The polymerization of methyl methacrylate with a new Nd(O-i-Pr)(3)-Al(i-Bu)(3) catalyst system

Methyl methacrylate (MMA) was polymerized with the rare earth coordination catalyst-system of Nd(O - i-Pr)(3) in toluene. The influences of various ligands in neodymium complexes, molar ratio of Al/Nd, catalyst concentration, catalyst aging time, solvents, the third component CCl4, temperature and time on the polymerization of MMA were studied. The results showed that the polymerization conversion reached more than 80% at a catalyst concentration of 9.2 x 10(-3) mol/L. The appropriate molar ratio of CCl4/Nd was 4. Hydrocarbon was preferred for the polymerzation to obtain a high conversion and a high <(M)over bar w> of PMMA. The H-1 NMR spectra of PMMA indicated that the lower the temperature, the higher the syndiotactic content of PMMA was obtained.

Effect of F- axial coordination on the electrochemistry of (TPP)Co

The axial coordination effect of F- on the redox behavior of (TPP)Co was investigated and spectroeletrochemistry in dichloroethane. It was verified that mono(F-) axial adduct (TPP)Co(II)(F-) could be reduced at 0.1 V(SCE). and bis(F-) axis adduct (TPP)Co(II)(F-)(2) formed with added F- molar ratio>1 could be reduced at the potential <-0.6 V(SCE). The equilibrium between (TPP)Co(II)(F-) and (TPP)Co(II)(F-)(2) was demonstrated.

Vapor phase esterification catalyzed by immobilized dodecatungstosilicic acid (SiW12) on activated carbon

The vapor phase esterification of acetic acid with ethanol and n-butanol catalyzed by SiW12 supported on activated carbon was studied in a flow fixed-bed reactor in the range of 358 to 433 K. The effects of the reaction temperature, liquid hourly space velocity (LHSV) as well as the molar ratio on the catalytic activity have been investigated. The kinetic studies showed that the rate of esterification was dependent on the partial pressures of the reactants and the addition of argon, an inert diluent in the system when the total pressure was kept at 1 atm. Also the alcohol structure has a profound effect on not only the rate of esterification, but also on the mechanism of esterification changing from a dual site mechanism for ethanol to a single site mechanism for n-butanol.

The effect of formulated molecular weight on temperature resistance and mechanical properties in polyimide based composites

This experimental study examines the role of formulated molecular weight between crosslink sites on the temperature resistance and mechanical properties of composites based on a polyimide containing a diphenyl thioether unit (PTI). The composites are fabricated by in situ polymerization of monomer reactants (PMR) using three monomeric ingredients: bis(3,4-dicarboxyphenyl) sulfide dianhydride (TDPA); 4,4'-methylene dianiline (MDA); and the monomethyl ester of norbornene anhydride (NE). By changing monomeric molar ratio, three formulations are prepared, in which formulated molecular weight between crosslink sites varies from 1487 to 3446 g mol(-1). Unidirectional composite laminates from each formulation and T300 carbon fibres are compression moulded and cut into a series of test specimens. By measuring the glass transition temperature (T-g), Mode I interlaminar fracture toughness (G(IC)) and other mechanical properties at room and elevated temperatures, the influences of formulated molecular weight on the temperature resistance and mechanical properties of PTI-based composites are investigated.

Ionic conductivity of gel electrolyte based on polydiethylene glycol dimethacrylate and its copolymer

Gel electrolytes were prepared by thermal polymerization of diethylene glycol dimethacrylate (DIEGD) or its copolymer with methoxy polyethylene glycol monomethacrylate, molecular weight 400 (PEM(400)), at a molar ratio of 3/1 in the presence of propylene carbonate (PC) and LiClO4. Conductivity was measured by impedance spectroscopy. It was found that the conductivity data follow the Arrhenius equation in the homopolymer gel system, while the VTF equation holds true in the copolymer gel system. An increase in conductivity was observed in the copolymer gel system. However, whether in the homopolymer or in the copolymer gel system, a maximum ambient temperature conductivity was found at a salt concentration near 1.50 mol/l. Further, the activation energy values calculated from Arrhenius plots for the homopolymer gel system tended to reach a minimum value with increasing salt concentration. (C) 1996 Elsevier Science Ltd

