道较少。对全国经营...【目的】玉米发酵生产燃料乙醇的副产物酒糟蛋白饲料(DDGS)常作为蛋白质替代饲料广泛用于动物生产中。随着DDGS产业链的扩大,其生产过程中所带来的抗生素的残留问题应该得到重视,但目前关于DDGS中抗生素的残留研究报道较少。对全国经营和使用环节的玉米DDGS进行抽样调查,对70种抗生素的残留含量进行分析测定,以了解目前中国饲料用DDGS中抗生素的残留情况。【方法】首先利用四级杆飞行时间质谱(quadrupole time-of-flight mass spectrometry,QTOF)建立了大环内酯类、氟喹诺酮类、磺胺类、喹恶啉类、β-内酰胺类、林可胺类、四环素类、酰胺醇类等共70种抗生素药物基于质量数、保留时间和特征碎片离子的数据库。在全国9个省、市、自治区抽取经营和使用环节的玉米DDGS样品74批次,筛查其中可能含有的抗生素药物。样品的前处理:取一定量的均质样品,加入乙腈和水的混合溶液进行提取,经涡旋、震荡、离心后,取上清液过NH2固相萃取柱,收集淋洗液N2气浓缩至一定体积,过0.22μm滤膜。样品的分析:首先利用QTOF建立的筛查列表对样品DDGS中可能残留的抗生素进行初步筛选,以确定残留抗生素的种类,而后采用液相色谱串联质谱法(liquid chromatography-tandem mass spectrometry,LC-MS/MS)对发现疑似含有抗生素残留的样品进行定量分析,以确定抗生素的残留量。【结果】欧盟指令2002/657/EC规定了在应用质谱仪对目标化合物进行确证时的准则。一个母离子为2分,一个子离子为2.5分。在本试验条件下所有抗生素的检测结果都能达到这个要求,符合对目标化合物的确证准则。经QTOF定性分析后,抽样的所有DDGS中有一批次样品中含有抗生素残留,种类为甲氧苄啶。样品母离子峰、二级特征离子碎片、出峰时间与标准品完全一致,样品和标准品所有提取碎片离子及离子丰度比一致。利用LC-MS/MS对残留抗生素进行定量分析后,确定其残留量为107.7 ng·g-1。甲氧苄啶在添加浓度为10—1 000ng·mL-1,平均添加回收率为75.2%—97.9%,线性相关系数大于0.99,日内标准偏差为2.8%—5%,日间标准偏差为8%—10%。【结论】利用QTOF建立DDGS中抗生素类药物的定性筛选方法可作为玉米DDGS中残留抗生素快速筛查方法。存在残留的甲氧苄啶抗生素,可能在玉米发酵生产DDGS前被添加,目的是抑制有害微生物的生长繁殖。抽样分析结果表明,目前中国玉米DDGS中抗生素残留的种类较少、残留量也较低,但DDGS中抗生素残留情况仍不容忽视,相关部门也未给出DDGS发酵过程中可使用的抗生素的种类范围、使用限量以及使用规范。此外,还应该研究直接采用QTOF进行定量分析的方法,以及研究包括维吉尼亚霉素在内的其他抗生素的QTOF分析方法。展开更多
OBJECTIVE Identification of pesticide residues in TCM herbs is important for drug safety and public health.However,it is very challenging for the development of an instrument-based multi-residue pesticide analysis met...OBJECTIVE Identification of pesticide residues in TCM herbs is important for drug safety and public health.However,it is very challenging for the development of an instrument-based multi-residue pesticide analysis method for theherbalproducts due to their complex matrix.This study aims to develop a rapid method for the high-throughput detection of pesticide residues in TCM herbal products using liquid chromatography coupled to quadrupoletime of flight(LC-QTOF)mass spectrometry.METHODS In this study,we attempt to investigate possible pesticide residues in TCM herbal products which are commonly available in Singapore and to consolidate a comprehensive pesticide database for more than 250 regulated pesticides in FDA Regulations.We also attempt to perform non-targeted and targeted screenings of pesticide residues in herbal products by searching our database.RESULTS The developed LC-QTOF method demonstrates have high mass accuracy,resolution and selectivity,which makes it a very suitable tool for monitoring both target and non-target pesticides with a limit of detection at the low ppb level.Moreover,the LC-QTOF technology permits to retain all spectral data in a single run.It may avoid many difficulties related to matrix effects and will save much manpower.CONCLUSIONThis means that a variety of TCM herbs can be easily detected by this method for the presence or absence of pesticide residues that must conform to government regulations.展开更多
