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Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant; however, it is a persistent organic pollutant as well as affects the human thyroid hormones and causes cancer. However, the degradation of HBCD has received little attention from researchers. Due to its bioaccumulative and hazardous properties, an appropriate strategy for its remediation is required. In this study, we investigated the biodegradation of HBCD using Shewanella oneidensis MR-1 under optimized conditions. The Box-Behnken design (BBD) was implemented for the optimization of the physical degradation parameters of HBCD. S. oneidensis MR-1 showed the best degradation performance at a temperature of 30 °C, pH 7, and agitation speed of 115 rpm, with an HBCD concentration of 1125 μg/L in mineral salt medium (MSM). The strain tolerated up to 2000 μg/L HBCD. Gas chromatography-mass spectrometry analysis identified three intermediates, including 2-bromo dodecane, 2,7,10-trimethyldodecane, and 4-methyl-1-decene. The results provide an insightful understanding of the biodegradation of HBCD by S. oneidensis MR-1 under optimized conditions and could pave the way for further eco-friendly applications. KEY POINTS: • HBCD biodegradation by Shewanella oneidensis • Optimization of HBCD biodegradation by the Box-Behnken analysis • Identification of useful metabolites from HBCD degradation., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Background: Gene therapy shows great promise for a broad array of diseases. However, we found that hypoxic tumor microenvironment (TME) exerted significant inhibitory effects on transfection efficiency of a variety of gene vectors (such as Lipo 2000 and PEI) in an oxygen-dependent manner. Solid tumors inevitably resulted in acute hypoxic areas due to the rapid proliferation of tumor cells and the aberrant structure of blood vessels. Thus, the hypoxic TME severely limited the efficiency and application of gene therapy., Methods: In our previous study, we constructed endoplasmic reticulum-targeted cationic liposomes, PAR-Lipo, which could effectively deliver genes and ensure high transfection efficiency under normoxia. Unsatisfactorily, the transfection efficiency of PAR-Lipo was rather poor under hypoxia. We believed that reoxygenation was the most direct and effective means to rescue the low transfection under hypoxia. Hence, we fabricated liposomes modified with perfluorooctyl bromide (PFOB@Lipo) to load oxygen and deliver it to tumor sites, which effectively alleviated the hypoxic nature of tumor. Then PAR-Lipo were applied to mediate high-efficiency delivery of tumor suppressor gene pTP53 to inhibit tumor progression., Results: The results showed that such staged strategy augmented the expression of P53 protein in tumors and extremely suppressed tumor growth., Conclusion: This work was the first attempt to utilize an oxygen nanocarrier to assist the therapeutic effect of gene therapy under hypoxia, providing a new reference for gene therapy in malignant tumors. GRAPHICAL ABSTARCT., (© 2021. The Author(s).)

Different approaches have been reported to enhance penetration of small drugs through physiological barriers; among them is the self-assembly drug conjugates preparation that shows to be a promising approach to improve activity and penetration, as well as to reduce side effects. In recent years, the use of drug-conjugates, usually obtained by covalent coupling of a drug with biocompatible lipid moieties to form nanoparticles, has gained considerable attention. Natural products isolated from plants have been a successful source of potential drug leads with unique structural diversity. In the present work three molecules derived from natural products were employed as lead molecules for the synthesis of self-assembled nanoparticles. The first molecule is the cytotoxic royleanone 7α-acetoxy-6β-hydroxyroyleanone (Roy, 1 ) that has been isolated from hairy coleus ( Plectranthus hadiensis (Forssk.) Schweinf). ex Sprenger leaves in a large amount. This royleanone, its hemisynthetic derivative 7α-acetoxy-6β-hydroxy-12-benzoyloxyroyleanone (12BzRoy, 2 ) and 6,7-dehydroroyleanone (DHR, 3 ), isolated from the essential oil of thicket coleus ( P. madagascariensis (Pers.) Benth.) were employed in this study. The royleanones were conjugated with squalene (sq), oleic acid (OA), and/or 1-bromododecane (BD) self-assembly inducers. Roy-OA, DHR-sq, and 12BzRoy-sq conjugates were successfully synthesized and characterized. The cytotoxic effect of DHR-sq was previously assessed on three human cell lines: NCI-H460 (IC 50 74.0 ± 2.2 µM), NCI-H460/R (IC 50 147.3 ± 3.7 µM), and MRC-5 (IC 50 127.3 ± 7.3 µM), and in this work Roy-OA NPs was assayed against Vero-E6 cells at different concentrations (0.05, 0.1, and 0.2 mg/mL). The cytotoxicity of DHR-sq NPs was lower when compared with DHR alone in these cell lines: NCI-H460 (IC 50 10.3 ± 0.5 µM), NCI-H460/R (IC 50 10.6 ± 0.4 µM), and MRC-5 (IC 50 16.9 ± 0.5 µM). The same results were observed with Roy-OA NPs against Vero-E6 cells as was found to be less cytotoxic than Roy alone in all the concentrations tested. From the obtained DLS results, 12BzRoy-sq assemblies were not in the nano range, although Roy-OA NP assemblies show a promising size (509.33 nm), Pdl (0.249), zeta potential (-46.2 mV), and spherical morphology from SEM. In addition, these NPs had a low release of Roy at physiological pH 7.4 after 24 h. These results suggest the nano assemblies can act as prodrugs for the release of cytotoxic lead molecules.

Redox flow batteries (RFB) are one of the most interesting technologies in the field of energy storage, since they allow the decoupling of power and capacity. Zinc-bromine flow batteries (ZBFB) are a type of hybrid RFB, as the capacity depends on the effective area of the negative electrode (anode), on which metallic zinc is deposited during the charging process. Gaseous bromine is generated at the positive electrode (cathode) during the charging process, so the use of bromine complexing agents (BCA) is very important. These BCAs are quaternary amines capable of complexation with bromine and generating an organic phase, immiscible with the aqueous electrolyte. One of the most commonly used BCAs in RFB technology is 4-methylethylmorpholinium bromide (MEM-Br). In this work, an alternative quaternary amine 4-methylpropylmorpholinium bromide (MPM-Br) was studied. MPM-Br was integrated into the electrolyte, and 200 charge-discharge cycles were performed on the resulting ZBFBs. The obtained results were compared with those when MEM-Br was used, and it was observed that the electrolyte with MPM-Br displays a higher resistance in voltage and higher energy efficiency, making it a promising alternative to MEM-Br.

Background: The decrease in asialoglycoprotein receptor (ASGPR) levels is observed in patients with chronic liver disease and liver tumor. The aim of our study was to develop ASGPR-targeted superparamagnetic perfluorooctylbromide nanoparticles (M-PFONP) and wonder whether this composite agent could target buffalo rat liver (BRL) cells in vitro and could improve R 2 ∗ value of the rat liver parenchyma after its injection in vivo., Methods: GalPLL, a ligand of ASGPR, was synthesized by reductive amination. ASGPR-targeted M-PFOBNP was prepared by a film hydration method coupled with sonication. Several analytical methods were used to investigate the characterization and safety of the contrast agent in vitro. The in vivo MR T 2 ∗ mapping was performed to evaluate the enhancement effect in rat liver., Results: The optimum concentration of Fe 3 O 4 nanoparticles inclusion in GalPLL/M-PFOBNP was about 52.79  µ g/mL, and the mean size was 285.6 ± 4.6 nm. The specificity of GalPLL/M-PFOBNP for ASGPR was confirmed by incubation experiment with fluorescence microscopy. The methyl thiazolyl tetrazolium (MTT) test showed that there was no significant difference in the optical density (OD) of cells incubated with all GalPLL/M-PFOBNP concentrations. Compared with M-PFOBNP, the increase in R 2 ∗ value of the rat liver parenchyma after GalPLL/M-PFOBNP injection was higher., Conclusions: GalPLL/M-PFOBNP may potentially serve as a liver-targeted contrast agent for MR receptor imaging., Competing Interests: The authors declare no conflicts of interest., (Copyright © 2021 Yang Li et al.)

