Prior to the advent of electrospray ionization (ESI), the primary use of mass spectrometry in natural product discovery was the structural elucidation of compounds that had been isolated with bioassay-guided fractionation. With the advent of commercial ESI and atmospheric-pressure chemical ionization (APCI) sources in the early 1990s [74,75], researchers gained access to LC-MS instrumentation that could be used to directly analyze natural product mixtures. This allowed the integration of mass spectrometry into the earliest stages of natural product discovery. The impact of ESI and APCI on natural products discovery has been the subject of recent reviews [76,77].
Most modern LC-MS dereplication systems use the basic configuration introduced by Constant et al. , which is shown schematically in Figure 6.5A.
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