文摘【目的】玉米发酵生产燃料乙醇的副产物酒糟蛋白饲料(DDGS)常作为蛋白质替代饲料广泛用于动物生产中。随着DDGS产业链的扩大,其生产过程中所带来的抗生素的残留问题应该得到重视,但目前关于DDGS中抗生素的残留研究报道较少。对全国经营和使用环节的玉米DDGS进行抽样调查,对70种抗生素的残留含量进行分析测定,以了解目前中国饲料用DDGS中抗生素的残留情况。【方法】首先利用四级杆飞行时间质谱(quadrupole time-of-flight mass spectrometry,QTOF)建立了大环内酯类、氟喹诺酮类、磺胺类、喹恶啉类、β-内酰胺类、林可胺类、四环素类、酰胺醇类等共70种抗生素药物基于质量数、保留时间和特征碎片离子的数据库。在全国9个省、市、自治区抽取经营和使用环节的玉米DDGS样品74批次,筛查其中可能含有的抗生素药物。样品的前处理:取一定量的均质样品,加入乙腈和水的混合溶液进行提取,经涡旋、震荡、离心后,取上清液过NH2固相萃取柱,收集淋洗液N2气浓缩至一定体积,过0.22μm滤膜。样品的分析:首先利用QTOF建立的筛查列表对样品DDGS中可能残留的抗生素进行初步筛选,以确定残留抗生素的种类,而后采用液相色谱串联质谱法(liquid chromatography-tandem mass spectrometry,LC-MS/MS)对发现疑似含有抗生素残留的样品进行定量分析,以确定抗生素的残留量。【结果】欧盟指令2002/657/EC规定了在应用质谱仪对目标化合物进行确证时的准则。一个母离子为2分,一个子离子为2.5分。在本试验条件下所有抗生素的检测结果都能达到这个要求,符合对目标化合物的确证准则。经QTOF定性分析后,抽样的所有DDGS中有一批次样品中含有抗生素残留,种类为甲氧苄啶。样品母离子峰、二级特征离子碎片、出峰时间与标准品完全一致,样品和标准品所有提取碎片离子及离子丰度比一致。利用LC-MS/MS对残留抗生素进行定量分析后,确定其残留量为107.7 ng·g-1。甲氧苄啶在添加浓度为10—1 000ng·mL-1,平均添加回收率为75.2%—97.9%,线性相关系数大于0.99,日内标准偏差为2.8%—5%,日间标准偏差为8%—10%。【结论】利用QTOF建立DDGS中抗生素类药物的定性筛选方法可作为玉米DDGS中残留抗生素快速筛查方法。存在残留的甲氧苄啶抗生素,可能在玉米发酵生产DDGS前被添加,目的是抑制有害微生物的生长繁殖。抽样分析结果表明,目前中国玉米DDGS中抗生素残留的种类较少、残留量也较低,但DDGS中抗生素残留情况仍不容忽视,相关部门也未给出DDGS发酵过程中可使用的抗生素的种类范围、使用限量以及使用规范。此外,还应该研究直接采用QTOF进行定量分析的方法,以及研究包括维吉尼亚霉素在内的其他抗生素的QTOF分析方法。
文摘OBJECTIVE Identification of pesticide residues in TCM herbs is important for drug safety and public health.However,it is very challenging for the development of an instrument-based multi-residue pesticide analysis method for theherbalproducts due to their complex matrix.This study aims to develop a rapid method for the high-throughput detection of pesticide residues in TCM herbal products using liquid chromatography coupled to quadrupoletime of flight(LC-QTOF)mass spectrometry.METHODS In this study,we attempt to investigate possible pesticide residues in TCM herbal products which are commonly available in Singapore and to consolidate a comprehensive pesticide database for more than 250 regulated pesticides in FDA Regulations.We also attempt to perform non-targeted and targeted screenings of pesticide residues in herbal products by searching our database.RESULTS The developed LC-QTOF method demonstrates have high mass accuracy,resolution and selectivity,which makes it a very suitable tool for monitoring both target and non-target pesticides with a limit of detection at the low ppb level.Moreover,the LC-QTOF technology permits to retain all spectral data in a single run.It may avoid many difficulties related to matrix effects and will save much manpower.CONCLUSIONThis means that a variety of TCM herbs can be easily detected by this method for the presence or absence of pesticide residues that must conform to government regulations.
