Design and Synthesis of Marine Polybrominated Diphenyl Ether Derivatives as Potential Anti-Inflammatory Agents.

Natural polybrominated diphenyl ethers are generally isolated from sponges and possess a broad range of biological activities. Through screening of our marine natural product library, we discovered that polybrominated diphenyl ethers 5 and 6 exhibit considerable anti-inflammatory activity. In order to expand our repertoire of derivatives for further biological activity studies, we designed and synthesized a series of 5-related polybrominated diphenyl ethers. Importantly, compound 5a showed comparable anti-inflammatory activity while much lower cytotoxicity on lipopolysaccharide (LPS)-induced RAW264.7 cells. Additionally, western blotting analysis showed that 5a reduced the expression of phosphorylated extracellular signal-regulated kinase (p-ERK). Besides, molecular docking experiments were conducted to predict and elucidate the potential mechanisms underlying the varying anti-inflammatory activities exhibited by compounds 5a, 5, and 6.

Computational Risk Assessment of Persistence, Bioaccumulation, and Toxicity of Novel Flame-Retardant Chemicals.

Novel brominated flame retardants (NBFRs) have emerged as chemicals of environmental concern, as they have been widely used as an alternative to polybrominated diphenyl ethers (PBDEs). Considering the similar structural features of NBFRs and PBDEs necessitates a comprehensive investigation to understand the physicochemical relationships of these compounds and their ability to alter biological functions. In this study, we investigated the persistent nature of NBFRs in terms of thyroid-disrupting potential by understanding the structure-stability aspects using density functional theory (DFT)-based reactivity parameters and interactions via molecular docking and molecular dynamics (MD) simulations. The results indicate that the DFT-based stability descriptor (chemical hardness) is associated with the persistent nature of NBFRs. The computed molecular interaction profile revealed prominent interactions between thyroid receptor-ß (TR-ß) and NBFRs. Stable trajectory and interactions with TR-ß were obtained with ATE, p-TBX, PBT, PBEB, and TBBPA-DBPE during 100 ns of MD simulation. The results of these studies have suggested that the presence of a higher number of halogenated atoms increases the stability vis-à-vis the persistence and endocrine disruption potential of NBFRs.

Exploring the biosynthetic possibilities of hydroxylated polybrominated diphenyl ethers from bromophenols in Prorocentrum donghaiense: Implications for bioremediation.

Bromophenols has been proven to synthesize hydroxylated polybrominated diphenyl ethers (OH-PBDEs), which may pose additional environmental and health risks in the process of bioremediation. In this study, the removal of 2,4-dibromophenol (2,4-DBP) and 2,4,6-tribromophenol (2,4,6-TBP) and the biosynthetic of OH-PBDEs by Prorocentrum donghaiense were explored. The removal efficiencies of 2,4-DBP and 2,4,6-TBP ranged from 32.71% to 76.89% and 31.15%-78.12%, respectively. Low concentrations of 2,4-DBP stimulated algal growth, while high concentrations were inhibitory. Furthermore, exposure to 10.00 mg L-1 2,4-DBP resulted in the detection of 2'-hydroxy-2,3',4,5'-tetrabromodiphenyl ether (2'-OH-BDE-68) within P. donghaiense. In contrast, increasing concentrations of 2,4,6-TBP considerably inhibited P. donghaiense growth, with 4'-hydroxy-2,3',4,5',6-pentabromodiphenyl ether (4'-OH-BDE-121) detected within P. donghaiense under 5.00 mg L-1 2,4,6-TBP. Metabolomic analysis further revealed that the synthesized OH-PBDEs exhibited higher toxicity than their precursors and identified the oxidative coupling as a key biosynthetic mechanism. These findings confirm the capacity of P. donghaiense to remove bromophenols and biosynthesize OH-PBDEs from bromophenols, offering valuable insights into formulating algal bioremediation to mitigate bromophenol contamination.

The role of iron materials in the abiotic transformation and biotransformation of polybrominated diphenyl ethers (PBDEs): A review.

Polybrominated diphenyl ethers (PBDEs), widely used as flame retardants, easily enter the environment, thus posing environmental and health risks. Iron materials play a key role during the migration and transformation of PBDEs. This article reviews the processes and mechanisms of adsorption, degradation, and biological uptake and transformation of PBDEs affected by iron materials in the environment. Iron materials can effectively adsorb PBDEs through hydrophobic interactions, π-π interactions, hydrogen/halogen bonds, electrostatic interactions, coordination interactions, and pore filling interactions. In addition, they are beneficial for the photodegradation, reduction debromination, and advanced oxidation degradation and debromination of PBDEs. The iron material-microorganism coupling technology affects the uptake and transformation of PBDEs. In addition, iron materials can reduce the uptake of PBDEs in plants, affecting their bioavailability. The species, concentration, and size of iron materials affect plant physiology. Overall, iron materials play a bidirectional role in the biological uptake and transformation of PBDEs. It is necessary to strengthen the positive role of iron materials in reducing the environmental and health risks caused by PBDEs. This article provides innovative ideas for the rational use of iron materials in controlling the migration and transformation of PBDEs in the environment.