Selective determination of mono- and dihydroxylated analogs of polybrominated diphenyl ethers in marine sponges by liquid-chromatography tandem mass spectrometry

Kato, Yoshihisa; Okada, Syohei; Atobe, Kazutaka; Endo, Tokiko; Haraguchi, Koichi

doi:10.1007/s00216-012-6132-2

Cited by 12 publications

(15 citation statements)

References 35 publications

(56 reference statements)

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“…The isomer denoted by ■ generates a single MS2 product ion corresponding to the loss of a bromine atom (Figure 3e), a characteristic feature for di-OH-BDEs that possess the two phenoxyls at the 2′ and 6 positions. 31 The other tetrabrominated di-OH-BDE isomer (8) demonstrated two major MS2 product ions that could be annotated to dibromophenol and dibromotrihydroxyphenol (Figure 3f). The observation of a trihydroxyphenol MS2 product ion clearly showed that 8 differs in the nature of the ether linkage from ■, in that all three oxygen atoms could be localized to a single ring.…”

Section: Resultsmentioning

confidence: 99%

“…Regio-isomerism within naturally produced di-OH-BDEs is similarly revealed by an EIC for 516.69 Da (Figure d), which corresponds to the dominant [M-H] 1– ion associated with the molecular formula C 12 H 6 Br 4 O 3 . The isomer denoted by ■ generates a single MS2 product ion corresponding to the loss of a bromine atom (Figure e), a characteristic feature for di-OH-BDEs that possess the two phenoxyls at the 2′ and 6 positions . The other tetrabrominated di-OH-BDE isomer ( 8 ) demonstrated two major MS2 product ions that could be annotated to dibromophenol and dibromotrihydroxyphenol (Figure f).…”

Section: Results and Discussionmentioning

confidence: 99%

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Complexity of Naturally Produced Polybrominated Diphenyl Ethers Revealed via Mass Spectrometry

Agarwal¹,

Li²,

Rahman³

et al. 2015

Environ. Sci. Technol.

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Polybrominated diphenyl ethers (PBDEs) are persistent and bioaccumulative anthropogenic and natural chemicals that are broadly distributed in the marine environment. PBDEs are potentially toxic due to inhibition of various mammalian signaling pathways and enzymatic reactions. PBDE isoforms vary in toxicity in accordance with structural differences, primarily in the number and pattern of hydroxyl moieties afforded upon a conserved core structure. Over four decades of isolation and discovery-based efforts have established an impressive repertoire of natural PBDEs. Based on our recent reports describing the bacterial biosyntheses of PBDEs, we predicted the presence of additional classes of PBDEs to those previously identified from marine sources. Using mass spectrometry and NMR spectroscopy, we now establish the existence of new structural classes of PBDEs in marine sponges. Our findings expand the chemical space explored by naturally produced PBDEs, which may inform future environmental toxicology studies. Furthermore, we provide evidence for iodinated PBDEs and direct attention toward the contribution of promiscuous halogenating enzymes in further expanding the diversity of these polyhalogenated marine natural products.

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Section: Resultsmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Complexity of Naturally Produced Polybrominated Diphenyl Ethers Revealed via Mass Spectrometry

Agarwal¹,

Li²,

Rahman³

et al. 2015

Environ. Sci. Technol.

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“…PBDEs and their metabolites (HO-PBDEs and MeO-PBDEs) are of interest because of their potential effects on people, − especially HO-PBDEs, which showed a more potent receptor activity compared to those of the parent PBDEs and corresponding MeO-PBDEs. ,, Previous studies showed that HO-PBDEs were detected even in human blood, which indicated that formation of HO-PBDEs from PBDEs might occur via endogenous transformation. Studies also showed that HO-PBDEs can be formed from naturally occurring MeO-PBDEs ,, and can be detected in various marine organisms, , which also posed another route of dietary exposure to HO-PBDEs by humans, this observation resulted in considerable concern about the toxic mechanism of these accumulative transformation products of naturally occurring and synthetic PBDEs. In our study, HO-PBDEs inhibited growth of E.…”

Section: Resultsmentioning

confidence: 99%

Mechanisms of Toxicity of Hydroxylated Polybrominated Diphenyl Ethers (HO-PBDEs) Determined by Toxicogenomic Analysis with a Live Cell Array Coupled with Mutagenesis in Escherichia coli

Lam

et al. 2014

Environ. Sci. Technol.

