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RATIONALE In the field of natural products, de****tion of complex mixtures hasbecomes usual practice to annotate known compounds and avoid their re-isolation. To this purpose, many groups rely on liquid chromatography coupled to high resolution mass spectrometry to deduce molecular formulae of compounds allowing comparison with public or in-house databases. Electrospray ionisation is usually considered as the method of choice to investigate a large panel of compounds but, in some cases, it may lead to unusual results as described in