Page 49 - Application Handbook - Liquid Chromatography
P. 49

Application  No.L497
    News

                                                  Table 1  Analytical Conditions
             [SFE]                                            [SFC]
             Solvent   : A) Super critical fluid of CO2       Column   : Shim-pack UC-RP (250 mm L. × 4.6 mm I.D., 5 μm)
                        B) 0.1 % Ammmonium formate in methanol  Mobile Phase   : A) Super critical fluid of CO2
             Flowrate   : 5 mL/min                                       B) 0.1 % Ammmonium formate in methanol
             Extraction   : 0-3 min. Static mode (B.Conc. 5 %)  Time Program  : B.Conc. 0 % (0 min.) → 10 % (11 min.) → 30% (14 min.) →
                        3-6 min. Dynamic mode (B.Conc. 5 %)              40 % (14.01-17 min.)
             Extraction                                       Flowrate   : 3 mL/min
             Vessel Temp.  : 40 °C                            Make-up   : 0.1 % Ammmonium formate in methanol (0.1 mL/min.)
             BPR Pressure  : A) 14.8 MPa, B) 15 MPa (split rate: 3 %)  Column Temp. : 40 °C
             Make-up   : 0.1 % Ammmonium formate in methanol (0.4 mL/min.)  BPR Pressure  : A) 15 MPa, B) 40 MPa
                                                              Detector   : LCMS-8050 MRM mode
            n Analysis of Standard Mixture of Pesticides
            The standard mixture sample of 510 pesticide components
            were mixed with a dehydrating agent and analyzed using   Ethofenprox  Hexa umuron  Benzofenap  Mepronil
                                                                                           2 ng/g
                                                                                                      1 ng/g
                                                                                1 ng/g
                                                                    1 ng/g
            the analytical conditions indicated in Table 1. Fig. 3 shows    1250       60000      35000
                                                                12500                             30000
            the results. Using the system, we were able to accomplish       1000       50000
                                                                10000                  40000      25000
            the entire process, from extraction to data acquisition, in   7500  750               20000
            about 45 minutes per analysis. For 327 components, we   5000    500        30000      15000
            obtained good repeatability for the concentration range   2500  250        20000      10000
                                                                                       10000
            from 1 to 100 ng/g (less than 30 %RSD for relative                                     5000
                                                                  0          0           0          0
            standard deviation for peak area at respective          12.0  13.0  13.0  14.0  12.0  13.0  13.0  14.0
            concentrations) and good linearity (contribution ratio of at   Prometyn  Fenamidone  Ethylchlozate  Imazosulfuron
            least R  = 0.99). Table 2 also shows how pesticides with a   1 ng/g  50000  2 ng/g  40000  1 ng/g  1 ng/g
                 2
            wide range of polarities were analyzed with good    20000      40000       35000      10000
            repeatability and linearity.                        15000                  30000
                                                                           30000       25000       7500
                                                                10000                  20000
                                                                           20000                   5000
                                                                                       15000
                                                                 5000      10000       10000       2500
                                                                                       5000
                                                                  0          0                      0
                                                                     11.0  12.0  14.0  15.0  13.0  14.0  15.0  16.0
                                                                  Bensulfuron methyl  Primisulfuron methyl   Halosulfuron methyl   Azimsulfuron
                                                                     1 ng/g     1 ng/g      1 ng/g    1 ng/g
                                                                125000
                                                                           25000       30000      40000
                                                                100000
                                                                           20000       25000
                                                                75000                  20000      30000
                                                                           15000
                                                                                       15000      20000
                                                                50000
                                                                           10000
                                                                                       10000
                                                                25000       5000        5000      10000
                                                                  0          0           0          0
                                                                   13.0  14.0   13.0  14.0  13.0  14.0  13.0  14.0
                                                                  Fig. 4  MRM Chromatograms of Representative Pesticides
             0.0  2.0  4.0  6.0  8.0  10.0  12.0  14.0 16.0 min  n Analysis of a Tomato
             Fig. 3  Mass Chromatogram of Standard Pesticide Mixture Solution  Analysis of 10 ng/g of 510 pesticide components added
                                                               to a tomato resulted in good repeatability (less than
             Table 2  Repeatability and Linearity for Representative Pesticides  20 %RSD for the relative standard deviation of the peak
             Compounds       LogPow  Repeatability  Range  R 2  area) and a good recovery rate (70 to 120 %) for 248
                                    (%RSD, n=5)  (ng/g)        components. Plots of LogPow and recovery rate results
             Ethofenprox      6.9      6.1     1-100  0.9991   are shown in Fig. 5. It shows that pesticides with a wide
             Hexaflumuron     5.68     6.8     1-100  0.9992   range of polarities were analyzed with good recovery.
             Benzofenap       4.69     1.4     2-200  0.9990
             Mepronil         3.66     4.6     1-100  0.9993
             Prometryn        3.34     2.7     1-100  0.9994
             Fenamidone       2.8      3.0     2-200  0.9991
             Ethylchlozate    2.5      3.0     1-100  0.9996
             Imazosulfuron    1.6      6.2     1-100  0.9998
             Bensulfuron methyl   0.79  8.1    1-100  0.9996
             Primisulfuron methyl   0.2  5.5   1-100  0.9994
             Halosulfuron methyl   -0.02  5.5  1-100  0.9996
             Azimsulfuron     -1.4     4.2     1-100  0.9998
            <Acknowledgments>                                      Fig. 5  LogPow vs. Recovery Rate for Tomato Analysis
            This Application News bulletin includes results obtained in cooperation with Osaka University, Kobe University, and the Miyazaki Agricultural Research
            Institute from the program for the "Development of Systems and Technology for Advanced Measurement and Analysis," sponsored by the Japan
            Science and Technology Agency (JST). We are deeply grateful to all those involved.
                                                                                                      First Edition: Oct. 2015


                                               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 its
                                               accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the
                                               use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject
                                               to change without notice.
       www.shimadzu.com/an/                                                                        © Shimadzu Corporation, 2015
   44   45   46   47   48   49   50   51   52   53   54