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As a part of an SAR study aimed at testing the antitumor activity of some C15 acetogenins related to mycalin A, we report here the synthesis of the C-1 debromo-derivative of laurenciallene, a substance recently isolated from the red alga Laurencia obtusa. This new substance has been obtained by the selective, reductive debromination of the terminal bromoallene moiety of laurenciallene with Zn/AcOH. Its structure has been fully characterized by spectral methods, including 2D-NMR spectra.

Polybrominated diphenyl ethers (PBDEs) are a kind of serious pollutants in the ocean. Biodegradation is considered as an economical and safe way for PBDEs removal and reductive debromination dominates the initial pathway of anaerobic degradation. On the basis of experimental study, Octa-BDE 197, Hepta-BDE 183, Hexa-BDE 153, Penta-BDE 99 and Tetra-BDE 47 were selected as the initial degradation objects, and their debromination degradation were studied using density functional theory. The structures were optimized by Gaussian 09 program. Furthermore, the molecular orbitals and charge distribution were analyzed. All C-Br bond dissociation energies at different positions including ortho, meta and para bromine atoms were calculated and the sequence of debromination was obtained. There is a close relationship between molecular structure, charge, molecular orbital and C-Br bond. All PBDEs exhibited similar debromination pathways with preferential removal of meta and para bromines.

2,2′,4,4′-Tretrabromodiphenyl ether (BDE47) is known as a typical polybrominated diphenyl ethers (PBDEs) due to its high environmental abundance, ecological toxicity, and bioaccumulation. In this study, the influences of three typical surfactants (CTAB, SDS, and TX-100) on BDE47 solubilization and degradation by the polyanionic cellulose–stabilized Pd/Fe (PAC-Pd/Fe) nanoparticles were investigated. The results showed that BDE47 solubilities increased linearly when surfactant concentrations were above their critical micelle concentrations (CMCs), and the solubilization capacities of surfactants for BDE47 followed the order of TX-100 > CTAB > SDS. The appropriate dosages of surfactants were favorable for BDE47 degradation due to enhancing solubilization and accelerating mass transfer, while excessive surfactants inhibited BDE47 degradation due to excessive and thicker micelles formed, but still higher than no surfactant. The influences of various factors (PAC-Pd/Fe nanoparticle dosage, solution pH, and temperature) on BDE47 degradation in TX-100 solution were also tested. The results showed that BDE47 degradation followed the pseudo first-order kinetics model. The degradation rates of BDE47 increased as PAC-Pd/Fe nanoparticle dosage and temperature increased. Weak acidic condition (pH 5.5) was favorable for BDE47 degradation with 96.8% BDE47 was removed within 7.5 min, while alkaline condition (9.0) was not conducive to the degradation of BDE47. The degradation of BDE47 by PAC-Pd/Fe nanoparticles was a catalytic reductive debromination process via active H-species attack, wherein the sequential debromination was the dominant reaction. This study suggests that in the presence of moderate surfactant, PAC-Pd/Fe nanoparticles may be potentially employed to eliminate BDE47 in contaminated water.

Recent progress has been made in the reductive debromination of polybrominated diphenyl ethers (PBDEs) by nanoscale zero-valent iron (nZVI). To better understand the mechanism of this reaction, seven selected BDE congeners and their anions were investigated at the density functional theory (DFT) level using four different methods, including B3LYP/6-31G(d), B3LYP/6-31+G(d), B3LYP/6-31G(d,p) and B3LYP/6-311G(d,p). The cleaved C–Br bonds observed in the equilibrium structures of anionic PBDEs were adopted as the probe of the susceptible debromination position of PBDEs in the presence of nZVI, and the proposed major reaction pathways based on our calculations can satisfactorily conform to the reported experimental results. The debromination preference is theoretically evaluated as meta-Br > ortho-Br > para-Br. In addition, both the calculated frontier orbital energies and adiabatic electronic affinities were found to be highly related to their experimental reductive debromination rate constants. The highest linear regression coefficient was observed in the case using the energy of lowest unoccupied molecular orbital as the molecular descriptor obtained from B3LYP/6-31G(d) (R2 = 0.961, n = 7) or B3LYP/6-31G(d,p) (R2 = 0.961, n = 7). The results clearly showed the evidence of an electron transfer mechanism associated with this reductive debromination reaction.

Polybrominated diphenyl ethers (PBDEs) are a class of widely used flame retardants that have been highly accumulated in sediments. It is reported that microorganisms play an important role in the reductive debromination of PBDEs in anaerobic sediments. However, little is known about the effects of electron donors on the microbial community structure and their debromination capacity in PBDE transformation. In this study, alternate carbon substrates were used as electron donors to enrich the PBDE-debrominating microbial consortia to evaluate the effects of electron donors on PBDE microbial debromination. Decabromodiphenyl ether (BDE-209) was found to be the dominant (more than 50%) PBDEs congener in all consortia, and the percentage of BDE-209 was deceased by 12% (methanol), 11% (ethanol), 8% (acetate), 9% (lactate), 5% (pyruvate), and 11% (no electron donors), while the relative abundances of most lesser-brominated PBDEs increased after 90-day incubation compared to the initial profile of PBDEs. Substantial shifts in the microbial community structure among different amendments were observed based on denaturing gradient gel electrophoresis results. Pseudomonas spp. were identified to be the predominant organisms and the abundances of Band R, which was associated with Pseudomonas sp. SCSWA09, was well correlated with the biodegradation rate of BDE-209. Finally, the microbial community structure was highly correlated with the concentration of deca-BDE, octa-BDE and total nitrogen. These results provide insights into in situ bioremediation of environments contaminated by PBDEs and our understanding of microbial ecology associated with PBDE-debromination.

* Highly efficient debromination of BDE-47 was achieved in the ZVZ/AA system. * BDE-47 debromination by the ZVZ/AA can be applied to a wide range of pH. * AA inhibit s the formation of (hydr)oxide and accelerates the corrosion of ZVZ. * Reduction mechanism of BDE-47 debromination by the ZVZ/AA system was proposed. A new technique of zero-valent zinc coupled with ascorbic acid (ZVZ/AA) was developed and applied to debrominate the 2,2′,4,4′-Tetrabromodiphenyl ether (BDE-47), which achieved high conversion and rapid debromination of BDE-47 to less- or non-toxic forms. The reaction conditions were optimized by the addition of 100 mg/L ZVZ particles and 3 mmol/L AA at original solution pH= 4.00 using the solvent of methanol/H 2O (v:v= 4:6), which could convert approximately 94% of 5 mg/L BDE-47 into lower-brominated diphenyl ethers within a 90 min at the ZVZ/AA system. The high debromination of BDE-47 was mainly attributed to the effect of AA that inhibits the formation of Zn(II)(hydr)oxide passivation layers and promotes the corrosion of ZVZ, which leads to increase the reactivity of ZVZ. Additionally, ion chromatography and gas chromatography mass spectrometry analyses revealed that bromine ion and lower-debromination diphenyl ethers formed during the reduction of BDE-47. Furthermore, based on the generation of the intermediates products, and its concentration changes over time, it was proposed that the dominant pathway for conversion of BDE-47 was sequential debromination and the final products were diphenyl ethers. These results suggested that the ZVZ/AA system has the potential for highly efficient debromination of BDE-47 from wastewater.