The first total synthesis of marine natural product, (-)-majusculoic acid ( 1 ) and its seven analogs ( 9 - 15 ), was accomplished in three to ten steps with a yield of 3% to 28%. The strategy featured the application of the conformational controlled establishment of the trans -cyclopropane and stereochemical controlled bromo-olefination or olefination by Horner-Wadsworth-Emmons (HWE) reaction. The potential anti-inflammatory activity of the eight compounds ( 1 and 9 - 15 ) was evaluated by determining the nitric oxide (NO) production in the lipopolysaccharide (LPS)-induced mouse macrophages RAW264.7. (-)-Majusculoic acid ( 1 ), methyl majusculoate ( 9 ), and (1 R ,2 R )-2-((3 E ,5 Z )-6-bromonona-3,5-dien-1-yl)cyclopropane-1-carboxylic acid ( 12 ) showed significant effect with inhibition rates of 33.68%, 35.75%, and 43.01%, respectively. Moreover, they did not show cytotoxicity against RAW264.7 cells, indicating that they might be potential anti-inflammatory agents.

Two typical brominated flame retardants (BFRs), namely, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), were persistent organic pollutants widely detected in various environmental media. This study aimed to successfully synthesize micro-nano-structured magnetite particles (MNMPs) with surface modification by citric acid molecules. The synthesized composites served as an adsorbent for extracting TBBPA and HBCD from environmental water samples followed by gas chromatography-mass spectrometry analysis. The obtained MNMPs were characterized in terms of crystal structure, morphology, size distribution, hydrophobic and hydrophilic performance and magnetism. The results indicated that the MNMPs exhibited high surface area, good dispersibility, and strong magnetic responsiveness for separation. The parameters affecting the extraction efficiency were optimized, including sample pH, amount of sorbents, extraction time and desorption conditions. Under the optimum conditions, the recovery was 83.5 and 107.1%, limit of detection was 0.13 and 0.35μg/mL (S/N = 3), and limit of quantification was 0.37 and 0.59 μg/mL (S/N = 10) for TBBPA and HBCD respectively. The relative standard deviations obtained using the proposed method were less than 8.7%, indicating that the MNMP magnetic solid-phase extraction method had advantages of simplicity, good sensitivity and high efficiency for the extraction of the two BFRs from environmental water., Competing Interests: All mentioned organizations neither served on the editorial board nor acted as an expert witness in relevant legal proceedings. Although the second author affiliations: Jiangsu Environmental Engineering Technology Co. LTD as a commercial affiliation, it does not alter our adherence to all PLOS ONE policies on sharing data and materials. It will not use the information to develop products, apply for patents.

The phase problem is a persistent bottleneck that impedes the structure-determination pipeline and must be solved to obtain atomic resolution crystal structures of macromolecules. Although molecular replacement has become the predominant method of solving the phase problem, many scenarios still exist in which experimental phasing is needed. Here, a proof-of-concept study is presented that shows the efficacy of using tetrabromoterephthalic acid (B4C) as an experimental phasing compound. Incorporating B4C into the crystal lattice using co-crystallization, the crystal structure of hen egg-white lysozyme was solved using MAD phasing. The strong anomalous signal generated by its four Br atoms coupled with its compatibility with commonly used crystallization reagents render B4C an effective experimental phasing compound that can be used to overcome the phase problem.

Mixtures of polyethylene oxide (PEO, M.W.~900,000) and imidazolium ionic liquids (ILs) are studied using high-pressure Fourier-transform infrared spectroscopy. At ambient pressure, the spectral features in the C-H stretching region reveal that PEO can disturb the local structures of the imidazolium rings of [BMIM] + and [HMIM] + . The pressure-induced phase transition of pure 1-butyl-3-methylimidazolium bromide ([BMIM]Br) is observed at a pressure of 0.4 GPa. Pressure-enhanced [BMIM]Br-PEO interactions may assist PEO in dividing [BMIM]Br clusters to hinder the aggregation of [BMIM]Br under high pressures. The C-H absorptions of pure 1-hexyl-3-methylimidazolium bromide [HMIM]Br do not show band narrowing under high pressures, as observed for pure [BMIM]Br. The band narrowing of C-H peaks is observed at 1.5 GPa for the [HMIM]Br-PEO mixture containing 80 wt% of [HMIM]Br. The presence of PEO may reorganize [HMIM]Br clusters into a semi-crystalline network under high pressures. The differences in aggregation states for ambient-pressure phase and high-pressure phase may suggest the potential of [HMIM]Br-PEO (M.W.~900,000) for serving as optical or electronic switches.

The expectation that antimony (Sb) compounds should display phosphorescence emissions based on the "heavy element effect" prompted our interest in the introduction of antimony to a biaryl as the bridging atom in a fused heterole system. Herein, the synthesis, molecular structures, and optical properties of novel benzene-fused heteroacenes containing antimony or arsenic atoms are described. The stiboles and arsole were prepared by the condensation of dibromo(phenyl)stibane or dichloro(phenyl)arsine with dilithium intermediates derived from the corresponding dibromo compounds. Nuclear magnetic resonance (NMR) spectroscopy and X-ray crystal analysis revealed that the linear pentacyclic stibole was highly symmetric in both the solution and crystal states. In contrast, the curved pentacyclic stibole adopted a helical structure in solution, and surprisingly, only M helical molecules were crystallized from the racemate. All synthesized compounds produced very weak or no emissions at room temperature or in the solid state. In contrast, the linear penta- and tetracyclic stiboles exhibited clear phosphorescence emissions in the CHCl 3 frozen matrix at 77 K under aerobic conditions.

The irradiation of halogen-bonded complexes with light leads to the homolysis of carbon-halogen bonds and the formation of the corresponding carbon radical species. However, the only methodology reported for these halogen-bonding complexes is using CBr 4 as the halogen-bond donor and its applicability is of great interest. In this study, the atom transfer radical addition (ATRA) reaction of olefins using bromomalonates as halogen-bonding donors was developed. Using 4-phenylpyridine as the halogen-bonding acceptor, the desired reaction proceeded well under external irradiation of 380 nm light to furnish the corresponding ATRA reaction product. The ATRA reaction was effective in generating the corresponding products for a variety of olefins. Furthermore, the ATRA reaction was applicable to bulky ketones, substrates, and malonate esters. The intermediates of the reaction were identified and a plausible reaction mechanism was proposed.

Marine algae contain various bromophenols that have been shown to possess a variety of biological activities, including antiradical, antimicrobial, anticancer, antidiabetic, anti-inflammatory effects, and so on. Here, we briefly review the recent progress of these marine algae biomaterials and their derivatives from 2011 to 2020, with respect to structure, bioactivities, and their potential application as pharmaceuticals.