SYNTHESES AND CRYSTAL-STRUCTURE OF -(ETA-5C5H5)3LN.OC4H8 (LN=CE, ER)

Tricyclopentadienyl cerium tetrahydrofuranate (THF) was prepared by the reaction of (NH4)2Ce(NO3)6 with sodium cyclopentadienide(C5H5Na) in THF at molar ratio of 1:6 to give a brown crystal of (eta5-C5H5)3Ce.OC4H8; tricyclopentadienyl erbium tetrahydrofur

SYNTHESES AND CRYSTAL-STRUCTURES OF (ETA-5-C5H5)3LN(THF) (LN=CE, ER)

Brown crystalline tricyclopentadienyl cerium tetrahydrofuranate (THF) complex (eta5-C5H5)3Ce(THF) was prepared by the reaction of (NH4)2Ce(NO3)6 with sodium cyclopentadienide (C5H5Na) in THF at molar ratio of 1:6. ErCl3.4THF reacts with potassium cyclooct

PHASE-BEHAVIOR IN THERMOTROPIC LIQUID-CRYSTALLINE POLYMER AND POLYARYLETHERSULFONE BLENDS

An experimental study of the phase morphology and miscibility of binary blends of poly-arylethersulfone (PES) and a liquid crystalline polymer (LCP) of p-oxybenzoate and ethylene terephthalate units in a 60/40 molar ratio (PET-60PHB) is described. Blends

SYNTHESIS AND CHARACTERIZATION OF POLYMER-SUPPORTED LANTHANIDE COMPLEXES AND BUTADIENE POLYMERIZATION BASED ON THEM

Poly(styrene-acrylic acid)-lanthanide (Ln.PSAA) and poly(ethylene-acrylic acid)-neodymium (NdPEAA) complexes have been prepared and characterized. The infrared and X-ray photoelectron spectra indicate that the lanthanide complexes possess the bidentate carboxylate structure Ln-O-C(R)-O (see structure B in text). The catalytic behavior of the complexes has been described. The catalytic activities of Nd.PSAA and Nd.PEAA are much greater than that of the corresponding low molecular weight catalyst for butadiene polymerization. The activities of various individual lanthanide elements are quite different from one another. Neodymium shows the highest activity. Europium, samarium and the heavy elements exhibit very low or no activities. The cis-1,4 content of the polybutadiene obtained is not affected by different lanthanide elements in the series. The complex with the intermediate content of the functional group has a higher activity than the others. The polymer-supported lanthanide complexes having different constitutions have different catalytic activities. When the molar ratio of lanthanide to the functional group is ca. 0.2, the activity of the complex is in the optimum state. The activity is influenced by the dispersion of the lanthanide metal immobilized on the polymer chain. Catalytic activity can be improved by adding other metals to the catalyst system.

SYNTHESIS AND CRYSTAL-STRUCTURE OF A NEW LANTHANIDE CYCLOOCTATETRAENE COMPLEX (ETA-8-C8H8)ER(MU-ETA-8-C8H8)K(MU-ETA-8-C8H8)ER(MU-ETA-8-C8H8)K(THF)4

The tetranuclear nearly-linear complex (eta-8-C8H8)Er(mu-eta-8-C8H8)K(mu-eta-8-C8H8)Er(mu-eta-8-C8H8)K(THF)4 (THF = tetrahydrofuran) is first synthesised by the reaction of benzylcyclopentadienyl erbium dichloride (PhCH2C5H4)ErCl2.3THF with cyclooctatetraenyl potassium K2C8H8 in 1:1 molar ratio in THF; a single crystal X-ray study has shown that the complex has the tetralayer-sandwich structure and that the adjacent Er3+ and K+ ions are bridged by eta-8-cyclooctatetraenyl group.

