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Coupling two stages of mass analysis (MS/MS) can
be very useful in identifying compounds in complex mixtures and in determining
structures of unknown substances. In product ion scanning, the most
frequently used MS/MS mode, product ion spectra of ions of any chosen
m/z value represented in the conventional mass spectrum are generated.
From a mixture of ions in the source region or collected in an ion trap,
ions of a particular m/z value are selected in the first stage of mass
analysis. These "parent" or "precursor" ions are fragmented and then
the product ions resulting from the fragmentation are analyzed in a
second stage of mass analysis (Figure 17). If the sample is a pure compound
and fragment-forming ionization is used, the product spectra obtained
from the fragment ions in the normal mass spectrum can provide much
additional information for structural analysis. If the sample is a mixture
and soft ionization is used to produce, for example, predominantly [M+H]+
ions, the second stage of MS can be used to obtain an identifying mass
spectrum for each component in the mixture. Mass spectrometry/mass spectrometry
can also be useful in eliminating interferences in SIM experiments when
ion signal at the m/z of interest is produced by more than one compound.
For sector, quadrupole and time-of-flight instruments, each stage of
mass analysis requires a separate mass analyzer. For quadrupole ion
trap or ICR mass spectrometers, the MS/MS experiment can be conducted
sequentially in time within a single mass analyzer. In Figure 16, only
the signals at m/z 158 and m/z 160 were monitored during a gas chromatographic
run. This procedure is known as selected ion monitoring (SIM) and is
different from the situation shown schematically in Figure 15 where
compete mass spectra are obtained and used to construct selected ion
profiles.

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