Species of Microcystis are the most common bloom‐forming cyanobacteria in several countries. Despite extensive studies regarding the production of bioactive cyanopeptides in this genus, there are limited data on isolated strains from Brazil. Three Microcystis sp. strains were isolated from the Salto Grande Reservoir (LTPNA01, 08 and 09) and investigated for the presence of mcy genes, microcystins and other cyanopeptides. Microcystin and microginin production was confirmed in two isolates using high‐resolution tandem mass spectrometry after electrospray ionization (ESI‐Q‐TOF), and the structures of two new microginin congeners were proposed (MG756 Ahda‐Val‐Leu‐Hty‐Tyr and MG770 MeAhda‐Val‐Leu‐Hty‐Tyr). The biosynthesis profile of the identified cyanopeptides was evaluated at different growth phases via a newly developed HPLC‐UV method. Results demonstrated no substantial differences in the production of microcystins and microginins after data normalization to cell quota, suggesting a constitutive biosynthesis. This study represents the first confirmed co‐production of microginins and microcystins in Brazilian strains of Microcystis sp. and highlights the potential of Brazilian cyanobacteria as a source of natural compounds with pharmaceutical interest.

In this brief overview, the authors describe mass spectral techniques for the detection and identification of microcystin toxins. Microcystins are secondary metabolites produced by cyanobacteria. Determination of these toxic compounds and discovery of new variants is very important as they pose a great danger to the human food chain. Cyanobacterial blooms frequently occur in many areas worldwide and have the potential to contaminate the water via cyanotoxin release, especially microcystins. Among the various analytical techniques used for analysis, mass spectrometry has become the most important method as it allows simultaneous quantification and structural characterization of multiple microcystin variants. This brief overview article focuses on mass spectrometry techniques for identification of microcystins, including ionization methods, mass spectral fragmentation routes, profiling techniques, tandem and high-resolution mass spectrometry as well as typing of cyanobacterial strains.

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Microcystins (MC) are a large group of toxic cyclic peptides, produced by cyanobacteria in eutrophic water systems. Identification of MC variants mostly relies on liquid chromatography (LC) combined with collision-induced dissociation (CID) mass spectrometry. Deviations from the essential amino acid complement are a common feature of these natural products, which makes the CID analysis more difficult and not always successful. Here, both CID and electron capture dissociation (ECD) were applied in combination with ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry to study a cyanobacteria strain isolated from the Salto Grande Reservoir in Sao Paulo State, Brazil, without prior LC separation. CID was shown to be an effective dissociation technique for quickly identifying the MC variants, even those that have previously been difficult to characterize by CID. Moreover, ECD provided even more detailed and complementary information, which enabled us to precisely locate metal binding sites of MCs for the first time. This additional information will be important for environmental chemists to study MC accumulation and production in ecosystems.