Aggregation of nanoparticles (NPs) can hinder the degradative reactivity of particles towards organic pollutants as it reduces available surface area for reaction. This limitation may be circumvented by applying dispersant to improve colloidal stability of nanoparticle suspension. This study examined the removal of hexabromocyclododecane (HBCD), a recently listed persistent organic pollutant, by carboxymethylcellulose (CMC) stabilized nanoscale zerovalent iron (CMC-NZVI) and bimetallic Ni/Fe nanoparticles (CMC-Ni/Fe) under the influence of suspension chemistry. The mass-normalized removal rate constants of HBCD by CMC-Ni/Fe NPs increased with lower particle aggregation. However, the coating could introduce diffusion resistance as HBCD diffused through the CMC layer to the Fe surface. The activation energy was estimated to be 26.8 kJ mol -1 , indicating the overall reaction process was neither surface-limited nor diffusion-controlled. The reactivity of CMC-Ni/Fe NPs toward HBCD was not affected by aqueous initial pH substantially. Common monoanions (Cl - , NO 3 - , and HCO 3 - ) generally enhanced HBCD adsorption but diminished its debromination. The removal rate did not differ significantly among the studied monoanions over a concentration of 2.5-10 mM except HCO 3 - . Overall, CMC coating can stabilize Ni/Fe NPs, increase their adsorption of HBCD, provide buffer pH capacity, and overcome common inhibition effects of anions in water. These findings suggested the high potential of using CMC-Ni/Fe NPs for in-situ remediation., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Background: Resistance developments against established antibiotics are an emerging problem for antibacterial therapies. Novel antibiotics are urgently needed. Materials & methods: We developed novel small-molecule antibacterials which are easily accessible in a simple one-pot synthesis. The central cyclopentaindole core is substituted with two indole residues. Various indole and cyclopentane substituents have been introduced. Additionally, first indole substituted propene compounds as ring-open variants of the cyclopentaindoles have been yielded and evaluated as antibacterials against Staphylococcus aureus and Enterococcus strains. Results: Most effective compounds have been those with a bromo cyclopentane and a chloro indole substitution. First lead compounds were identified with promising activities similar to that observed in vitro for last resort antibiotics, so that the novel compounds enriche the pool of perspective small-molecule antibacterial drug candidates.

Neuronal nicotinic acetylcholine receptor (nAChR)-based therapeutics are sought as a potential alternative strategy to opioids for pain management. In this study, we examine the antinociceptive effects of 3-(2-chlorophenyl)-5-(5-methyl-1-(piperidin-4-yl)-1 H -pyrazol-4-yl)isoxazole (CMPI), a novel positive allosteric modulator (PAM), with preferential selectivity to the low agonist sensitivity (α4)3(β2)2 nAChR and desformylflustrabromine (dFBr), a PAM for α4-containing nAChRs. We used hot plate and tail flick tests to measure the effect of dFBr and CMPI on the latency to acute thermal nociceptive responses in rats. Intraperitoneal injection of dFBr, but not CMPI, dose-dependently increased latency in the hot plate test. In the tail flick test, the effect achieved at the highest dFBr or CMPI dose tested was only <20% of the maximum possible effects reported for nicotine and other nicotinic agonists. Moreover, the coadministration of dFBr did not enhance the antinociceptive effect of a low dose of nicotine. Our results show that the direct acute effect of dFBr is superior to that for CMPI, indicating that selectivity to (α4)3(β2)2 nAChR is not advantageous in alleviating responses to acute thermal nociceptive stimulus. However, further studies are necessary to test the suitability of (α4)3(β2)2 nAChR-selective PAMs in chronic pain models.

Brominated flame retardants (BFRs) have been using to reduce the flammability of plastics contained in many products, such as household articles, furniture, mattresses, textiles or insulation. Considering the fact that these compounds may be released into the environment leading to the exposure of living organisms, it is necessary to study their possible effects and mechanisms of action. Proteins play a crucial role in all biological processes. For this reason, a simple model of human serum albumin (HSA) was chosen to study the mechanism of BFRs' effect on proteins. The study determined interactions between selected BFRs, i.e., tetrabromobisphenol A (TBBPA), tetrabromobisphenol S (TBBPS), 2,4-dibromophenol (2,4-DBP), 2,4,6-tribromophenol (2,4,6-TBP) and pentabromophenol (PBP), and HSA by measurement of fluorescence of intrinsic tryptophan and absorbance of circular dichroism (CD). In addition, in order to understand the possible effect of these compounds in their native environment, the effect of BFRs on membrane proteins of human erythrocytes (red blood cells, RBCs) was also assessed. Among bromophenols, PBP had the strongest oxidative effect on RBC membrane, and 2,4-DBP demonstrated the weakest fluorescence-quenching effect of both membrane tryptophan and HSA. By contrast to PBP, 2,4-DBP and 2,4,6-TBP caused spatial changes of HSA. We have observed that among all analyzed BFRs, TBBPA caused the strongest oxidation of RBC membrane proteins and the model HSA protein, causing reduction of fluorescence of tryptophan contained in them. TBBPA also changed albumin conformation properties, leading to impairment of the α-helix structure. However, TBBPS had the weakest oxidative effect on proteins among studied BFRs and did not affect the secondary structure of HSA.

The persistent organic pollutant, brominated flame retardant, hexabromocyclododecane (HBCD), identified as an emerging contaminant has been detected in various environmental matrix. The increased level of this toxic organic compound in the environment has been associated with serious human health risks. The results obtained from this study revealed that various Rhodopseudomonas palustris strains isolated from paddy soil in Taiwan possessed good HBCD biodegradation capability when they were cultured aerobically. Among these strains, YSC3 was considered as one of the most potential isolates for HBCD degradation. The optimum HBCD biodegradation occurred at neutral pH and at 35 °C in all our pH and temperature tests at an initial HBCD concentration of 1 ppm. HBCD degradation kinetics generally decreased with the increase of initial HBCD concentration. The study also suggested that the cultivation temperature played a vital role on YSC3 for its initiation of cellular HBCD degradation. The relative-molar ratio of the released bromide ions during the biodegradation of HBCD was observed in the range between 1 and 3.5, suggesting that the debromination reactions occurred. Concomitant with the loss of HBCD, there was a concurrent production of two metabolites, pentabromocyclododecanol and pentabromocyclododecene, which were determined by liquid chromatography and mass spectrometry techniques. On the basis of the obtained results, the possible biodegradation pathways were also proposed in this study., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Hexabromocyclododecane (HBCD) has been listed in Annex A of the Stockholm Convention on Persistent Organic Pollutants (POPs) in 2013, but till now there is a lack of efficient methods for its degradation. In this study, nanoscale zero-valent aluminum (nZVAl), an excellent reductant with a very low redox potential of E 0 (Al 3+ /Al 0 ) = -1.662 V and strong electron transfer ability, was used to reductively degrade HBCD. Nearly 100% HBCD was degraded within 8 h reaction at 25 °C in ethanol/water (v/v, 50/50) solution without pH adjustment. And about 67% cyclododecatriene (CDT) was obtained, which is the complete debromination product. What's more, the yield of Br - could achieve nearly 100% after optimizing conditions. The reaction was strongly promoted by increasing the dosages of nZVAl or decreasing the initial concentration of HBCD. The temperature had the most significant influence and the degradation was completed in 40 min with elevating the reaction temperature to 45 °C. The reaction mechanism was further revealed through the characterization of nZVAl particles before and after the reaction by SEM-EDS, TEM, HRTEM, XRD, and XPS. It was found that, after corrosion of the oxide film on the surface of nZVAl, metallic aluminum inside was exposed. The reactive sites were provided and electrons released were transferred from nZVAl to HBCD, causing HBCD degraded to dibromocyclododecadiene (DBCD) and then CDT by reductive debromination. These findings imply that nZVAl can degrade HBCD efficiently with no extra energy input and this offers a new idea for better treatment of HBCD., Competing Interests: Declaration of competing interest There are no known conflicts of interest., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Methyl bromide (CH 3 Br) is one of the largest natural sources of bromine in the stratosphere, where it leads to ozone depletion. This paper reported the photochemical production of CH 3 Br from syringic acid (SA) that has been used as an environmentally relevant model compound for terrestrially-derived dissolved organic matter. The formation of CH 3 Br increased with the increase of bromide ion concentration ranging from 0.8 to 80 mmol L -1 . Ferric ions (Fe(III)) enhanced CH 3 Br production, while chloride inhibited it, with or without Fe(III). Meanwhile, methyl chloride (CH 3 Cl) was generated in the presence of chloride and was inhibited by Fe(III). The different effects of Fe(III) on the formation of CH 3 Cl and CH 3 Br indicate their diverse formation paths. Based on the intermediates identified by liquid chromatography-mass spectrometry and the confirmation of the formation of Fe(III)-SA complexes, it was proposed that there were two formation paths of CH 3 Br from SA in the bromide-enriched water under simulated sunlight irradiation. One path was via nucleophilic attack of Br - on the excited state protonation of SA; the other was via the combination of methyl radical and bromine radical when Fe(III) was present. This work suggests that the photochemical formation of CH 3 Br may act as a potential natural source of CH 3 Br in the bromide-enriched environmental matrix, and helps in better understanding the formation mechanism of CH 3 Br.

