Simultaneous Determination Of 74 Kinds Of Pesticides In .

PO-CON1555ESimultaneous determination of 74 kindsof pesticides in Chinese herbal medicinelisted in Chinese pharmacopoeia (2015)by GPC-GC-MS/MSASMS 2015ThP 034Huiyan Yang, Jun Fan, Taohong Huang,Shin-ichi Kawano, Yuki HashiShimadzu Global COE, Shimadzu (China) Co., Ltd.

Simultaneous determination of 74 kinds of pesticides inChinese herbal medicine listed in Chinese pharmacopoeia (2015)by GPC-GC-MS/MSOverviewA method for quantitative analysis of 74 pesticides in Chinese herbal medicine by GPC-GCMSMS according to theforthcoming Chinese pharmacopoeia (2015) was successfully applied.IntroductionChinese herbal medicine has been widely used, but thepesticides residue in herbal medicine is still a serious issue.The 2015 edition of Chinese pharmacopoeia provides aninternal standard method based on the QuEChERSpretreatment and the GC-MS/MS system to determine 74kinds of pesticides in herbal medicine. Instead of theGC-MS/MS system, we apply the GPC-GC-MS/MS system.Compare with the GC-MS/MS system, the online GPCcleanup technique of the GPC GC-MS/MS system canpurify the sample to some degree so the matrixinterference can be decreased. Meanwhile, theGPC-GC-MS/MS system provides a much larger samplevolume which can reach 20 μl, so the detection limit ofGPC-GC-MS/MS is much lower than GC-MS/MS.MethodsSample PreparationThe crushed herb sample was soaked in 1% acetic acidsolvent for 30 minutes. Then the acetonitrile and internalstandards were added into the solvent to extract targetcompounds. After the extraction, dispersive SPEpurification by PSA, MgSO4, C18, GCB and silica gel wasemployed to remove matrix interferences such ascholesterol. Then the obtained extract was concentrated.The final extract was analyzed by GPC-GC-MS/MS system.GPC-GC-MS/MS AnalysisThe GPC system was LC-20A of Shimadzu with aCLNpack EV-200 (2.0 mmi.d. x 150 mm) GPC column ofShodex Co.The GC-MS/MS system was GCMS-TQ 8040 (Shimadzu).The GC column was made up of an empty column (5 mx 0.53 mm), a precolumn (InertCap 5MS/NP, 5 m x 0.25mm x 0.25 μm) and a main column (InertCap 5MS/NP,25 m x 0.25 mm x 0.25 μm).2

Simultaneous determination of 74 kinds of pesticides inChinese herbal medicine listed in Chinese pharmacopoeia (2015)by GPC-GC-MS/MSAnalytical ConditionsColumn temperatureCarrier pressureInjection modeInjector temperatureIon source temperatureInterface temperatureAquisition mode: 82 ºC (5 min) 8 ºC/min 300 ºC (7.75 min): 120 kPa (0 min) 100 kPa/min 180 kPa (4.4 min)-49.8 kPa/min 120 kPa (33.8 min): Splitless: 120 ºC (5 min) 100 ºC/min 250 ºC (33.7 min): 200 ºC: 300 ºC: EI-MRMFigure 1 Schematic diagram of the GPC-GC-MS/MS system.Table 1 GPC time programTime (min)UnitCommandValue0.1Option Box vpValve A Position00.1Option Box vpValve B Position03.26Option Box vpValve A Position13.86ControllerEvent15.26Option Box vpValve A Position05.46Option Box vpValve B Position18.14Option Box vpDegassing Unit StateOperate8.24Option Box vpDegassing Unit StateOFF8.26Option Box vpValve B Position045ControllerStop3

Simultaneous determination of 74 kinds of pesticides inChinese herbal medicine listed in Chinese pharmacopoeia (2015)by GPC-GC-MS/MSResultsThe online GPC purification was realized by valve switch.The GPC system injected the purified sample into thePTV injector and then the analysis was performed byGC-MS/MS.All target pesticides are included in the SmartDatabaseso the MRM method can be created after one scanmode acquirement to get the retention time of eachcompound.Internal standard method was applied to quantitativeanalysis. Fenthion-d6 was added into the sample as internalstandard. The method showed good linearity in the rangeof 1 50 ng/mL. The linear correlation coefficient r isbigger than 0.995. With 10 μL sample volume, the LODs ofmost of the pesticides were less than 0.5ng/mL. The RSD of6 continuous test was less than 10%. The recoveries of allthe pesticides were between 60% 120%.Figure 2 MRM chromatograms of standard mixture (50 ng/mL 00.00.026.2526.50endrin27.5027.75Endosulfan sulfate30.0030.25mirexFigure 3 MRM Chromatograms of 6 pesticides (5 ng/mL each)4

Simultaneous determination of 74 kinds of pesticides inChinese herbal medicine listed in Chinese pharmacopoeia (2015)by GPC-GC-MS/MSFigure 4 Calibration curve of 6 pesticidesTable 2 Test results of representative compoundsCompoundrLOD (μg/L)RSD %(n 6)Recovery5 014.2378.59Chlorpyrifos0.99980.014.8384.515

Simultaneous determination of 74 kinds of pesticides inChinese herbal medicine listed in Chinese pharmacopoeia (2015)by GPC-GC-MS/MSConclusionsAn online GPC-GC-MS/MS system was successfully applied to analyze 74 pesticides in Chinese herbal medicine. Withthe purification ability and the large volume sample injection, this system provided good repeatability, low LODs andsatisfactory recoveries which can meet the requirements of the Chinese pharmacopoeia (2015).First Edition: June, 2015www.shimadzu.com/an/For Research Use Only. Not for use in diagnostic procedures.The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu.The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to itsaccuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to theuse of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subjectto change without notice. Shimadzu Corporation, 2015

forthcoming Chinese pharmacopoeia (2015) was successfully applied. Introduction Chinese herbal medicine has been widely used, but the pesticides residue in herbal medicine is still a serious issue. The 2015 edition of Chinese pharmacopoeia provides an internal standard method based on the QuEChERS pretreatment and the GC-MS/MS system to .