2.4. (LC-)ESI-MS analysis
Our literature search yielded a single article [44] in which the
ESI-MS fragmentation mechanism of bisindole alkaloids, namely
VLB and VCR, is discussed. The ESI mass spectra of VLB and VCR
were recorded on a low-resolution ion trap mass spectrometer.
Fig. 7 shows the putative structures of the main characteristic
fragments outlined by the authors. The fragmentation mechanism
and the molecular structures of the fragments were proposed by
analogy with the results of the high-resolution EI-MS measurements
performed during the 1960s. Fragments K and O are the
analogues of fragment B and J2, respectively. Fragment N is the
analogue of the EI-MS fragment G obtained by the well-known
retro Diels–Alder rearrangement. On the basis of the above fragmentation
mechanism fragment L is produced exclusively by loss
of a CH3COOH from position C(17). In our own work aimed at
identifying new VLB- and VCR-related impurities, an in-depth
high-resolution tandem MS analysis of VLB and VCR was performed
[45], and on the basis of MSn experiments we could prove that parallel
to the loss of CH3COOH, in a similar ratio the loss of HCOOCH3
can also occur from C(16). This observation could be utilized when
we had to identify a VLB impurity by on-line LC–MS/MS in which
the structural alteration affected the C(16)-COOMe moiety [46].