Partitioning of dissolved chlorinated ethenes into vegetable oil

Food-grade soybean oil (SoyOil) has been used to enhance in situ anaerobic bioremediation at sites contaminated with chlorinated ethenes (CEs). The abiotic interactions of SoyOil with the CEs may be significant and need to be better understood. The oil: water partition coefficients (Kp) of dissolved CEs into SoyOil were measured in batch tests and ranged from 22 to 1200 with increasing chlorination. CE mixtures significantly reduced the Kp for tetrachloroethene (PCE), but not the other CEs. Simple flow tests were used to quantify the mass transfer coefficients (kL) of dissolved CEs into SoyOil. Higher kL values corresponded to the CEs with higher diffusivity in water. CE mixtures reduced the kL for all of the CEs. The results can be used to predict abiotic interactions and distribution of contaminant mass expected after SoyOil injection, and thus provide a more accurate estimate of the mass of CEs removed due to enhanced biodegradation.     

Absorption and metabolism of the mycotoxin zearalenone and the growth promotor zeranol in Caco-2 cells in vitro

Scope: Zearalenone (ZEN) and α‐zearalanol (α‐ZAL, zeranol) were studied in differentiated Caco‐2 cells and in the Caco‐2 Millicell^® system in vitro to simulate their in vivo intestinal absorption and metabolism in humans. Methods and results: In addition to metabolic reduction/oxidation, extensive conjugation with glucuronic acid and sulfate of the parent compounds and their phase I metabolites was observed. The positional isomers of the glucuronides and sulfates were unambiguously identified: Sulfonation occurred specifically at the 14‐hydroxyl group, whereas glucuronidation was less specific and, in addition to the preferred 14‐hydroxyl group, involved the 16‐ and 7‐hydroxyl groups. Using the Caco‐2 Millicell^® system, an efficient transfer of the glucuronides and sulfates of ZEN and α‐ZAL and their phase I metabolites into both the basolateral and the apical compartment was observed after apical administration. The apparent permeability coefficients (P_app values) of ZEN, α‐ZAL and the ZEN metabolite α‐zearalenol were determined, using an initial apical concentration of 20 μM and a permeation time of 1 h. Conclusion: According to the P_app values, the three compounds are expected to be extensively and rapidly absorbed from the intestinal lumen in vivo and reach the portal blood both as aglycones and as glucuronide and sulfate conjugates in humans.     

Fluorinated Zinc Phthalocyanine as Donor for Efficient Vacuum‐Deposited Organic Solar Cells

Efficient single bulk heterojunction organic solar cells based on blends of a fluorinated zinc phthalocyanine as electron donor and fullerene C₆₀ as electron acceptor are reported. In comparison to the commonly used absorber zinc phthalocyanine, the fluorination of the molecule to F₄ZnPc leads to an increase in ionisation potential and subsequently to an improvement of about 170 mV in the open circuit voltage of organic solar cells, while the short circuit current density and fill factor remain nearly unchanged. Similar to ZnPc:C₆₀‐based devices, the device characteristics of F₄ZnPc:C₆₀ solar cells can be further enhanced by improving the blend layer morphology by substrate heating during deposition. F₄ZnPc is an efficient donor material that can achieve a 4.6% power conversion efficiency in single heterojunction organic solar cells.     

Glucuronidation of zearalenone,zeranol and four metabolites in vitro: Formation of glucuronides by various microsomes and human UDP‐glucuronosyltransferase isoforms

Glucuronidation constitutes an important pathway in the phase II metabolism of the mycotoxin zearalenone (ZEN) and the growth promotor α‐zearalanol (α‐ZAL, zeranol), but the enzymology of their formation is yet unknown. In the present study, ZEN, α‐ZAL and four of their major phase I metabolites were glucuronidated in vitro using hepatic microsomes from steer, pig, rat and human, intestinal microsomes from humans, and eleven recombinant human UDP‐glucuronosyltransferases (UGTs). After assigning chemical structures to the various glucuronides by using previously published information, the enzymatic activities of the various microsomes and UGT isoforms were determined together with the patterns of glucuronides generated. All six compounds were good substrates for all microsomes studied. With very few exceptions, glucuronidation occurred preferentially at the sterically unhindered phenolic 14‐hydroxyl group. UGT1A1, 1A3 and 1A8 had the highest activities and gave rise to the phenolic glucuronide, whereas glucuronidation of the aliphatic hydroxyl group was mostly mediated by UGT2B7 with low activity. Based on these in vitro data, ZEN, α‐ZAL and their metabolites must be expected to be readily glucuronidated both in the liver and intestine as well as in other extrahepatic organs of humans and various animal species.     

Stimulation of estradiol glucuronidation: a protective mechanism against estradiol-mediated carcinogenesis?

17beta-Estradiol (E2) and its catechol and methoxy metabolites are believed to play important roles in the mechanism of E2-mediated tumor formation. Because conjugation with glucuronic acid lowers tissue levels by facilitating excretion, we have determined the kinetic parameters of the glucuronidation of E2, estrone (E1), and seven phase I metabolites using human liver microsomes. The catechol estrogens 2- and 4-hydroxy-E2/E1 exhibited the highest clearance, exceeding that of E2, E1, and the methoxy metabolites by factors of 6-44. Homotropic activation kinetics were observed for the 3-glucuronidation of E2 but not for any of the metabolites. None of the metabolites affected the kinetics of the 3-glucuronidation of E2. In contrast, the isoflavone daidzein stimulated the formation of E2-3-glucuronide, as has been reported previously. This heterotropic activation by daidzein appears to be specific for the glucuronidation of E2 because daidzein did not affect the glucuronidation of the 2- and 4-hydroxy metabolites of E2. However, daidzein may lower the glucuronidation of 2-methoxy-E2 in vivo due to its preferential glucuronidation. The decreased tissue levels of E2 and increased concentrations of 2-methoxy-E2, as implied by this study and the previous one, may contribute to the protective effect of daidzein against breast and endometrial cancer.     

Fate of toxic cyanobacterial cells and disinfection by-products formation after chlorination

Drinking water sources in many regions are subject to proliferation of toxic cyanobacteria (CB). Chlorination of source water containing toxic cyanobacterial cells for diverse treatment purposes might cause cell damage, toxin release and disinfection by-products (DBP) formation. There is limited information available on chlorination of different toxic CB cells and DBP formation potentials. This work: (1) determines the extent of lysis and toxins/taste and odor compound release in chlorinated natural water from CB cells (Anabaena circinalis, Microcystis aeruginosa, Cylindrospermopsis raciborskii, and Aphanizomenon issatsckenka) from laboratory cultures and natural blooms; (2) assesses the rates of oxidation of toxins by free chlorine under environmental conditions; (3) studies the DBP formation associated with the chlorination of CB cell suspensions. With chlorine exposure (CT) value of <4.0 mg min/L >60% cells lost viability causing toxin release. Cell membrane damage occurred faster than oxidation of released toxins. Kinetic analysis of the oxidation of toxins in natural water revealed significant differences in their susceptibility to chlorine, saxitoxins being the easiest to oxidize, followed by cylindrospermopsin and microcystin-LR. Furthermore, concentrations of trihalomethanes and haloacetic acids (<40 μg/L) and N-nitrosodimethylamine (<10 ng/L) as chlorination by-products were lower than the guideline values even at the highest CT value (220 mg min/L). However, the DBP concentrations in environmental bloom conditions with very high cell numbers were over the guideline values.