Synthesis of poly(phenylenesulfidephenylenamine) by self-polycondensation of methyl-(4-anilinophenyl) sulfide with antimony pentachloride

Poly(phenylenesulfidephenylenamine)(PPSA) an alternating copolymer and the hybrid structure of poly(phenylene sulfide)(PPS) and polyaniline(PAn), was synthesized by self-polycondensation of methyl-(4-anilino-phenyl) sulfide with antimony pentachloride and by the acid-induced self-polycondensation of methyl-(4-anilino-phenyl) sulfoxide.

Vibrational spectra and structure of zinc phthalocyanine

Semi-empirical molecular orbital calculations using PM3 Hamiltonian were employed to determine qualitative assignments of the vibrational spectrum of zinc phthalocyanine (ZnPc). The assignments are from the potential energy distribution calculations in the normal coordinate analysis and optimized geometry in the PM3 calculations. The structure of the ZnPc molecule is also deduced. (C) 1999 Elsevier Science B.V. All rights reserved.

Compatibilization of blends of polystyrene and zinc salt of sulfonated polystyrene by poly(styrene-b-4-vinylpyridine) diblock copolymer

The compatibilizing effect and mechanism of poly(styrene-b-4-vinylpyridine) diblock copolymer, P(S-b-4VPy), on the immiscible blend of polystyrene (PS)/zinc salt of sulphonated polystyrene (Zn-SPS) were studied. SEM results show that the domains of the dispersed phase in the blend become finer. DSC experiments reveal that the difference between the two T-g's corresponding to the phases in the blends becomes larger on addition of P(S-b-4VPy), mainly resulting from dissolving of the poly(4-vinylpyridine (P4VPy) block in the Zn-SPS phase. FTIR analysis shows that compatibility of P4VPy and Zn-SPS arises from the stoichiometric coordination of the zinc ions of Zn-SPS and pyridine nitrogens of P4VPy. SAXS analysis indicates the effect of the P(S-b-4VPy) content on the structure of the compatibilized blends. When the content of the block copolymer is lower than 4.1 wt%, the number of ion pairs in an aggregate in the Zn-SPS becomes smaller, and aggregates in ionomer in the blend become less organized with increasing P(S-b-4VPy). When the P(S-b-4VPy) content in the blend is up to 7.4 wt%, a fraction of P(S-b-4VPy) form a separate domain in the blend. (C) 1999 Elsevier Science Ltd. All rights reserved.

Dependence of linear electro-optic coefficient on difference in the atomic sizes in zinc blende crystals

Covalent radii of the bonding elements have strong effects on the linear electro-optic coefficients of zinc blende crystals; these effects can be quantitatively determined by investigating the relation between the difference in the atomic sizes rho and the magnitude of the linear electro-optic tensor coefficient r(41). It is interesting to note that for the same cation Zn2+, Ga3+, or In3+ the magnitude of r(41) increases with increased covalent radius of the bonded anion r(beta). Especially with the increasing tendency of the parameter rho, the magnitude of r(41) of crystals that have a same cation will increase suddenly when the value of r(beta) becomes larger. (C) 1997 Academic Press.

Effect of physical aging on phenolphthalein polyethersulfone/poly(phenylene sulfide) blend .1. Mechanical properties

The effect of physical aging at 210 degrees C on the mechanical properties of phenolphthalein polyether sulfone (PES-C) and a PES-C/poly(phenylene sulfide) (PPS) blend, with 5% content of PPS, were studied using DMA, tensile experiments, an instrumented impact tester, and SEM observations. The blend shows good mechanical properties in comparison with the corresponding PES-C. The mechanical properties of both materials exhibit characteristics of physical aging, with only the aging rate of the blend relatively slower, which should be attributed to the constraint effect of PPS particles and the good interfacial adhesion. The morphology of the PPS phase in the blend did not change with aging time. The principal role of PPS particles is to induce crazes, which dissipate energy, under applied loading; thus, the blend shows good toughness. On the other hand, the multiple crazing mechanism depends on the molecular mobility or structural state of the matrix. (C) 1996 John Wiley & Sons, Inc.

Enhanced glass fiber-reinforced phenolphthalein poly(ether ketone) composites by blending poly(phenylene sulfide)

The mechanical properties of glass fiber-reinforced phenolphthalein poly(ether ketone)/poly(phenylene sulfide) (PEK-C/PPS) composites have been studied. The morphologies of fracture surfaces were observed by scanning electron microscope. Blending a semicrystalline component, PPS, can improve markedly the mechanical properties of glass fiber-reinforced PEK-C composites. These results can be attributed to the improvement of fiber/matrix interfacial adhesion and higher fiber aspect ratio. (C) 1996 John Wiley & Sons, Inc.