Proton exchange membrane fuel cells (PEMFCs) with 0.1 and 0.4 mg Pt cm -2 cathode catalyst loadings were separately contaminated with seven organic species: Acetonitrile, acetylene, bromomethane, iso-propanol, methyl methacrylate, naphthalene, and propene. The lower catalyst loading led to larger cell voltage losses at the steady state. Three closely related electrical equivalent circuits were used to fit impedance spectra obtained before, during, and after contamination, which revealed that the cell voltage loss was due to higher kinetic and mass transfer resistances. A significant correlation was not found between the steady-state cell voltage loss and the sum of the kinetic and mass transfer resistance changes. Major increases in research program costs and efforts would be required to find a predictive correlation, which suggests a focus on contamination prevention and recovery measures rather than contamination mechanisms.

Hexabromocyclododecane (HBCDD) has frequently been detected in wildlife. However, there is limited research on its bioaccumulation and biomagnification in insect-dominated aquatic and terrestrial food webs. This study investigated the occurrence of HBCDD in insects and their predators collected from a former e-waste contaminated pond and its surrounding region. The concentrations of ƩHBCDD (sum concentrations of α-, β-, and γ-HBCDDs) ranged from nd to 179 ng g -1 lipid weight. α-HBCDD was the predominant diastereoisomer in all biotic samples, and the contribution of α-HBCDD was higher in predators than in prey insects. A significantly positive linear relationship was found between ƩHBCDD concentrations (lipid weight) and trophic levels based on δ 15 N in aquatic organisms (p < 0.05), while trophic dilution was observed in the terrestrial food web. This result indicates an opposite trophic transfer tendency of HBCDD in terrestrial and aquatic ecosystems. The biomagnification factor (BMF) for α-HBCDD was higher in terrestrial birds (2.03) than in frogs (0.29), toads (0.85), and lizards (0.63). This may be due to differences between poikilotherms and homeotherms in terrestrial ecosystems., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The sorption of hexabromocyclododecanes (HBCDs) on sediment affects the fate and transport of HBCDs in rivers. The sorption of HBCDs on sediment from the Weihe River was investigated by performing batch equilibration experiments, and the effects of changing the pH ionic, strength, and humic acid concentration (HA) on sorption were evaluated. The obtained results indicated that fast rather than slow sorption was the dominant process. Nonlinear sorption isotherms were acquired, and the Freundlich (R 2 0.94-0.98) and Langmuir (R 2 0.95-0.99) models both described the sorption of HBCDs well. The adsorption capacity for α-HBCD, β-HBCD, and γ-HBCD were calculated using the Langmuir model, and were 443.56, 614.29 and 1146.37 mg/kg, respectively. Thermodynamic analysis shows that HBCDs sorption on sediment is a spontaneous exothermic process. HBCDs sorption was affected by the HA concentration and ionic strength. The amounts of HBCDs sorbed to the sediment decreased as the ionic strength increased, and first increased and then decreased as the HA concentration increased. Changes in pH did not clearly affect the sorption of HBCDs. Synchrotron radiation Fourier-transform infrared spectra (SR-FTIR) was used to characterize the adsorption mechanism, and the obtained result indicated that hydrophobic interactions dominated the mechanism involved in HBCDs sorption on sediment.

Bromophenols are a class of compounds occurring in red algae that are thought to play a role in chemical protection; however, their exact function is still not fully known. In order to investigate their occurrence, pure standards of seven bromophenols were isolated from a methanolic extract of the epiphytic red alga Vertebrata lanosa collected in Brittany, France. The structures of all compounds were determined by NMR and MS. Among the isolated substances, one new natural product, namely, 2-amino-5-(3-(2,3-dibromo-4,5-dihydroxybenzyl)ureido)pentanoic acid was identified. An HPLC method for the separation of all isolated substances was developed using a Phenomenex C8(2) Luna column and a mobile phase comprising 0.05% trifluoroacetic acid in water and acetonitrile. Method validation showed that the applied procedure is selective, linear (R 2 0.999), precise (intra-day ≤ 6.28%, inter-day ≤ 5.21%), and accurate (with maximum displacement values of 4.93% for the high spikes, 4.80% for the medium spikes, and 4.30% for the low spikes). For all standards limits of detection (LOD) were lower than 0.04 μg/mL and limits of quantification (LOQ) lower than 0.12 μg/mL. Subsequently, the method was applied to determine the bromophenol content in Vertebrata lanosa samples from varying sampling sites and collection years showing values between 0.678 and 0.005 mg/g dry weight for different bromophenols with significant variations between the sampling years. Bioactivity of seven isolated bromophenols was tested in agar diffusion tests against Staphylococcus aureus and Escherichia coli bacteria. Three compounds showed a small zone of inhibition against both test organisms at a concentration of 100 µg/mL., Competing Interests: The authors declare no conflict of interest.

In this study, the levels and distribution patterns of HBCD diastereoisomers in air, water, soil, and sediment samples in South Korea were investigated after optimizing the UPLC-MS/MS analytical process. Extraction and cleanup efficiencies were tested using several different extraction solvents and adsorbents. Dichloromethane was selected as the base extraction solvent, and multi-layer silica gel (MSG) and MSG-alumina columns were selected for the removal of HBCDs from complex environmental matrices. The concentration of Ʃ 3 HBCDs was 22-133 pg/m 3 , 10-128 ng/g, 0.2-151 ng/L, and 0.5-552 ng/g dw for air, soil, water, and sediment samples, respectively. Relatively higher concentrations of Ʃ 3 HBCDs were observed at stations adjacent to industrial facilities (e.g., rubber and plastic, textile, chemical, fabricated metal, and wholesale trade factories) associated with the use of commercial HBCDs. The proportion of γ-HBCD in the soil (48.3-86.2%) and sediment (54.2-78.1%, except for one station) samples was similar to that found in technical and commercial HBCDs. In contrast, α-HBCD (52.3-71.2%) was dominant in all air samples, while the water samples displayed no clear trend in their diastereoisomer profiles. As the first nationwide report on HBCD diastereoisomers in the environment, this study demonstrates that most environmental compartments in South Korea are moderately contaminated with HBCDs., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Naturally occurring three-dimensional (3D) biopolymer-based matrices that can be used in different biomedical applications are sustainable alternatives to various artificial 3D materials. For this purpose, chitin-based structures from marine sponges are very promising substitutes. Marine sponges from the order Verongiida (class Demospongiae) are typical examples of demosponges with well-developed chitinous skeletons. In particular, species belonging to the family Ianthellidae possess chitinous, flat, fan-like fibrous skeletons with a unique, microporous 3D architecture that makes them particularly interesting for applications. In this work, we focus our attention on the demosponge Ianthella flabelliformis (Linnaeus, 1759) for simultaneous extraction of both naturally occurring ("ready-to-use") chitin scaffolds, and biologically active bromotyrosines which are recognized as potential antibiotic, antitumor, and marine antifouling substances. We show that selected bromotyrosines are located within pigmental cells which, however, are localized within chitinous skeletal fibers of I. flabelliformis . A two-step reaction provides two products: treatment with methanol extracts the bromotyrosine compounds bastadin 25 and araplysillin-I N20 sulfamate, and a subsequent treatment with acetic acid and sodium hydroxide exposes the 3D chitinous scaffold. This scaffold is a mesh-like structure, which retains its capillary network, and its use as a potential drug delivery biomaterial was examined for the first time. The results demonstrate that sponge-derived chitin scaffolds, impregnated with decamethoxine, effectively inhibit growth of the human pathogen Staphylococcus aureus in an agar diffusion assay.

