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1522_C02.fm  Page 76  Wednesday, November 12, 2003  9:36 AM









                                    urine. Urine samples were applied on cation-trapping exchange column,
                                    washed with ammonium acetate, and after column switching the drugs were
                                    eluted and separated on analytical cation exchange column in ACN–ammo-
                                    nium acetate (70:30). The detection was done with ESI-MS in full scan or
                                    SIM mode. Protonated quasi-molecular ions or acetonitrile adducts were


                                                              1
                                                                                 5
                                      (a)  100
                                                                         3
                                                                  2
                                                                                                 m/z 370
                                         %                                                       m/z 328
                                                                                                 m/z 302
                                                                              4
                                                                                                 m/z 300
                                         0                                                       m/z 286
                                                5.00   10.00  15.00  20.00  25.00  30.00  35.00
                                                                Retention Time (min)

                                                                                     +
                                                                                370[M+H]
                                      (b)

                                         %
                                                                                      411[M+H+CH CN] +
                                                                                              3
                                         0
                                           120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500
                                                                      m/z
                                                                                +
                                                                           328[M+H]
                                      (c)

                                         %
                                                                                 +
                                                                     286[M−CH COO+2H]
                                                                           3
                                                                                 369[M+H+CH CH] +
                                                                                        3
                                         0
                                           120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500
                                                                       m/z
                                    Figure 2.4  Mass chromatograms (a) obtained for a urine sample spiked with
                                    diacetylmorphine (1), monoacetylmorphine (2), codeine (3), morphine (4), and
                                    dihydrocodeine (5) to the concentration of 100 mg/l. Mass spectra produced for
                                    diacetylmorphine, monoacetylmorphine and morphine are presented as (a), (b),
                                    and (c), respectively. (Reprinted from Katagi M., Nishikawa M., Tatsuno M., Miki
                                    A., and Tsushihashi H., Column switching high-performance liquid chromatog-
                                    raphy-electrospray ionization mass spectrometry for identification of heroin
                                    metabolites in human urine. J. Chromatogr. B 751, 177, 2001. Copyright 2001,
                                    with permission from Elsevier Science.)



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