THERMAL AND MECHANICAL-PROPERTIES OF PHENOLPHTHALEIN POLYETHERSULFONE POLY(PHENYLENE SULFIDE) BLENDS

The thermal and mechanical properties of phenolphthalein polyethersulfone/poly(phenylene sulfide) (PES-C/PPS) blends were studied using a differential scanning calorimeter, a dynamic mechanical analyzer, and mechanical characterization. The morphologies of fracture surfaces were observed by scanning electron microscopy. The blends are multiphase systems with strong interaction between the two phases. It is of interest that, although the strength and ductility of PPS are lower than those of PES-C, the addition of PPS can improve markedly the impact strength of PES-C without changing its higher strength. The PPS can also act as a flow aid for PES-C. (C) 1995 John Wiley and Sons, Inc.

STRUCTURE OF CIS-DIAQUABIS(1,10-PHENANTHROLINE)ZINC SULFATE HEXAHYDRATE

[Zn(C12H8N2)2(H2O)2]SO4.6H2O, M(r) = 665.98, triclinic, P1BAR, a = 10.070 (4), b = 12.280 (3), c = 13.358 (2) angstrom, alpha = 109.12 (2), beta = 92.58 (2), gamma = 110.85 (2)-degrees, V = 1433.9 (7) angstrom 3, Z = 2, D(x) = 1.54 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 10.1 cm-1, F(000) = 692, T = 293 K, R = 0.044 for 3985 observed reflections. The Zn atom is coordinated in a distorted octahedral geometry by four N atoms from two 1,10-phenanthroline (phen) ligands and two water molecules. The intermolecular ring-stacking interactions between the phen ligands occur in two forms: infinite chains and discrete dimers. Hydrogen bonds further stabilize the structure.

The structure of Aquifex aeolicus sulfide:quinone oxidoreductase, a basis to understand sulfide detoxification and respiration

Sulfide: quinone oxidoreductase (SQR) is a flavoprotein with homologues in all domains of life except plants. It plays a physiological role both in sulfide detoxification and in energy transduction. We isolated the protein from native membranes of the hyperthermophilic bacterium Aquifex aeolicus, and we determined its X-ray structure in the "as-purified,'' substrate-bound, and inhibitor-bound forms at resolutions of 2.3, 2.0, and 2.9 angstrom, respectively. The structure is composed of 2 Rossmann domains and 1 attachment domain, with an overall monomeric architecture typical of disulfide oxidoreductase flavoproteins. A. aeolicus SQR is a surprisingly trimeric, periplasmic integral monotopic membrane protein that inserts about 12 angstrom into the lipidic bilayer through an amphipathic helix-turn-helix tripodal motif. The quinone is located in a channel that extends from the si side of the FAD to the membrane. The quinone ring is sandwiched between the conserved amino acids Phe-385 and Ile-346, and it is possibly protonated upon reduction via Glu-318 and/or neighboring water molecules. Sulfide polymerization occurs on the re side of FAD, where the invariant Cys-156 and Cys-347 appear to be covalently bound to polysulfur fragments. The structure suggests that FAD is covalently linked to the polypeptide in an unusual way, via a disulfide bridge between the 8-methyl group and Cys-124. The applicability of this disulfide bridge for transferring electrons from sulfide to FAD, 2 mechanisms for sulfide polymerization and channeling of the substrate, S2-, and of the product, S-n, in and out of the active site are discussed.

Characterizing a monotopic membrane enzyme. Biochemical, enzymatic and crystallization studies on Aquifex aeolicus sulfide:quinone oxidoreductase

Monotopic membrane proteins are membrane proteins that interact with only one leaflet of the lipid bilayer and do not possess transmembrane spanning segments. They are endowed with important physiological functions but until now only few of them have been studied. Here we present a detailed biochemical, enzymatic and crystallographic characterization of the monotopic membrane protein sulfide:quinone oxidoreductase. Sulfide:quinone oxidoreductase is a ubiquitous enzyme involved in sulfide detoxification, in sulfide-dependent respiration and photosynthesis, and in heavy metal tolerance. It may also play a crucial role in mammals, including humans, because sulfide acts as a neurotransmitter in these organisms. We isolated and purified sulfide:quinone oxidoreductase from the native membranes of the hyperthermophilic bacterium Aquifex aeolicus. We studied the pure and solubilized enzyme by denaturing and non-denaturing polyacrylamide electrophoresis, size-exclusion chromatography, cross-linking, analytical ultracentrifugation, visible and ultraviolet spectroscopy, mass spectrometry and electron microscopy. Additionally, we report the characterization of its enzymatic activity before and after crystallization. Finally, we discuss the crystallization of sulfide:quinone oxidoreductase in respect to its membrane topology and we propose a classification of monotopic membrane protein crystal lattices. Our data support and complement an earlier description of the three-dimensional structure of A. aeolicus sulfide:quinone oxidoreductase (M. Marcia, U. Ermler, G. Peng, H. Michel, Proc Natl Acad Sci USA, 106 (2009) 9625-9630) and may serve as a reference for further studies on monotopic membrane proteins. (C) 2010 Elsevier B.V. All rights reserved.