The formation of carcinogenic bromate ions is a constraint when ozone is used for the remediation of water containing brominated organic materials. With its strong oxidizing ability, ozone rapidly transforms bromide in aqueous media to bromate, through a series of reactions involving hydroxyl radicals. Several strategies, such as limiting the ozone concentration, maintaining pH < 6, or the use of ammonia or hydrogen peroxide were explored to minimize bromate generation. However, most of the above strategies had a negative effect on the ozonation efficiency. The advanced oxidation processes, using catalysts together with ozone, have proven to be a promising technology for the degradation of pollutants in wastewater, but very few studies have been conducted to find ways to minimize bromate formation during this approach. The proposed article, therefore, presents a comprehensive review on recent advances in bromate reduction in water by catalytic ozonation and proposes reaction mechanisms associated with the catalytic process. The main aim is to highlight any gaps in the reported studies, thus creating a platform for future research and a quest to find environment friendly and efficacious catalysts for minimizing bromate formation in aqueous media during ozonation of brominated organic compounds.

An operationally simple nickel-catalyzed hydroarylation reaction for alkynes is described. This three-component coupling reaction utilizes commercially available alkynes and aryl bromides, along with water and Zn. An air-stable and easily synthesized Ni(II) precatalyst is the only entity used in the reaction that is not commercially available. This reductive cross-coupling reaction displays a fairly unusual anti selectivity when aryl bromides with ortho substituents are used. In addition to optimization data and a preliminary substrate scope, complementary experiments including deuterium labeling studies are used to provide a tentative catalytic mechanism. We believe this report should inspire and inform other Ni-catalyzed carbofunctionalization reactions.

Chloroperoxidase (CPO) is a hybrid of two different families of enzymes, peroxidases and P450s. However, it is poorly understood on CPO's multiple catalytic functions. Herein, phenol was selected as a model substrate to investigate the multiple catalytic roles of CPO. Results showed that phenol was readily transformed into a variety of brominated organic compounds (BOCs) via the CPO-mediated oxidative process. A total of 16 BOCs were identified using gas and liquid chromatography coupled with mass spectrometry. Possible reaction pathways could be attributable to four CPO-mediated processes, including bromination, radical coupling, intramolecular cyclization and debromination. Higher bromide concentrations and lower pH conditions both facilitated the formation of brominated products. While a higher bromination capacity was observed in pH 3.0 solutions, CPO-mediated radical couplings were more favorable at pH 5.0 and 6.0. Although CPO might catalyze chlorination when chloride and bromide coexisted in the solution, BOCs were the dominant products of CPO-mediated phenol oxidation. Results of this study suggest that various catalytic roles of CPO may contribute to the biotic formation of BOCs in the natural environment., (Copyright © 2019 Elsevier Inc. All rights reserved.)

In this study the direct and indirect photolysis of the novel brominated flame retardant 2,4,6-Tris-(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) in an organic solvent mixture (60:30:10, ACN:MeOH:THF) under UV-(C) and simulated sunlight irradiation was investigated, and the formed photo-transformation products were identified for the first time. TTBP-TAZ was almost completely degraded within 10 min under UV-(C) irradiation. Due to the fast degradation no specific kinetic order could be observed. In comparison, the reaction under simulated sunlight irradiation was much slower and thus, the kinetic first-order could be determined. The observed photolysis rate constant k as well as the half-life time t 1/2 were estimated to be k = (0.0163 ± 0.0002) h -1 and t 1/2  = 42.3 h, respectively. The addition of 2-propanol and hydrogen peroxide to investigate the influence of indirect photolysis under UV-(C) irradiation causes no influence on the degradation of TTBP-TAZ. Nevertheless, the removal of TTBP-TAZ under UV-(C) and simulated sunlight without additional chemicals (except solvent) indicates that the direct photolysis plays a significant role in the degradation mechanism of TTBP-TAZ. In both irradiation experiments, TTBP-TAZ was quantitatively degraded that involve the formation of previously unknown PTPs. Overall, two main PTPs were determined when irradiated with UV-(C) and eight sequential debromination products were observed when irradiated by simulated sunlight. These were determined by HPLC-DAD and - MS/(MS), respectively. Based on the chosen experimental conditions the consecutive debromination as well as photo-Fries rearrangement was confirmed as the main degradation pathway by high resolution mass spectrometry and X-ray diffraction., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The individual degradation rates of the three dominant stereoisomers (α, β, γ) of hexabromocyclododecane (HBCDD) with bisulfide and polysulfides were investigated at pH 9 in methanol/water solutions at two different temperatures (25 °C and 40 °C). Under all conditions investigated, α-HBCDD reacts 10 to 20 times slower with bisulfide than β-HBCDD and γ-HBCDD. The difference in reactivity of HBCDD isomers can be explained by the different populations of stable conformers with large dihedral angle between the vicinal bromine atoms. It was also observed that the reaction of HBCDD with polysulfides is about six times faster than with bisulfide. The experiments performed in solvent mixtures with increased water content at 40 °C indicated that the reaction of HBCDD with bisulfide is faster with higher percentage of water. The much slower abiotic reaction of α-HBCDD compared to β-HBCDD and γ-HBCDD could potentially contribute to the fact that α-HBCDD is more persistent in the environment than γ-HBCDD. Only one isomer of tetrabromocyclododecene (TBCDe-5) was identified as a degradation product of the reaction of HBCDD with reduced sulfur species. TBCDe-5 itself reacts about ten times slower with bisulfide and twenty times slower with polysulfide than HBCDD. The study demonstrates that polysulfides and bisulfides can reduce HBCDD sufficiently in natural anoxic environments and the dominant pathway for the degradation of HBCDD by reduced sulfur species is very likely to be the reductive debromination of vicinal dibromides via concerted anti-elimination., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this study, the acute and subchronic toxicity of 1-alkyl-3-methyl imidazole bromide ionic liquids (ILs) [C n mim]Br (n = 2, 4, 6, 10, 12) was evaluated utilizing earthworms (Eisenia fetida) as a basis for their impact on terrestrial ecosystems. The filter paper tests and artificial soil tests were conducted as acute toxicity tests to investigate the LC 50 of ILs, while in subchronic toxicity tests, earthworms were exposed to ILs in artificial soil (5, 10, 20 and 40 mg kg -1 ) for 28 d. Reactive oxygen species (ROS), antioxidant enzymes, detoxifying enzymes and oxidative damage were measured to determine subchronic effects of ILs on E. fetida. The results showed that when the earthworms were exposed to these five ILs in acute toxicity experiments, [C 2 mim]Br had the lowest toxicity, as the alkyl length increased, the toxicity increased up to [C 10 mim]Br: a "cut-off effect" (decreased toxicity) was observed at [C 12 mim]Br. The results highlight the varying toxicity of ILs with different alkyl chains to E. fetida and provide valuable data for detailing the impact of ILs on ecological receptors., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Short-chain chlorinated paraffins (SCCPs) are polyhalogenated hydrocarbons as are hexachlorocyclohexanes (HCHs) and hexabromocyclododecanes (HBCDs). They all have been classified as persistent organic pollutants (POPs) under the UN Stockholm Convention. Per se such compounds are transformed slowly in the environment, transported over long distances and accumulate in biota. Several Sphingomonadacea strains isolated from HCH dump sites have evolved to express enzymes that can transform HCHs and HBCDs. We hypothesized that LinA2, a dehydrohalogenase expressed in such bacteria, may also transform CPs to chlorinated olefins (COs). Three mixtures of penta- to deca-chlorinated undecanes (C 11 ), dodecanes (C 12 ) and tridecanes (C 13 ) were exposed to LinA2. High-resolution full-scan mass spectra (R∼8'000) of CPs and COs were obtained applying a soft ionization method, enhancing chloride-adduct [M+Cl] - formation. A mathematical deconvolution procedure was used to separate interfering spectra to verify that LinA2 indeed catalyzed the conversion of CPs to COs. About 20-40% of the material was transformed in 24 h, about 50-70% was converted in 200 h. A bimodal first-order kinetic model could describe transformations of reactive and persistent CPs. Under the given conditions reactive CPs (τ 1/2  = 1.4-6.9 h) were converted 30 to 190-times faster than the persistent ones (τ 1/2  = 150-260 h). Proportions of persistent isomers (p p ) varied from 60 to 80%. Lower chlorinated homologues contained higher proportions of persistent isomers. In conclusion, SCCP mixtures contain both, material that is readily converted by LinA2, and persistent material that is not or only slowly transformed., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Brominated flame retardants are often associated with adverse environmental effects. Nevertheless, these chemicals are required in order to comply with fire safety standards. Therefore, a better environmental profile is desirable. A "new" class of flame retardants is claimed to fulfil this request while still being feasible for established industrial processes. Different to previous brominated flame retardants, this new group is based on a polymeric structure that could indeed lead to a better environmental profile. However, not much is known about the long-term behaviour of such flame retardants. This short review summarizes what has already been published. With an annual production volume of 26,000 metric tons, "Polymeric FR" is currently the only industrially produced representative of this group. It has been shown to degrade under specific circumstances (following UV and heat exposure). Detected degradation products cause almost no acute toxicity, whereas chronic toxicity might be relevant. Nevertheless, as long as polymeric flame retardants are only used in building insulation, the actual risk seems to be rather limited., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The intermolecular interaction in difluoromethane, dichloromethane, dibromomethane, and diiodomethane dimers has been investigated using high level quantum chemical methods. The potential energy curve of intermolecular interaction along the C⋯C bond distance obtained using the coupled-cluster theory with singles, doubles, and perturbative triples excitations CCSD(T) were compared with values given by the same method, but applying the local (LCCSD(T)) and the explicitly correlated (CCSD(T)-F12) approximations. The accuracy of other theoretical methods-Hartree-Fock (HF), second order Møller-Plesset perturbation (MP2), and dispersion corrected DFT theory-were also presented. In the case of MP2 level, the canonical and the local-correlation cases combined with the density-fitting technique (DF-LMP2)theories were considered, while for the dispersion-corrected DFT, the empirically-corrected BLYP-D and the M06-2Xexchange-correlation functionals were applied. In all cases, the aug-cc-pVTZ basis set was used, and the results were corrected for the basis set superposition error (BSSE) using the counterpoise method. For each molecular system, several dimer geometries were found, and their mutual orientations were compared with the nearest neighbor orientations obtained in recent neutron scattering studies. The nature of the intermolecular interaction energy was discussed.

