Complexity of Naturally Produced Polybrominated Diphenyl Ethers Revealed via Mass Spectrometry

Agarwal, Vinayak; Li, Jie; Rahman, Imran R; Borgen, Miles; Aluwihare, Lihini I.; Biggs, Jason S.; Paul, Valerie J.; Moore, Bradley S.

doi:10.1021/es505440j

Cited by 47 publications

(61 citation statements)

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“…Consistent with our previous characterization of PBDEs from Dysideidae 8 , the most abundant natural product in Clade Ia specimens was 5 , together with minor amounts of 1 as detected by LC/MS/MS (Supplementary Figure 3). In contrast, molecule 1 dominated the product profile of Clade Ib.…”

Section: Resultssupporting

confidence: 91%

“…While we recently reported the biosynthetic basis for the natural production of polybrominated phenolics, including PBDEs, by marine γ -proteobacteria 4 , the most prodigious natural sources of PBDEs in the marine environment are the benthic filter feeding marine sponges (Porifera) within the family Dysideidae 5-8 . In Dysideidae, PBDEs can exceed 10% of the sponge tissue by dry weight 9,10 .…”

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Metagenomic discovery of polybrominated diphenyl ether biosynthesis by marine sponges

et al. 2017

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Naturally produced polybrominated diphenyl ethers (PBDEs) pervade the marine environment and structurally resemble toxic man-made brominated flame retardants. PBDEs bioaccumulate in marine animals and are likely transferred to the human food chain. However, the biogenic basis for PBDE production in one of their most prolific sources, marine sponges of the order Dysideidae, remains unidentified. Here, we report the discovery of PBDE biosynthetic gene clusters within sponge microbiome-associated cyanobacterial endosymbionts by employing an unbiased metagenome mining approach. By expression of PBDE biosynthetic genes in heterologous cyanobacterial hosts, we correlate the structural diversity of naturally produced PBDEs to modifications within PBDE biosynthetic gene clusters in multiple sponge holobionts. Our results establish the genetic and molecular foundation for the production of PBDEs in one of the most abundant natural sources of these molecules, further setting the stage for a metagenomic-based inventory of other PBDE sources in the marine environment.

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Section: Resultssupporting

confidence: 91%

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Metagenomic discovery of polybrominated diphenyl ether biosynthesis by marine sponges

et al. 2017

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“…Moreover, the fact that the polyhalogenated diphenyl core of 2 closely resembles the structure of p oly b rominated d iphenyl e ther (PBDE) anthropogenic and natural persistent organic compounds, such as from marine bacteria 49 and sponges, 347–349 suggests that deiodinases might also be engineered for bioremediation function, a role predominantly entertained for bacterial B 12 -dependent RDHs. 350,351 Structural understanding of thyroid hormone deiodinases may also provide insight into the mechanisms of toxicity of endocrine-disrupting PBDE molecules.…”

Section: Enzymatic Dehalogenationmentioning

confidence: 99%

“…Particularly with respect to natural product halogenation biochemistry, for instance, filter-feeding benthic marine invertebrates such as sponges are one of the most prolific producers where halogenated natural products can constitute up to 10% of the sponge dry weight. 34,347,446,447 Marine sponges are the ‘petri-dishes of the oceans’ harboring an extraordinary diversity of endosymbiotic microbiome that has been postulated, and in many cases experimentally verified, to be the source of the natural product diversity. 448–451 It is thus noteworthy that while the inventory of FDHs from sponge-microbiome consortia has attracted recent interest, 452,453 to the best of our knowledge, no sponge-derived FDH, V-CPO, V-BPO, or SAM-dependent halogenase has been confirmed within genomic or biochemical context for the production of a halogenated natural product.…”

Section: Future Perspectivesmentioning

confidence: 99%

Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse

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Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature’s halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

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“…[Moore et al, 1996;Amin et al, 2012] However, it is unlikely for a dibromo compound to be produced by haloperoxidases, and it is more likely that this compound is produced by a more specific biosynthetic pathway. Agarwal et al, , 2015 Several iodine containing compounds also appear in the surface and 20m samples. It is possible that they are also produced by haloperoxidases, although the retention times and distribution of these iodine coumpounds are significantly different than their bromine counterparts.…”

Section: Appendix 52: Halogenated Compounds In the Upwelling Communitymentioning

confidence: 99%

Molecular determination of marine iron ligands by mass spectrometry

Boiteau¹

2016

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Abstract:Marine microbes produce a wide variety of metal binding organic ligands that regulate the solubility and availability of biologically important metals such as iron, copper, cobalt, and zinc.In marine environments where the availability of iron limits microbial growth and carbon fixation rates, the ability to access organically bound iron confers a competitive advantage. Thus, the compounds that microbes produced to acquire iron play an important role in biogeochemical carbon and metal cycling. However, the source, abundance, and identity of these compounds are poorly understood. To investigate these processes, sensitive methodologies were developed to gain a compound-specific window into marine iron speciation by combining trace metal clean sample collection and chromatography with inductively coupled plasma mass spectrometry (LC-ICPMS) and electrospray ionization mass spectrometry (LC-ESIMS). Coupled with isotope pattern assisted search algorithms, these tools provide a means to quantify and isolate specific iron binding ligands from seawater and marine cultures, identify them based on their mass and fragmentation spectra, and investigate their metal binding kinetics.Using these techniques, we investigated the distribution and diversity of marine iron binding ligands. In cultures, LC-ICPMS-ESIMS was used to identify new members of siderophore classes produced by marine cyanobacteria and heterotrophic bacteria, including synechobactins and marinobactins. Applications to natural seawater samples from the Pacific Ocean revealed a wide diversity of both known and novel metal compounds that are linked to specific nutrient regimes. Ferrioxamines B, E, and G were identified in productive coastal waters near California and Peru, in oligotrophic waters of the North and South Pacific Gyre, and in association with zooplankton grazers. Siderophore concentrations were up to five-fold higher in iron-deficient offshore waters (9pM) and were dominated by amphibactins, amphiphilic siderophores that partition into cell membranes. Furthermore, synechobactins were detected within nepheloid layers along the continental shelf. These siderophores reflect adaptations that impact dissolved iron bioavailability and thus have important consequences for marine ecosystem community structures and primary productivity. The ability to map and characterize these compounds has opened new opportunities to better understand mechanisms that link metals with the microbes that use them. 4Acknowledgements:

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Complexity of Naturally Produced Polybrominated Diphenyl Ethers Revealed via Mass Spectrometry

Cited by 47 publications

References 48 publications

Metagenomic discovery of polybrominated diphenyl ether biosynthesis by marine sponges

Metagenomic discovery of polybrominated diphenyl ether biosynthesis by marine sponges

Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse

Molecular determination of marine iron ligands by mass spectrometry

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