Authigenic sulfide minerals and their sulfur isotopes in sediments of the northern continental slope of the South China Sea and their implications for methane flux and gas hydrate formation

This is a report of the study of the authigenic sulfide minerals and their sulfur isotopes in a sediment core (NH-1) collected on the northern continental slope of the South China Sea, where other geophysical and geochemical evidence seems to suggest gas hydrate formation in the sediments. The study has led to the findings: (1) the pyrite content in sediments was relatively high and its grain size relatively large compared with that in normal pelagic or hemipelagic sediments; (2) the shallowest depth of the acid volatile sulfide (AVS) content maximum was at 437.5 cm (> 2 mu mol/g), which was deeper than that of the authigenic pyrite content maximum (at 141.5-380.5 cm); (3) delta S-34 of authigenic pyrite was positive (maximum: +15 parts per thousand) at depth interval of 250-380 cm; (4) the positive delta S-34 coincided with pyrite enrichment. Compared with the results obtained from the Black Sea sediments by Jorgensen and coworkers, these observations indicated that at the NH-1 site, the depth of the sulfate-methane interface (SMI) would be or once was at about 437.5-547.5 cm and the relatively shallow SMI depth suggested high upward methane fluxes. This was in good agreement with the results obtained from pore water sulfate gradients and core head-space methane concentrations in sediment cores collected in the area. All available evidence suggested that methane gas hydrate formation may exist or may have existed in the underlying sediments.

Concentrations of Cadmium and Zinc in Seawater of Bohai Bay and Their Effects on Biomarker Responses in the Bivalve Chlamys farreri

Both in-field chemical investigation and in the laboratory toxic tests were carried out to systematically understand the pollution status of cadmium (Cd) and zinc (Zn) in Bohai Bay. Samples collected from surface seawater were determined to describe the distributions of Cd and Zn in Bohai Bay. The average values in our study of Cd and Zn were 0.15 mu g/L and 19.68 mu g/L, respectively. Both of them were lower than the first class limit of seawater quality standard in China. In the laboratory, antioxidant enzymes [SOD (Cu/Zn-SOD, Mn-SOD), CAT], lipid peroxidation (MDA), phase I and phase II enzymes (CYP4501A and GST) were investigated in the bivalves Chlamys farreri exposed to Cd and Zn at the concentration levels of Bohai Bay seawater, which were obtained from our in-field investigation. The reduced SOD, CAT, and EROD (7-ethoxyresorufin-O-deethylase) activities (with the inhibitory rate of 16.8%, 31.5%, and 51.6%, respectively) in Cd treatment were observed and resulted in obvious lipid peroxidation damage. However, treatment of Zn showed elevations in SOD and GST by 13.3% and 29.9%, respectively, and with no influence on lipid peroxidation. In summary, seawater quality in Bohai Bay seawater was ranked as good in general, but it seemed that Cd might possess a potential environmental risk by effecting pro-oxidant/antioxidant balance and phase I detoxification in C. farreri.

Cloning, characterization, and expression analysis of extracellular copper/zinc superoxide dismutase gene from bay scallop Argopecten irradians

Extracellular superoxide dismutase (ECSOD) is a major extracellular antioxidant enzyme that protects organs from damage by reactive oxygen species (ROS). We cloned a novel ECSOD from the bay scallop Argopecten irradians (AiECSOD) by 3' and 5' RACE. The full-length cDNA of AiECSOD was 893 bp with a 657 bp open reading frame encoding 218 amino acids. The deduced amino acid sequence contained a putative signal peptide of 20 amino acids, and sequence comparison showed that AiECSOD had low degree of homology to ECSODs of other organisms. The genomic length of the AiECSOD gene was about 5276 bp containing five exons and six introns. The promoter region contained many putative transcription factor binding sites such as c-Myb, Oct-1, Sp1, Kruppel-like, c-ETS, NF kappa B, GATA-1, AP-1, and Ubx binding sites. Furthermore, tissue-specific expressions of AiECSOD and temporal expressions of AiECSOD in haemocytes of bay scallops challenged with bacteria Vibrio anguillarum were quantified using qRT-PCR. High levels of expression were detected in haemocytes, but not in gonad and mantle. The expression of AiECSOD reached the highest level at 12 h post-injection with V. anguillarum and then returned to normal between 24 h and 48 h post-injection. These results indicated that AiECSOD was an inducible protein and that it may play an important role in the immune responses against V anguillarum. Crown Copyright (C) 2008 Published by Elsevier Ltd. All rights reserved.