Neuronal nicotinic acetylcholine receptors are cell membrane-bound ion channels that are widely distributed in the central nervous system. The α4β2 subtype of neuronal nicotinic acetylcholine receptor plays an important role in modulating the signaling pathways for pain. Previous studies have shown that agonists, partial agonists, and positive allosteric modulators for the α4β2 receptors are effective in relieving pain. Desformylflustrabromine is a compound that acts as an allosteric modulator of α4β2 receptors. The aim of this study was to assess the effects of desformylflustrabromine on chemically induced pain. For this purpose, the formalin-induced pain test and the acetic acid-induced writhing response test were carried out in CD-1 mice. Both tests represent chemical assays for nociception. The results show that desformylflustrabromine is effective in producing an analgesic effect in both tests used for assessing nociception. These results suggest that desformylflustrabromine has the potential to become a clinically used drug for pain relief.

The dissociative ionization and Coulomb explosion of molecular bromocyclopropane (BCP) has been experimentally investigated by time-of-flight mass spectrum and dc-slice imaging technology. The sliced 2D images, kinetic energy releases and angular distributions of the fragment ions are obtained under the intense femtosecond laser fields (8.0 × 10 13 ⁻2.0 × 10 14 W/cm²). The results indicated that the low kinetic energy release (KER) components come from dissociative ionization of BCP⁺, while the high KER components come from Coulomb explosion of BCP 2+ . The chemical reaction path of BCP⁺ has been calculated by ab initio calculation, furthermore, the C-Br bond cleavage involved Coulomb explosion channels have been revealed, and the corresponding dehydrogenation mechanism has been confirmed.

Recent and reliable human biomonitoring data on brominated flame retardants (BFRs), either legacy or new BFRs, are still needed to assess human exposure. The aim of this work was therefore to develop and validate an accurate, fast and user-friendly analytical strategy for the determination of 15 legacy and novel BFRs in human serum namely 8 polybrominated diphenylethers (BDE-28, -47, -99, -100, -153, -154, -183, and -209), 1 hexabromobiphenyl (PBB-153), and 6 novel BFRs (pentabromotoluene, hexabromobenzene, pentabromoethylbenzene, 2-ethylhexy-2,3,4,5-tetrabromobenzoate, 1,2-bis(2,4,6-tribromophenoxy)ethane, and decabromodiphenylethane). This analytical procedure consisted in a simple liquid-liquid extraction followed by elution on a PHREE cartridge avoiding further laborious purification steps. The final determination was performed by gas chromatography coupled to mass spectrometry in electron capture negative ionization mode (GC-ECNI-MS). The 15 m long RTX-1614 allowed the simultaneous measurement of the 15 BFRs including low and high brominated species within a single injection on a single column. Except for 2-ethylhexy-2,3,4,5-tetrabromobenzoate (EHTBB) which showed very high response variations resulting in poor linearity, trueness and precision, and decabromodiphenylethane for which very low sensitivity was achieved, the 13 other BFRs passed the validation process with recoveries varying between 56 and 82%, and limits of quantification (LOQs) ranging from 2.5 to 6.0 pg/ml (34.5 pg/ml for BDE-209). Within the validated range of concentrations, the relative bias from the introduced levels were below 20% while the intra and inter precisions were maintained below 15%. The reliability of the technique was confirmed by successfully analyzing interlaboratory test materials (AMAP ring test for POPs in human serum)., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Brominated flame retardants (BFRs) are widely used as additives in plastics, textiles and electronics materials. Here, we investigated the photodegradation of four BFRs including decabromobiphenylether (BDE-209), tetrabromobipsphenol A (TBBPA), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE) and tetrabromobisphenol A bis (allyl) ether (TBBPA-BAE). Experiments were carried out in polystyrene (PS) films using monochromatic and polychromatic irradiations. For comparison, irradiations were also carried in a solvent (tetrahydrofuran: THF). Monitoring of BFR degradation was performed using bulk and surface infrared (IR) measurements, as well as by extraction and HPLC-UV. Photoproducts were characterized using HPLC-high resolution electrospray ionization mass spectrometry (HPLC-ESI-Orbitrap-MS). All four BFRs underwent photochemical transformation in THF at 290 nm with a quantum yield (Φ) ranging from 0.05 for TBBPA to 0.27 for BDE-209, indicating an increase of photoreactivity with the number of Br atoms in BFRs. On the other hand, no major difference in the Φ values was observed when BFRs were embedded in PS films (Φ: 0.82-0.89). The higher photoreactivity in PS appears to be associated with a fast oxidation of PS as revealed by infrared (IR) analysis and yellowing of the films. Interestingly, the faster the yellowing occurred, the faster the BFR degradation was inhibited due to light screening effect. Several major photoproducts were identified for TBBPA and TBBPA-DBPE. Additional photoproducts possibly arising from PS oxidation and bromination by Br ● were observed for the first time. This work provides a better understanding of the reactivity and fate of BFRs in polymers allowing for a better assessment of their environmental impacts., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Human biomonitoring is a reliable method for evaluating human exposure to specific contaminants. Although blood is an ideal matrix for monitoring purposes, it is regarded as an invasive matrix. Therefore, current developments in the field of human biomonitoring are based on introducing new methods that use non-invasive matrices, such as hair. In this study, we examined the efficiencies of several extraction methods for the analysis of hexabromocyclododecane (HBCD) and tetrabromobisphenol-A (TBBPA) in human hair. The selected pretreatment method was validated through a general QA/QC process that included spiking experiments, and then, the method was used for the determination of HBCD and TBBPA concentrations in scalp hair samples collected from individuals in Korea (n = 24) and Iran (n = 15). The HBCD and TBBPA concentrations in the collected hair samples ranged from ND to 3.24 ng g -1 and ND to 16.04 ng g -1 , respectively. Significantly higher concentrations of TBBPA were found in hair samples from Korea than those in hair samples from Iran (p < 0.05), which is expected to be the result of the large market and higher exposure of TBBPA in Korea. HBCD was not detected in hair samples from Iran. According to our knowledge this is the first study demonstrating the presence of TBBPA in human hair with nonspecific exposure. Lastly, we investigated the important factors that influence the interpretation of the contributions of endogenous and exogenous contaminations in hair. Based on the information, the HBCD and TBBPA in the collected hair samples were most likely from endogenous exposure. Therefore, our study showed that hair is potentially a suitable indicator for the monitoring of internal exposure to HBCD and TBBPA in different populations., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

