[ADMAdda⁵]‐microcystins in Planktothrix agardhii strain PH‐123 (cyanobacteria)— importance for monitoring of microcystins in the environment

Two major and two minor microcystins (MCYST) were isolated from a hepatotoxic Danish strain of Planktothrix agardhii (Gomont) Anagnostidis et Komárek by reversed-phase high-performance liquid chromatography. The microcystins were characterized by UV spectroscopy, amino acid analysis, fast atom bombardment mass spectrometry (FABMS), and high-resolution FABMS. The major microcystins were further analysed by collisionally induced tandem electrospray ionization MS. The microcystins were found to be demethylated variants of MCYST-HtyR (homotyrosine-arginine) and MCYST-LR (leucine-arginine). The two major microcystins contained an acetyl-demethyl variant (ADMAdda) of 3-amino-9-acetoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (Adda). This is the first report of [ADMAdda5]-microcystins in Planktothrix. The two [ADMAdda5]-microcystins inhibited protein phosphatase activity but showed low cross-reactivity with antibodies of an enzyme-linked immunosorbent assay (ELISA), emphasizing the potential underestimation of the toxicity of natural blooms dominated by Planktothrix when microcystin content is quantified using only an ELISA.