Induction of hepatic cytochrome P4501A1/2B activity and disruption of thyroglobulin synthesis/secretion by mono-ortho polychlorinated biphenyl and its hydroxylated metabolites in rat cell lines

As the active metabolites of polychlorinated biphenyl (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs) are found in wildlife and human tissues. They have been proposed as main contributors for endocrine disruption of PCBs in living organisms. In this study, mono-ortho PCB 156 and its hydroxylated metabolites 4'-OH-PCB 159, 4'-OH-PCB 121, and 4'-OH-PCB 72 were selected to investigate the toxic effects on rat hepatoma H4IIE cell line and rat thyroid follicle FRTL-5 cell line at concentrations of 1, 10(2), 10(4) nM. 7-Ethoxyresorufin-O-deethylase (EROD) and 7-pentoxyresorufin-O-dealkylase (PROD) activities were determined with micro-EROD/PROD to indicate cytochrome P4501 A1 (CYP1A1) and cytochrome P4502B (CYP2B) induction in the H4IIE cell after exposure for 72 h. To assess thyroid disruption of these compounds, thyroglobulin concentrations also were detected inside FRTL-5 cell with immunocellularchemistry and in its medium with radioimmunoassay after exposure for 24 It. Significant inductions of EROD activity by PCB 156 at 102 and 104 nM (p < 0.05) were observed, but no effects by the three OH-PCBs in H4IIE cell line. 7-Pentoxyresorufin-O-dealkylase activities were induced only by 10(4) nM of PCB156 and the three OH-PCBs (p < 0.05). Meanwhile, significant increases of thyroglobulin concentrations were observed in the medium of FRTL-5 cell exposed to 4'-OH-PCB 121 and 4'-OH-PCB 72 at all of the test concentrations (p < 0.05), but not to the other compounds. The results demonstrated that mono-ortho PCBs mainly could be metabolized to hydroxylated metabolites through CYP1A1 instead of CYP2B. Moreover, after being metabolized, OH-PCBs still sustained the ability to induce PROD activity and did exhibit the disruption on thyroglobulin synthesis/excretion in rat cells.

Novel Oligo-9,9 '-spirobifluorenes through ortho-Linkage as Full Hydrocarbon Host for Highly Efficient Phosphorescent OLEDs

4-Bromo-9,9'-spirobifluorene is facilely synthesized, and from this precursor, two ortho-linked oligo-9,9'-spirobifluorenes, 44BSF and 24TSF, are constructed. Devices with 24TSF as the full-hydrocarbon host material and Ir(ppy)(3) or (ppq)(2)Ir(acac) as the triplet emitter show maximum external quantum efficiencies of 12.6 and 10.5% for green and red electrophosphorescence, respectively.

Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

Studies of the ortho effect in fragmentations of acetyl ion adducts of disubstituted benzenes

The ion-molecule reactions of disubstituted benzenes under chemical ionization conditions with acetyl chloride as reagent gas were examined, and the fragmentation reactions of the adduct ions (mostly proton and acetyl ion adducts) were studied by collision-induced dissociation. Electron-releasing substituents favored the adduct reactions, and electron-withdrawing groups did not. The position and properties of substituting groups had an effect on the relative abundances of the adduct ions. Several examples of the ortho effect were observed. The fragmentation reaction of the adduct ions formed by ortho-benzenediamine with the acetyl ion was similar to the reductive alkylation reaction of amines in the condensed phase. Copyright (C) 2001 John Wiley & Sons, Ltd.

Gas permeability and permselectivity of polyimides prepared from phenylenediamines with methyl substitution at the ortho position

Polyimides were prepared from diamines: 2,4,6-trimethyl-1,3-phenylenediamine (3MPDA) and 2,3,4,5-tetramethyl-1,4-phenylenediamine (4MPDA). 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3'-4,4'-diphenylsulphone tetracarboxylic dianhydride (SO(2)PDA), 3,3',4,4'-diphenylsulphide tetracarboxylic dianhydride (SPDA), pyromellitic dianhydride (PMDA), and 2,2'-bis(3,4-dicarboxyphenyl)hexa-fluoroisopropane dianhydride (6FDA) were used as dianhydride. The gas permeabilities of H-2, O-2 and N-2 through the polyimides were measured at temperatures from 30 degrees C to 90 degrees C. The results show that as methyl and trifluoromethyl substitution groups densities increase from 7.73 x 10(-3) molcm(-3) to 13.50 x 10(-3)molcm(-3), the peameability of H-2 increases 10-fold at 60% loss of permselectivity of H-2/N-2 however, the permeability of O-2 increases 20-fold at 20% loss of permselectivity of O-2/N-2. For O-2/N-2 separation, PMDA-3MPDA has similar performance to 6FDA-3MPDA and 6FDA-4MPDA; all have higher permeabilities for O-2 than normal polyimides, and the P(O-2)/alpha(O-2/N-2) trade-off relationships lie on the upper bound line for polymers. (C) 1999 Society of Chemical Industry.

Luminescence properties of the ternary terbium complexes with (ortho and para) aminobenzoic acids and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Ternary complexes of terbium with ortho (and pam) aminobenzoic acid and 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the solid-state samples was studied during the sol-gel aging process by means of emission. excitation spectra, lifetimes and quantum efficiencies.

