The three-dimensional structure of 3,3',4,4'-tetrachlorobiphenyl, a dioxin-like polychlorinated biphenyl (PCB)

The crystal structure of PCB 77 (3,3',4,4'-tetrachlorobiphenyl, C(12)H(6)Cl(4)), a dioxin-like PCB congener, is described. The dihedral angle of PCB 77 is 43.94(6) degrees, which is slightly larger than calculated or experimental dihedral angles of biphenyl derivatives in solution but smaller than experimental dihedral angles in the gas phase.     

Building resilience to climate change – the role of cooperation in alpine tourism networks

While there is ample – though partially contradictory – evidence regarding the effects climate change will have on various regions of the world, there is only very limited work dedicated to the analysis of different governance structures, and how these structures are likely to influence the resilience of alpine tourism systems in the face of climate change. We present an analytical framework based on network theory, and apply this to the Swiss case study destination of Engelberg, in order to deduct a number of insights for the future assessment of resilience based on the cooperation of local actors. The main aim of the paper is to come up with comparable resilience metrics based on social network analysis in order to assess the structural strengths and weaknesses of a geographically delimited tourism system in the face of climate change. Together with the action potential of the individual actors these structural properties influence the adaptive capacity of both individual actors, and the tourism system as a whole. In line with comparable studies, we identify structural strengths and weaknesses around the core-periphery distribution (centrality), subgroups (modularity) and information flows (path length). We find that the Engelberg network follows an almost ideal-typical scale-free structure and the overall cooperation rate (density) is comparable to other tourism networks. The main weaknesses of the network with regard to climate change resilience are the lacking integration of public sector actors and the relatively high number of actors in the periphery of the network.     

Octachlorinated dioxin in pulps and effluents: Where does it come from?

Studies on the formation/destruction of dioxins associated with the pulping of wood artificially impregnated with an industrial grade of pentachlorophenol lend support to an earlier observation that ambient dioxins deposition may not necessarily be a unique source of the higher chlorinated dioxins occasionally found in pulps and final effluent discharges. These dioxins, which seemingly occur in products from a wide range of pulping technologies including recycle operations, may also originate from pentachlorophenol-based fungicides.     

Breaking the dogma: PCB-derived semiquinone free radicals do not form covalent adducts with DNA,GSH, and amino acids

Covalent bond formations of free radical metabolites with biomolecules like DNA and proteins are thought to constitute a major mechanism of toxicity and carcinogenesis. Glutathione (GSH) is generally accepted as a radical scavenger protecting the cell. In the present study, we investigated a semiquinone radical (SQ^●-) metabolite of the semivolatile 4-chlorobiphenyl, using electron paramagnetic resonance spectroscopy, and oxygen consumption. Proton nuclear magnetic resonance (¹H NMR) and liquid chromatography–mass spectrometry (LC-MS) were also employed to elucidate the radical interaction with DNA, amino acids, and GSH. We found that DNA and oligonucleotides stabilized SQ^●- by electron delocalization in the π-stacking system, resulting in persistent radical intercalated, rather than forming a covalent bond with SQ^●-. This finding was strongly supported by the semiempirical calculation of the semioccupied molecular orbital and the linear combination of the atomic orbitals, indicating 9.8 kcal mol^?1 energy gain. The insertion of SQ^●- into the DNA strand may result in DNA strand breaks and interruption of DNA replication process or even activate radical mediated secondary reactions. The presence of amino acids resulted in a decrease of the electron paramagnetic resonance (EPR) signal of SQ^●- and correlated with their isoelectric points. The pH shifts the equilibrium of the dianions of hydroquinone and influenced indirectly the formation of SQ^●-. Similar findings were observed with GSH and Cys. GSH and Cys functioned as indirect radical scavengers; their activities depend on their chemical equilibria with the corresponding quinones, and their further reaction via Michael addition. The generally accepted role of GSH as radical scavenger in biological systems should be reconsidered based upon these findings, questioning the generally accepted view of radical interaction of semiquinones with biologically active compounds, like DNA, amino acids, proteins, and radical scavengers like GSH.     

Synthesis of fluorinated polybrominated diphenyl ethers (F-PBDEs) as internal standards for environmental analysis

Polybrominated diphenyl ethers (PBDEs) have become widely distributed as environmental contaminants due to their wide-spread use as flame retardants. Their structural similarity to other halogenated organic pollutants, for example polychlorinated biphenyls (PCBs), has led to speculation that they may have similar toxicological properties and effects. Recent focus on PBDEs as possible priority pollutants has also led to an increasing need for reference standards of PBDEs for toxicological studies and for environmental analysis. In this work we synthesized a series of fluorinated PBDEs (F-PBDEs) which can be used as possible internal standards, as an alternative to high-cost alternatives, such as the (13)C-labelled analogues. F-PBDEs have been synthesized by using different coupling reactions and by bromination of fluorinated starting materials.     

Monofluorinated analogues of polychlorinated biphenyls (F-PCBs): synthesis using the Suzuki-coupling, characterization, specific properties and intended use

An improved method, a palladium-catalyzed cross-coupling reaction the so-called Suzuki-coupling, was used to synthesize 19 monofluorinated analogues (F-PCBs) of polychlorinated biphenyls (PCBs), including analogues of PCBs 28, 52 and 81. The coupling of chlorinated and/or fluorinated isomers of aryl boronic acids with bromo- and/or iodobenzenes gave the desired F-PCB congeners in good to excellent yields. The self-coupling product of the aryl boronic acids was the major impurity, but this limitation could be minimized. The influence of ortho-substitution by chlorine on the reaction time was studied in detail. The F-PCBs were characterized by means of ¹H and ¹⁹F NMR and mass spectrometry (MS). F-PCBs show remarkably similar characteristics in many aspects to those of the corresponding non-fluorinated parent PCBs. Since fluorine is generally resistant to degradation, once incorporated into a substrate it functions as an indelible label that can be used to monitor structures and dynamics. F-PCBs may prove their usefulness as markers and tracers in mechanistic and toxicological studies. The aim of further research will be to test the suitability of fluorine as a sensitive probe in a broad range of applications, including synthesis, analytical, mechanistic and toxicological studies.