Identification of a novel hydroxylated metabolite of 2,2′,3,5′,6-pentachlorobiphenyl formed in whole poplar plants

Polychlorinated biphenyls (PCBs) are a group of persistent organic pollutants consisting of 209 congeners. Oxidation of several PCB congeners to hydroxylated PCBs (OH-PCBs) in whole poplar plants has been reported before. Moreover, 2,2′,3,5′,6-pentachlorobiphenyl (PCB95), as a chiral congener, has been previously shown to be atropselectively taken up and transformed in whole poplar plants. The objective of this study was to determine if PCB95 is atropselectively metabolized to OH-PCBs in whole poplar plants. Two hydroxylated PCB95s were detected by high-performance liquid chromatography-mass spectrometry in the roots of whole poplar plants exposed to racemic PCB95 for 30 days. The major metabolite was confirmed to be 4′-hydroxy-2,2′,3,5′,6-pentachlorobiphenyl (4′-OH-PCB95) by gas chromatography-mass spectrometry (GC-MS) using an authentic reference standard. Enantioselective analysis showed that 4′-OH-PCB95 was formed atropselectively, with the atropisomer eluting second on the Nucleodex β-PM column (E2-4′-OH-PCB95) being slightly more abundant in the roots of whole poplar plants. Therefore, PCB95 can at least be metabolized into 4′-OH-PCB95 and another unknown hydroxylated PCB95 (as a minor metabolite) in whole poplar plants. Both atropisomers of 4′-OH-PCB95 are formed, but E2-4′-OH-PCB95 has greater atropisomeric enrichment in the roots of whole poplar plants. A comparison with mammalian biotransformation studies indicates a distinctively different metabolite profile of OH-PCB95 metabolites in whole poplar plants. Our observations suggest that biotransformation of chiral PCBs to OH-PCBs by plants may represent an important source of enantiomerically enriched OH-PCBs in the environment.     

What stops the ‘diploid male vortex’?—A simulation study for species with single locus complementary sex determination

The survival of hymenopteran populations especially that of ecologically and economically important pollinators and parasitoids, has become a major topic for empirical and theoretical studies. Complementary sex determination (CSD) in Hymenoptera may impose a substantial genetic load through the production of inviable or sterile diploid males. Modelling and laboratory studies have indicated that this genetic load may trigger a ‘diploid male vortex’ leading to rapid extinction of populations.Here we take a broader theoretical approach to analyze why populations exhibiting CSD persist in nature, even if they contain large proportions of homozygous diploid individuals. Using an individual-based model of spatially structured hymenopteran populations, we show that (i) inviability or reduced fertility of homozygous individuals, (ii) female-biased sex ratio, and (iii) strong intra-specific competition can mitigate the negative influence of CSD on population persistence and that (iv) already extremely low dispersal rates will result in long term survival. These findings underline the importance of life history traits for population survival and demonstrate that rather specific conditions must be met to initiate the ‘diploid male vortex’.     

Synthesis of polychlorinated biphenyls (PCBs) using the Suzuki-coupling

An improved synthesis of polychlorinated biphenyls (PCBs) utilizing a palladium-catalyzed cross-coupling reaction (Suzuki-coupling) is described. The coupling of (chlorinated) aryl boronic acids 1-3 with bromochlorobenzenes 4 using the standard conditions of the Suzuki-coupling gave the desired PCB congeners 5-7 in good to excellent yields. The self-coupling product of the aryl boronic acids is the major impurity of this reaction. 3,4,5-trichlorophenyl derivatives such as 10 can be synthesized by coupling of an aryl boronic acid with the corresponding bromochloroaniline 8. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

Synthesis of hydroxylated PCB metabolites with the Suzuki-coupling

An improved synthesis of hydroxylated polychlorinated biphenyls (PCBs) which are structurally related to the major hydroxy PCB congeners identified in human plasma is described. The coupling of (chlorinated) aryl boronic acids with bromochloro anisoles using the standard conditions of the Suzuki coupling gave the desired hydroxylated PCB metabolites in good to excellent yields. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

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.     

Dioxion-/Furan-’Verbrennungsprofile’ aus Hochtemperaturprozessen

Present knowledge assumes that different mechanisms acting downstream in high temperature processes lead to the formation of polychlorinated dibenzo(p)dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Concerning the 17 2,3,7,8-Cl-substituted PCDD/F congeners in particular, there is new evidence for a single-step reaction type (recently reported in this publication series, of. also parts 1 and 2). A formation based on a combination of the several mechanisms, which have been proposed and discussed since 1985, becomes more and more unlikely. Qualitatively the PCDD/F formation downstream from high temperature processes depends rather on a thermodynamically forced single reaction step, and on pure statistical distribution quantitatively. This may be a new ‘Thermostat Synthesis’ instead of ‘de novo’.     

Research Articles: Special Issue “Impact Studies on Cloned Poplars”

Practical considerations, characteristic physiological features, as well as the availability of hybrids with different resistances to air pollutants play an important role in the decision to use poplar cuttings as experimental plants for impact studies. This paper demonstrates the effect of the hybridization of two poplar clones on the resistance to different air pollutants and, additionally, presents a new concept of bioindication involving these two clones with different degrees of resistance to SO₂ and O₃. This concept, which is based on the results of fumigation experiments conducted in open-top chambers, uses six-week-old vital poplar cuttings as bioindicators. Both the anabolic defense reactions of younger leaves and the catabolic stress reactions of older leaves are examined. The measurement results obtained from cv. Loenen and cv. Rochester clones which differ in their sensitivities to individual pollutants, are examined to determine the specific relationships. The results can be verified by measuring the premature leaf losses of a third clone, cv. Unal, which reacts to both SO₂ and O₃ with highly pronounced leaf loss. To prevent false interpretations, it is necessary to standardize the plant material as far as possible by choosing clones of a defined age and number of leaves, and by selecting reproducible cultivation and exposure conditions. The impact criteria are methodologically simple and therefore suitable for routine examinations.