LinB is a haloalkane dehalogenase found in Sphingobium indicum B90A, an aerobic bacterium isolated from contaminated soils of hexachlorocyclohexane (HCH) dumpsites. We showed that this enzyme also converts hexabromocyclododecanes (HBCDs). Here we give new insights in the kinetics and stereochemistry of the enzymatic transformation of δ-HBCD, which resulted in the formation of two pentabromocyclododecanols (PBCDols) as first- (P 1δ , P 2δ ) and two tetrabromocyclododecadiols (TBCDdiols) as second-generation products (T 1δ , T 2δ ). Enzymatic transformations of δ-HBCD, α 1 -PBCDol, one of the transformation products, and α 2 -PBCDol, its enantiomer, were studied and modeled with Michaelis-Menten (MM) kinetics. Respective MM-parameters K M , v max , k cat /K M indicated that δ-HBCD is the best LinB substrate followed by α 2 - and α 1 -PBCDol. The stereochemistry of these transformations was modeled in silico, investigating respective enzyme-substrate (ES) and enzyme-product (EP) complexes. One of the four predicted ES-complexes led to the PBCDol product P 1δ , identical to α 2 -PBCDol with the 1R,2R,5S,6R,9R,10S-configuration. An S N 2-like substitution of bromine at C6 of δ-HBCD by Asp-108 of LinB and subsequent hydrolysis of the alkyl-enzyme led to α 2 -PBCDol. Modeling results further indicate that backside attacks at C1, C9 and C10 are reasonable too, selectively binding leaving bromide ions in a halide pocket found in LinB. Docking with α 2 -PBCDol, also allowed productive enzyme binding. A TBCD-1,5-diol with the 1S,2S,5R,6R,9S,10R-configuration is the predicted second-generation product T 1δ . In conclusion, in vitro- and in silico findings now allow a detailed description of step-wise enzymatic dehalohydroxylation reactions of δ-HBCD to specific PBCDols and TBCDdiols at Å-resolution and predictions of their stereochemistry., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Hexabromocyclododecane (HBCD), a commonly used brominated flame retardant (BFR), has been listed as a persistent organic pollutant (POP). In order to remediate HBCD in the environment, the influence of microscale zerovalent iron (MZVI) on the HBCD degrading microcosm was evaluated. In the acclimated microcosm collected from river sediment, 49% of HBCD was initially removed through adsorption and then 30% of HBCD was biodegraded through non-debromination processes. In contrast to MZVI only, over 60% of HBCD was gradually degraded by MZVI through a debromination reaction. In the microcosm-MZVI combined system, the biodegradation ability of the microcosm was inhibited. The aqueous chemistry was changed by the addition of MZVI, which led to the alteration of microbial composition and biodegradation ability. These better understandings can facilitate an evaluation of the impact of MZVI on HBCD biodegradation when ZVI was used to remediate this BFR., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The concentrations of α-, β-, and γ-hexabromocyclododecane (HBCDD) diastereomers in atmospheric particle phase samples were determined at four United States Integrated Atmospheric Deposition Network (IADN) sites located in the North American Great Lakes basin collected between 1 January and 31 December 2014. The concentrations ranged from 0.37 to 8.9 pg/m 3 , 0.12-4.0 pg/m 3 , and 0.26-22 pg/m 3 for α-, β-, and γ-HBCDD, respectively among the four sampling sites. The median ΣHBCDD concentrations for the four sites were 2.0 pg/m 3 , 2.1 pg/m 3 , 1.7 pg/m 3 and 5.2 pg/m 3 for Chicago, Cleveland, Sturgeon Point and Sleeping Bear Dunes, respectively. Higher levels of ∑HBCDD were observed at the remote site of Sleeping Bear Dunes with comparable levels at the remaining three sites. α-HBCDD and γ-HBCDD were the dominant isomers with an average contribution of about 40% and 50% to ΣHBCDD concentrations, respectively. These HBCDD concentrations were compared with the levels of other brominated flame retardants measured in these samples, including polybrominated diphenyl ethers (PBDEs), 2,3,4,5-tetrabromoethylhexyl benzoate (EHTBB), bis(2-ethylhexyl) tetrabromophthalate (BEHTBP), and decabromodiphenylethane (DBDPE). ∑HBCDD concentrations were significantly lower than or indistinguishable from those of PBDEs, EHTBB, BEHTBP, and DBDPE at all sites except Sleeping Bear Dunes. No significant correlations were found between ΣHBCDD and ΣPBDE, EHTBB, BEHTBP, and DBDPE concentrations, suggesting a different source of HBCDD contamination. This is the first study reporting concentrations of HBCDD isomers in the Great Lakes ambient air, and our results indicate that HBCDD is ubiquitous in the Great Lakes basin, including at remote sites., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The search for reactions where KO t Bu and other tert -alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX₄, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr₄ under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr₄. We now report evidence from experimental and computational studies that KO t Bu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr₄ or CCl₄, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane.

While there are no regulatory fire safety obligations for polystyrene (PS) when used as packaging material, concerns exist that such packaging material may contain the flame retardant hexabromocyclododecane (HBCDD) as a result of uncontrolled recycling activities. To evaluate these concerns, we collected 50 samples of PS packaging materials from the UK and 20 from Ireland. HBCDD was detected in 63 (90%) of samples, with concentrations in 4 samples from Ireland exceeding the EU's low POP concentration limit (LPCL) of 0.1% above which articles may not be recycled. Moreover, 2 further samples contained HBCDD >0.01%. While our samples were obtained in the 12 month period prior to the March 2016 introduction of the EU's 0.01% concentration limit above which articles may not be placed on the market, our data suggest that continued monitoring is required to assess compliance with this limit value. Ratios of α vs. γ-HBCDD in our EPS packaging samples (average = 0.63) exceeded significantly (p = 0.025) those in EPS building insulation material samples (average = 0.24) reported previously for Ireland. This shift towards α-HBCDD in packaging EPS is consistent with the additional thermal processing experienced by recycled PS and suggests the source of HBCDD in PS packaging is recycled PS insulation foam. This is of concern owing to the higher bioavailability and lower metabolic clearance of α-HBCDD compared to the β- and γ-isomers., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A practical Pd-catalyzed carbonylation of (hetero)aryl bromides using a crystalline carbon monoxide (CO) surrogate, 2,4,6-trichlorophenyl formate (TCPF), was developed. This reaction proceeds without the slow addition technique that was previously required and with a low catalyst loading (1 mol%). The utility of this Pd-catalyzed external-CO-free carbonylation using TCPF was demonstrated in the synthesis of a histone deacetylase inhibitor.

