title: Sulfated phenolic acids from Dasycladales siphonous green algae.
abstract: Sulfated aromatic acids play a central role as mediators of chemical interactions and physiological processes in marine algae and seagrass. Among others, Dasycladus vermicularis (Scopoli) Krasser 1898 uses a sulfated hydroxylated coumarin derivative as storage metabolite for a protein cross linker that can be activated upon mechanical disruption of the alga. We introduce a comprehensive monitoring technique for sulfated metabolites based on fragmentation patterns in liquid chromatography/mass spectrometry and applied it to Dasycladales. This allowed the identification of two new aromatic sulfate esters 4-(sulfooxy)phenylacetic acid and 4-(sulfooxy)benzoic acid. The two metabolites were synthesized to prove the mass spectrometry-based structure elucidation in co-injections. We show that both metabolites are transformed to the corresponding desulfated phenols by sulfatases of bacteria. In biofouling experiments with Escherichia coli and Vibrio natriegens the desulfated forms were more active than the sulfated ones. Sulfatation might thus represent a measure of detoxification that enables the algae to store inactive forms of metabolites that are activated by settling organisms and then act as defense.
authors.affiliation: Friedrich Schiller University Jena, Institute for Inorganic and Analytical Chemistry, Bioorganic Analytics, Lessingstraße 8, 07743 Jena, Germany.
authors.forename: Caroline
authors.initials: C
authors.lastname: Kurth
authors.affiliation: Friedrich Schiller University Jena, Institute for Inorganic and Analytical Chemistry, Bioorganic Analytics, Lessingstraße 8, 07743 Jena, Germany.
authors.forename: Matthew
authors.initials: M
authors.lastname: Welling
authors.affiliation: Friedrich Schiller University Jena, Institute for Inorganic and Analytical Chemistry, Bioorganic Analytics, Lessingstraße 8, 07743 Jena, Germany. Electronic address: georg.pohnert@uni-jena.de.
authors.forename: Georg
authors.initials: G
authors.lastname: Pohnert
mesh_terms: D001565:Benzoates / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology; D018441:Biofilms / Q000187:drug effects / Q000254:growth & development; D000460:Chlorophyta / Q000737:chemistry* / Q000378:metabolism*; D017753:Ecosystem; D004926:Escherichia coli / Q000187:drug effects / Q000502:physiology; D005431:Florida; D062385:Hydroxybenzoates / Q000737:chemistry* / Q000494:pharmacology; D010648:Phenylacetates / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology; D013431:Sulfates / Q000737:chemistry*; D013463:Sulfuric Acid Esters / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology; D014733:Vibrio / Q000187:drug effects / Q000502:physiology
chemical_list: D001565:Benzoates; D062385:Hydroxybenzoates; D010648:Phenylacetates; D013431:Sulfates; D013463:Sulfuric Acid Esters; C017616:phenolic acid
keywords: Activated defense; Anti-fouling metabolites; Dasycladales; Marine chemical ecology; Siphonous green algae; Sulfatase; Sulfated phenolic acids