PROTONIC ACID-DOPING OF POLY-ORTHO-METHYLANILINE

Poly-o-methylaniline (poly-o-toluidine) was doped by some protonic acids. It was found that the acidity, molecular size and oxidizing ability of protonic acids affected the doping level and conductivity of polymer obtained to some extent. The organic acid

SYNTHESIS AND CHARACTERIZATION OF POLY-ORTHO-METHYLANILINE WITH DIFFERENT DEGREES OF OXIDATION

Poly-ortho-methylanilines (POT) in three states fully oxidized, fully reduced and oxidized in varying degrees were synthesized by the reaction of common POT (C-POT) having nearly equal amounts of benzenediamine and quinonediimine units with iodine or phenyl-hydrazine, and the resulting polymers were characterized by IR, C-13-NMR, SEM and elemental analysis. The results showed that the quinonediimine unit in C-POT could be reduced by phenylhydrazine to the benzenediamine unit, forming the polymer with low OD (oxidation degree) or in a fully reduced state and that iodine-oxidation resulted in the increase of quinonediimine unit and decrease of benzenediamine unit. The solubility and flexibility of the formed polymers depend strongly on the amount of quinonediimine unit in it. It is necessary to reduce the content of quinonediimine structure unit in order to improve the solubility of aniline-class polymers.

A STUDY OF ION KINETIC-ENERGY SPECTROMETRY OF ORTHO-DICHLORO, META-DICHLORO AND PARA-DICHLORO BENZENE DOUBLY CHARGED IONS [C6H4CL2]2+ AND [C6H3CL]2+ IN GAS-PHASE

The unimolecular Charge separation reactions of the doubly charged ions [C6H4Cl2]2+, [C6H3Cl]2+ produced in the ion source by electron impact from o-, m-, and p-dichloro benzene have been studied using mass analysed ion kinetic energy spectrometry. The values of kinetic energy releases (T) can be calculated from the energy dispersion of product ions. As T essentially reflects the release of coulombic energy, which can be used to calculate the approximate distances R between the two charges immediately before decomposition of the ions. From these data, some structural information about transiton states could be provided. The ECID and CID processes of above doubly charged ions, have also been studied. We found that the CID reactions of (C6H4Cl2)2+ could be used to distinguish three dichloro benzene isomers.

ON THE IODINE-DOPING OF POLYANILINE AND POLY-ORTHO-METHYLANILINE

The reactions of polyaniline and poly-omicron-methylaniline of different oxidation degrees with I2 were followed by FTIR and electrical conductivity measurements. The results showed that the reaction of common polyanilines with I2 was oxidation in nature whereas that of the fully reduced ones was doping. The latter took place in two steps: oxidation of benzene-diamine units into quinone-diimine units (redox between I2 and the polymer chain) and formation of a conjugated system consisting of four aromatic rings (intramolecular chain redox).

THE INFLUENCE OF PROTONIC ACIDS ON THE CHEMICAL POLYMERIZATION OF ORTHO-METHYLANILINE

The chemical polymerization of ortho-methylaniline (MAn) is performed in aqueous solution of six protonic acids. The MAn polymerization conversion, and the electrical conductivity and doping level as well as molecular chain structure of the polymers obtained depend not only on the acid concentration but also on their acidity and molecular size.

Discovery of Late Cretaceous garnet two-pyroxene granulite in the southern Lhasa terrane, Tibet and its tectonic significances

The Lhasa terrane, located between the Bangonghu-Nujiang suture zone and the Indus-Yalung Tsangpo suture zone in the southern Tibetan Plateau, was considered previously as a Precambrian continental block. Mesozoic and Cenozoic tectonic evolution of the Lhasa terrane is closely related to the subduction of the Tethys ocean and the collision between the Indian and European continents; so it is one of the keys to reveal the formation and evolution of the Tibetan plateau. The garnet two-pyroxene granulite which was found at the Nyingtri rock group of the southeastern Lhasa terrene consists of garnet, clinopyroxene, orthopyroxene, labradorite, Ti-rich amphibolite and biotite, with a chemical composition of mafic rock. The metamorphic conditions were estimated to be at T = 747 similar to 834 degrees C and P = 0.90 similar to 1.35GPa, suggesting a formation depth of 45km. The zircon U-Pb dating for the garnet amphibolite and marble associated with the granulite give a metamorphic age of 85 similar to 90Ma. This granulite-facies metamorphic event together with a contemporaneous magmatism demonstrated that the southern Lhasa terrane has undergone an Andean-type orogeny at Late Mesozoic time.

大型浅水湖泊——巢湖内源磷负荷的时空变化特征及形成机制

通过对大型浅水富营养化湖泊——巢湖湖水、间隙水以及沉积物中磷形态及吸附行为时空变化的研究发现,富营养化较为严重的巢湖西区湖水、间隙水中的正磷酸盐(orthophosphate,Ortho-P)、总磷(total phosphorus,TP)显著高于东湖区,这与西湖区有大量的营养物质通过入湖河道输入有密切关系；此外水柱中颗粒态磷(particulate phosphorus,PP)亦有同样的空间分布规律,且PP的含量与微囊藻的生物量呈显著正相关关系,表明微囊藻在吸收与储藏磷方面比其它藻类更具优势。夏季浮游藻

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r(2) > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.