A highly sensitive method was developed for the simultaneous determination of 8 steroid hormones in high-fat fish tissues using ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The 8 s...A highly sensitive method was developed for the simultaneous determination of 8 steroid hormones in high-fat fish tissues using ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The 8 steroid hormones were extracted from the tissues with diethyl ether.Differing from other common purification methods,the extract solutions were cleaned by gel permeation chromatography(GPC) using ethyl acetate-cyclohexane solution(1:1,v/v) as the mobile phase.The separation of target compounds was carried out by a BEH C18 column and a gradient elution consisting of acetonitrile and 0.2% aqueous formic acid(v/v).The compounds were detected under the multiple reaction monitoring(MRM) mode and quantified with external standard method.This method was validated with respect to linearity,specificity,accuracy and precision.A linearity with correlation coefficient larger than 0.995 was achieved in the range of 0.5 to 50 ng m L^(-1).The average recoveries at the spiked levels of 1.0,5.0,and 10.0 μg kg^(–1) varied between 81.7% and 90.8%,with the relative standard deviations(n=5) ranged from 3.50% to 10.0%.The limit of quantification(LOQ) for 8 steroid hormones ranged from 0.2 to 1.5 μg kg^(-1).It was concluded that this method can be successfully applied for the determination of 8 steroid hormones in complicated matrices including high-fat fish tissues.展开更多
The measurement of 23 organochlorine, organophosphorus, and pyrethroid pesticides in typical traditional Chinese medicine (TCM), flos lonicerae, was made using gel permeation chromatography (GPC) purification and gas ...The measurement of 23 organochlorine, organophosphorus, and pyrethroid pesticides in typical traditional Chinese medicine (TCM), flos lonicerae, was made using gel permeation chromatography (GPC) purification and gas chroma- tography-mass spectrometry (GC-MS) detection. The pesticides were extracted with ultrasonic device and 5.0 mL mixture of ethyl acetate and cyclohexane (1:1, v/v). Coextractants from sample matrices which may have interfere to the qualitative and quantitative analysis, such as pigments, were removed using GPC purification. Simultaneous full scan and selective ion monitor (scan/SIM) mode for GC-MS was used for qualitative and quantitative analysis, which pro- vided retention time and characteristic fragments ratio for each pesticide so as to positively identify each analyte. Rela- tive standard deviations (RSDs) were within 7.7% (5.0 - 22.5 μg/kg, n = 3). The recoveries of pesticide standards at the spiked concentration of 5.0 - 22.5 μg/kg were between 87.1% and 110.9%. Limits of detection (LODs) for the analytes were 0.16 - 3.2 μg/kg, which could meet the demand of routine analysis and TCM quality control.展开更多
As the roles of glycans in health and disease continue to be unraveled,it is becoming apparent that glycans’immense complexity cannot be ignored.To fully delineate glycan structures,we developed an integrative approa...As the roles of glycans in health and disease continue to be unraveled,it is becoming apparent that glycans’immense complexity cannot be ignored.To fully delineate glycan structures,we developed an integrative approach combining a set of cost-effective,widespread,and easy-to-handle analytical methods.The key feature of our workflow is the exploitation of a removable fluorescent label—exemplified by 9-fluorenylmethyl chloroformate(Fmoc)—to bridge the gap between diverse glycoanalytical methods,especially multiplexed capillary gel electrophoresis with laser-induced fluorescence detection(xCGELIF)and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOFMS).Through the detailed structural analysis of selected,dauntingly complex N-glycans from chicken ovalbumin,horse serum,and bovine transferrin,we illustrate the capabilities of the presented strategy.Moreover,this approach“visualizes”N-glycans that have been difficult to identify thus far—such as the sulfated glycans on human immunoglobulin A—including minute changes in glycan structures,potentially providing useful new targets for biomarker discovery.展开更多
目的建立加速溶剂萃取-凝胶渗透色谱-气相色谱-串联质谱法同时测定鱼类中7种新型有机污染物(咔唑和卤代咔唑类化合物)的分析方法。方法样品与硅藻土研磨混匀后经加速溶剂萃取仪提取,使用凝胶渗透色谱法净化并氮吹至近干,用1mL丙酮复溶...目的建立加速溶剂萃取-凝胶渗透色谱-气相色谱-串联质谱法同时测定鱼类中7种新型有机污染物(咔唑和卤代咔唑类化合物)的分析方法。方法样品与硅藻土研磨混匀后经加速溶剂萃取仪提取,使用凝胶渗透色谱法净化并氮吹至近干,用1mL丙酮复溶。目标化合物采用多反应监测(multiplereactionmonitoring,MRM)模式分析,外标法进行定量。结果咔唑、3-氯咔唑、3-溴咔唑和3,6-二氯咔唑在0.5~50.0μg/kg范围内线性关系良好,相关系数r>0.997;3,6-二溴咔唑、2,7-二溴咔唑和1,3,6,8-四溴咔唑在1.0~100.0μg/kg范围内线性关系良好,相关系数r>0.998。定量限(limits of quantification,LOQs)在0.50~1.00μg/kg之间,在各目标物的1LOQs、2LOQs和10LOQs3个加标水平下,7种咔唑和卤代咔唑类化合物的平均回收率为87.22%~107.27%,相对标准偏差(relative standard deviations,RSDs)为2.70%~8.17%(n=6)。结论该方法自动化程度高、灵敏度高、稳定性好,适用于鱼类中7种咔唑和卤代咔唑类化合物的检测。展开更多
基金supported by the Natural Science Foundation of Zhejiang Province,China(No.LY17C200009)the Foundation of Zhejiang Educational Committee(No.Y201328477)
文摘A highly sensitive method was developed for the simultaneous determination of 8 steroid hormones in high-fat fish tissues using ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The 8 steroid hormones were extracted from the tissues with diethyl ether.Differing from other common purification methods,the extract solutions were cleaned by gel permeation chromatography(GPC) using ethyl acetate-cyclohexane solution(1:1,v/v) as the mobile phase.The separation of target compounds was carried out by a BEH C18 column and a gradient elution consisting of acetonitrile and 0.2% aqueous formic acid(v/v).The compounds were detected under the multiple reaction monitoring(MRM) mode and quantified with external standard method.This method was validated with respect to linearity,specificity,accuracy and precision.A linearity with correlation coefficient larger than 0.995 was achieved in the range of 0.5 to 50 ng m L^(-1).The average recoveries at the spiked levels of 1.0,5.0,and 10.0 μg kg^(–1) varied between 81.7% and 90.8%,with the relative standard deviations(n=5) ranged from 3.50% to 10.0%.The limit of quantification(LOQ) for 8 steroid hormones ranged from 0.2 to 1.5 μg kg^(-1).It was concluded that this method can be successfully applied for the determination of 8 steroid hormones in complicated matrices including high-fat fish tissues.
