title: Biosynthesis-assisted structural elucidation of the bartolosides, chlorinated aromatic glycolipids from cyanobacteria.
abstract: The isolation of the bartolosides, unprecedented cyanobacterial glycolipids featuring aliphatic chains with chlorine substituents and C-glycosyl moieties, is reported. Their chlorinated dialkylresorcinol (DAR) core presented a major structural-elucidation challenge. To overcome this, we discovered the bartoloside (brt) biosynthetic gene cluster and linked it to the natural products through in vitro characterization of the DAR-forming ketosynthase and aromatase. Bioinformatic analysis also revealed a novel potential halogenase. Knowledge of the bartoloside biosynthesis constrained the DAR core structure by defining key pathway intermediates, ultimately allowing us to determine the full structures of the bartolosides. This work illustrates the power of genomics to enable the use of biosynthetic information for structure elucidation.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge MA, 02138 (USA).|Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093 (USA).|Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Rua dos Bragas, 289, 4050-123 Porto (Portugal).
authors.forename: Pedro N
authors.initials: PN
authors.lastname: Leão
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge MA, 02138 (USA).
authors.forename: Hitomi
authors.initials: H
authors.lastname: Nakamura
authors.affiliation: Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Rua dos Bragas, 289, 4050-123 Porto (Portugal).
authors.forename: Margarida
authors.initials: M
authors.lastname: Costa
authors.affiliation: Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093 (USA).
authors.forename: Alban R
authors.initials: AR
authors.lastname: Pereira
authors.affiliation: Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Rua dos Bragas, 289, 4050-123 Porto (Portugal).|Centre of Health and Environmental Research-CISA, ESTSP, Polytechnic Institute of Porto, Rua Valente Perfeito 322, 4400-330 Vila Nova de Gaia (Portugal).
authors.forename: Rosário
authors.initials: R
authors.lastname: Martins
authors.affiliation: Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Rua dos Bragas, 289, 4050-123 Porto (Portugal). vmvascon@fc.up.pt.|Department of Biology, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169-007 Porto (Portugal). vmvascon@fc.up.pt.
authors.forename: Vitor
authors.initials: V
authors.lastname: Vasconcelos
authors.affiliation: Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093 (USA). wgerwick@ucsd.edu.|Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego, La Jolla, CA 92093 (USA). wgerwick@ucsd.edu.
authors.forename: William H
authors.initials: WH
authors.lastname: Gerwick
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge MA, 02138 (USA). balskus@chemistry.harvard.edu.
authors.forename: Emily P
authors.initials: EP
authors.lastname: Balskus
mesh_terms: D002236:Carbohydrate Conformation; D002713:Chlorine / Q000737:chemistry*; D000458:Cyanobacteria / Q000737:chemistry*; D006017:Glycolipids / Q000096:biosynthesis* / Q000737:chemistry* / Q000302:isolation & purification
chemical_list: D006017:Glycolipids; D002713:Chlorine
keywords: biosynthesis; cyanobacteria; dialkylresorcinol; glycolipids; structure elucidation