This study was conducted with the aim of achieving the simultaneous screening of various additives in polymer materials by utilizing a solvent-free pyrolyzer/thermal desorption gas chromatography mass spectrometry (Py/TD-GC-MS) method. As a first step to achieve this goal, simultaneous screening has been examined by selecting major substances representing plasticizers and flame retardants, such as short chain chlorinated paraffins (SCCPs), decabromodiphenyl ether (DecaBDE), hexabromocyclododecane (HBCDD), and di(2-ethylhexyl) phthalate (DEHP). A quantitative MS analysis was performed to check for the peak areas and sensitivities. Since Py/TD-GC-MS is fraught with the risk of thermal degradation of the sample, temperatures during the analytical process were finely tuned for securing reliable results. The instrumental sensitivity was confirmed by the S/N ratio on each component. The detection limits of all components were less than 50 mg/kg, which are sufficiently lower than the regulatory criteria. With regard to reproducibility, a relative standard deviation (RSD) of about 5% was confirmed by employing a spike recovery test on a polystyrene polymer solution containing mixed standard solution (ca. 1000 mg/kg). In conclusion, the results obtained in this study indicate that Py/TD-GC-MS is applicable for the screening of major flame retardants and plasticizers in real samples with sufficient reproducibility at regulatory levels., Competing Interests: All the authors have read the manuscript, approved this submission and declared that there are no conflicts of interest.

Hypothesis: In contrast to anionic and nonionic amphiphilic substances, bio-based cationic ones are very rare. Cationic amphiphiles are mostly based on quaternary ammonium, pyridinium or imidazolium groups that are either badly biodegradable or have toxic residues even after degradation. In the search for green alternatives to cationic hydrotropes and amphiphiles, natural l-carnitine could be a promising candidate for a cationic headgroup., Experiments: By esterification of carnitine in one step and with low cost, cationic molecules with alkyl chain length of n=2-14 could be obtained. Their thermal properties, aggregation behaviour and cytotoxicity were determined. Hydrophobic compounds were solubilized in their aqueous solutions and the PIT-slope method was applied to determine a relative hydrophilicity., Findings: It was found that some pure carnitine ester bromides were liquid at room temperature and thus can be classified as ionic liquids. They are highly water-soluble, and in aqueous solutions, they showed hydrotrope or surfactant behaviour depending on their alkyl chain length. Their high hydrotropic efficiency was demonstrated by solubilizing Disperse Red 13, while also biomolecules, like vanillin, could be dissolved in reasonable amounts. In all tests, they performed at least as good as the tested reference substances, while showing similar cytotoxicity towards human skin keratinocytes, thus demonstrating their potential as green functional amphiphilic molecules of positive charge., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) have been used in a broad array of polymeric materials such as plastics, foams, resins and adhesives to inhibit the spread of fires since the 1970s. The widespread environmental contamination and well documented toxic effects of PBDEs have led to bans and voluntary withdrawals in many jurisdictions. Replacement novel brominated flame retardants (NBFRs) have, however, exhibited many of the same toxic characteristics as PBDEs and appear to share similar environmental fate. This paper presents a critical review of the scientific literature regarding PBDE and NBFR contamination of surface soils internationally, with the secondary objective of identifying probable pollution sources. An evaluation of NBFR distribution in soil was also conducted to assess the suitability of the newer compounds as replacements for PBDEs, with respect to their land contamination potential. Principle production of PBDEs and NBFRs and their consequent use in secondary polymer manufacture appear to be processes with strong potential to contaminate surrounding soils. Evidence suggests that PBDEs and NBFRs are also released from flame retarded products during disposal via landfill, dumping, incineration and recycling. While the land application of sewage sludge represents another major pathway of soil contamination it is not considered in this review as it is extensively covered elsewhere. Both PBDEs and NBFRs were commonly detected at background locations including Antarctica and northern polar regions. PBDE congener profiles in soil were broadly representative of the major constituents in Penta-, Octa- and Deca-BDE commercial mixtures and related to predicted market place demand. BDE-209 dominated soil profiles, followed by BDE-99 and BDE-47. Although further research is required to gain baseline data on NBFRs in soil, the current state of scientific literature suggests that NBFRs pose a similar risk to land contamination as PBDEs., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This study explored the fate and adverse effects of 3 main hexabromocyclododecane diastereoisomers (α-, β-, and γ-HBCDDs) in a soil pot system planted with ryegrass (Lolium perenne L.) using a short-term (8 weeks) experiment. At the end of the experiment, soil urease activity in planted spiked soil increased and catalase activity decreased; while there was no obvious change in sucrase and peroxidase activities. HBCDDs mainly accumulated in the root of ryegrass, with root concentration factors (RCF) in the range of 1.46-4.43 and only a small part was transferred to the stem (SCF: 0.198-0.305) and leaf (LCF: 0.042-0.062). The concentration factors varied for different HBCDD diastereoisomers, being in the order of α- > β- > γ-HBCDD for all tissues, indicating preferential accumulation of α-HBCDD in ryegrass tissues. Moreover, the enantiomeric analysis revealed an enrichment of (+)-α-, (-)-β- and (+)-γ-HBCDD enantiomers in ryegrass tissues. β- and γ-HBCDDs (up to 1.90% and 4.11%, respectively) were transformed to aα-HBCDD in ryegrass, while no isomerization product from α-HBCDD was found. Hydroxylated HBCDDs metabolites, such as monoOHHBCDDs and diOHHBCDDs were found in ryegrass tissues for the first time., (Copyright © 2017. Published by Elsevier Ltd.)

Expanded polystyrene (EPS) is a major component of marine debris globally. Recently, hazardous hexabromocyclododecanes (HBCDDs) were detected in EPS buoys used for aquaculture farming. Subsequently, enrichment of HBCDDs was found in nearby marine sediments and mussels growing on EPS buoys. It was suspected that EPS buoys and their debris might be sources of HBCDDs. To confirm this, the release of HBCDDs from EPS spherules detached from a buoy to seawater was investigated under field (open sea surface and closed outdoor chambers with sun exposure and in the dark) and laboratory (particle-size) conditions. In all exposure groups, initial rapid leaching of HBCDDs was followed by slow desorption over time. Abundant release of HBCDDs was observed from EPS spherules exposed to the open sea surface (natural) and on exposure to sunlight irradiation or in the dark in controlled saline water. Water leaching and UV-light/temperature along with possibly biodegradation were responsible for about 37% and 12% of HBCDDs flux, respectively. Crumbled EPS particles (≤1 mm) in samples deployed on the sea surface for 6 months showed a high degree of weathering. This implies that surface erosion and further fragmentation of EPS via environmental weathering could enhance the leaching of HBCDDs from the surface of EPS. Overall, in the marine environment, HBCDDs could be released to a great extent from EPS products and their debris due to the cumulative effects of the movement of large volumes of water (dilution), biodegradation, UV-light/temperature, wave action (shaking), salinity and further fragmentation of EPS spherules., (Copyright © 2017 Elsevier Ltd. All rights reserved.)