文摘The measurement of 23 organochlorine, organophosphorus, and pyrethroid pesticides in typical traditional Chinese medicine (TCM), flos lonicerae, was made using gel permeation chromatography (GPC) purification and gas chroma- tography-mass spectrometry (GC-MS) detection. The pesticides were extracted with ultrasonic device and 5.0 mL mixture of ethyl acetate and cyclohexane (1:1, v/v). Coextractants from sample matrices which may have interfere to the qualitative and quantitative analysis, such as pigments, were removed using GPC purification. Simultaneous full scan and selective ion monitor (scan/SIM) mode for GC-MS was used for qualitative and quantitative analysis, which pro- vided retention time and characteristic fragments ratio for each pesticide so as to positively identify each analyte. Rela- tive standard deviations (RSDs) were within 7.7% (5.0 - 22.5 μg/kg, n = 3). The recoveries of pesticide standards at the spiked concentration of 5.0 - 22.5 μg/kg were between 87.1% and 110.9%. Limits of detection (LODs) for the analytes were 0.16 - 3.2 μg/kg, which could meet the demand of routine analysis and TCM quality control.
基金support from the German Federal Ministry of Education and Research(BMBF)under the project“Die Golgi Glykan Fabrik 2.0”(031A557C for Samanta Cajic and Erdmann Rapp)the European Commission(EC)under the project“HighGlycan”(278535 for RenéHennig and Erdmann Rapp)the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)under the project“The concert of dolicholbased glycosylation:from molecules to disease models”(FOR2509 for Valerian Grote and Erdmann Rapp).
文摘As the roles of glycans in health and disease continue to be unraveled,it is becoming apparent that glycans’immense complexity cannot be ignored.To fully delineate glycan structures,we developed an integrative approach combining a set of cost-effective,widespread,and easy-to-handle analytical methods.The key feature of our workflow is the exploitation of a removable fluorescent label—exemplified by 9-fluorenylmethyl chloroformate(Fmoc)—to bridge the gap between diverse glycoanalytical methods,especially multiplexed capillary gel electrophoresis with laser-induced fluorescence detection(xCGELIF)and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOFMS).Through the detailed structural analysis of selected,dauntingly complex N-glycans from chicken ovalbumin,horse serum,and bovine transferrin,we illustrate the capabilities of the presented strategy.Moreover,this approach“visualizes”N-glycans that have been difficult to identify thus far—such as the sulfated glycans on human immunoglobulin A—including minute changes in glycan structures,potentially providing useful new targets for biomarker discovery.
文摘目的建立加速溶剂萃取-凝胶渗透色谱-气相色谱-串联质谱法同时测定鱼类中7种新型有机污染物(咔唑和卤代咔唑类化合物)的分析方法。方法样品与硅藻土研磨混匀后经加速溶剂萃取仪提取,使用凝胶渗透色谱法净化并氮吹至近干,用1mL丙酮复溶。目标化合物采用多反应监测(multiplereactionmonitoring,MRM)模式分析,外标法进行定量。结果咔唑、3-氯咔唑、3-溴咔唑和3,6-二氯咔唑在0.5~50.0μg/kg范围内线性关系良好,相关系数r>0.997;3,6-二溴咔唑、2,7-二溴咔唑和1,3,6,8-四溴咔唑在1.0~100.0μg/kg范围内线性关系良好,相关系数r>0.998。定量限(limits of quantification,LOQs)在0.50~1.00μg/kg之间,在各目标物的1LOQs、2LOQs和10LOQs3个加标水平下,7种咔唑和卤代咔唑类化合物的平均回收率为87.22%~107.27%,相对标准偏差(relative standard deviations,RSDs)为2.70%~8.17%(n=6)。结论该方法自动化程度高、灵敏度高、稳定性好,适用于鱼类中7种咔唑和卤代咔唑类化合物的检测。