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Results of previous studies have indicated that 6-HO-BDE-47, the addition of the hydroxyl (HO) group to the backbone of BDE-47, significantly increased the toxicity of the chemical compared to its postulated precursor analogues, BDE-47 and 6-MeO-BDE-47. However, whether such a result is conserved across polybrominated diphenyl ether (PBDE) congeners was unknown. Here, cytotoxicity of 32 PBDE analogues (17 HO-PBDEs and 15 MeO-PBDEs) was further tested and the underlying molecular mechanism was investigated. A total of 14 of the 17 HO-PBDEs inhibited growth of Escherichia coli during 4 or 24 h durations of exposure, but none of the MeO-PBDEs was cytotoxic at the concentrations tested. 6-HO-BDE-47 and 2-HO-BDE-28 were most potent with 4 h median effect concentrations (EC50) of 12.13 and 6.25 mg/L, respectively, which trended to be lesser with a longer exposure time (24 h). Expression of 30 modulated and validated genes by 6-HO-BDE-47 in a previous study was also observed after exposure to other HO-PBDE analogues. For instance, uhpT was upregulated by 13 HO-PBDEs, and three rRNA operons (rrnA, rrnB, and rrnC) were downregulated by 8 HO-PBDEs. These unanimous responses suggested a potential common molecular signaling modulated by HO-PBDEs. To explore new information on mechanisms of action, this work was extended by testing the increased susceptibility of 182 mutations of transcriptional factors (TFs) and 22 mutations as genes modulated by 6-HO-BDE-47 after exposure to 6-HO-BDE-47 at the 4 h IC50 concentration. Although a unanimous upregulation of uhpT was observed after exposure to HO-PBDEs, no significant shift in sensitivity was observed in uhpT-defective mutants. The 54 genes, selected by cut-offs of 0.35 and 0.65, were determined to be responsible for "organic acid/oxoacid/carboxylic acid metabolic process" pathways, which supported a previous finding.

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“…PBDEs molecular weights vary from 249 (for mono-BDEs) to 959 (for deca-BDE) with typical 79 Br (50.5%) and 81 Br (49.5%) isotope distribution patterns [28]. Hence, depending on bromination degree, ten PBDE classes may be pointed out: mono-BDEs (BDE-1, -2 and -3), di-BDEs (BDE-4 to BDE-15), tri-BDEs (BDE-16 to BDE-39), tetra-BDEs (BDE-40 to BDE-81), penta-BDEs (BDE-82 to BDE-127), hexa-BDEs (BDE-128 to BDE-169), hepta-BDEs (BDE-170 to BDE-193), octa-BDEs (BDE-194 to BDE-205), nona-BDEs (BDE-206, -207 and -208) and deca-BDE (also referred to as BDE-209).…”

Section: Polybrominated Diphenyl Ethersmentioning

confidence: 99%

“…A number of different ionization modes have been applied in seafood studies, mostly ESI, but also IS and APCI all operating in negative mode [51,69,72,79,89]. The IDLs of OH-PBDEs using the aforementioned ionization techniques in LCeMS varied between 0.01 and 9.1 pg/mL [51,69,79].…”

Section: Column Systemmentioning

confidence: 99%

Polybrominated diphenyl ethers and metabolites – An analytical review on seafood occurrence

Cruz

Cunha

Marques

et al. 2017

TrAC Trends in Analytical Chemistry

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a b s t r a c tEnvironmental health is systematically compromised by persistent toxic substances, which may have serious implications in terms of food safety issues and, thus, in general public health. In this context, polybrominated diphenyl ethers (PBDEs) and their biologically active metabolites have been increasingly assessed in seafood, the main route of human exposure.As a consequence, a multiplicity of solvent-assisted analytical approaches is now available to accurately determine tiny amounts of these contaminants in complex matrices, like seafood. However, the majority of analytical procedures lead to high organic solvent consumption, thereby also contributing to the deterioration of environmental health.The current review provides up-to-date information and critical discussion regarding the most common methodologies applied in the determination of PBDEs and their metabolites in seafood (2006 e2016), from sample preparation to instrumental analysis. The ultimate goals of this comprehensive survey are to sensitize field researchers to work under the principles of green chemistry and to improve the global consciousness on the potential necessity of their regulation in foodstuffs.

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Selective determination of mono- and dihydroxylated analogs of polybrominated diphenyl ethers in marine sponges by liquid-chromatography tandem mass spectrometry

Cited by 12 publications

References 35 publications

Complexity of Naturally Produced Polybrominated Diphenyl Ethers Revealed via Mass Spectrometry

Complexity of Naturally Produced Polybrominated Diphenyl Ethers Revealed via Mass Spectrometry

Mechanisms of Toxicity of Hydroxylated Polybrominated Diphenyl Ethers (HO-PBDEs) Determined by Toxicogenomic Analysis with a Live Cell Array Coupled with Mutagenesis in Escherichia coli

Polybrominated diphenyl ethers and metabolites – An analytical review on seafood occurrence

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