SYNTHESES AND CRYSTAL-STRUCTURES OF TRIINDENYLLANTHANIDE COMPLEXES (ETA-5-C9H7)3LN.OC4H8 (LN=ND,GD,ER)

The complexes named in the title (eta-5-C9H7)3Ln.OC4H8 (Ln = Nd, Gd, Er) were synthesized by the reaction of anhydrous lanthanide trichlorides with indenyl potassium and cyclooctadienyl potassium (1:2:1 molar ratio) in THF. The complexes were characterized by elemental analysis, infrared and H-1-NMR spectroscopy, and mass spectrometry. In addition, the crystal structures of (eta-5-C9H7)3Nd.OC4H8 (1) and (eta-5-C9H7)3Gd.OC4H8 (2) were determined by an X-ray diffraction study. Complexes 1 and 2 belong to hexagonal space group P6(3) with unit cell parameters a = b = 11.843(3), c = 10.304(4) angstrom, V = 1251.7(9) angstrom-3, D(c) = 1.49 g.cm-3, Z = 2 for 1, and a = b = 11.805(2), c = 10.236(2) angstrom, V = 1235.4(6) angstrom-3 D(c) = 1.54 g.cm-3, Z = 2 for 2. The structures were solved by Patterson and Fourier techniques and refined by least-squares to final discrepancy indices of R = 0.049, R(w) = 0.053 using 925 independent reflections with I greater-than-or-equal-to 3-sigma(I) for 1, and R = 0.023, R(w) = 0.025 using 1327 independent reflections with I greater-than-or-equal-to 3-sigma(I) for 2. Coordination numbers for Nd3+ and Gd3+ are 10; the average bond lengths Nd-O and Gd-O are 2.557(21) and 2.459(13) angstrom, respectively. The structural studies showed the complexes to have 3-fold symmetry, but the THF molecule has no such symmetry; consequently the arrangement of carbon atoms in the THF molecule are disordered.

An acidic polysaccharide with xylose branches from Porphyra yezoensis

An acidic polysaccharide (PY3) was isolated from the hot water extract of the red algae Porphyra yezoensis by successive column chromatographies over DEAE-cellulose and Sephadex G-200. PY3 with an average molecular weight of 1.8x10(5) was demonstrated to be composed of galactose (Gal), 3,6-anhydrogalactose (3,6-AnGal), 6-OSO3-galactose (6-OSO3-Gal) and xylose (Xyl) in an approximate molar ratio of 25 : 15, 10, 1. In view of Smith degradation and methylation and on the basis of spectral evidence including those of IR, GC, GC-MS, and H-1 and C-13 NMR, the most probable repeating unit of PY3 could be proposed as [(1-->3)beta -D-Gal(1 --> 4)alpha -L-3,6-AnGal](3)-[(1 --> 3)beta -D-Gal(1 --> 4)alpha -L-6-OSO3-Gal](2) with a xylose moiety at the C-6 of one of every twenty-five beta -D-Gal residues. To our knowledge, PY3 was shown to be the first porphyran possessing occasional xylose branches.

Molecular cloning and expression of a novel Kazal-type serine proteinase inhibitor gene from Zhikong scallop Chlamys farreri, and the inhibitory activity of its recombinant domain

Serine proteinase inhibitors (SPIs) play important roles in host physiological and immunological processes in all multicellular organisms. A novel Kazal-type SPI gene was cloned from the Zhikong scallop Chlamys farreri (designated as CfKZSPI) by expressed sequence tag (EST) and rapid amplification of cDNA ends (RACE) approaches. The full-length cDNA of CfKZSPI was of 1788 nucleotides with a canonical polyadenylation signal sequence AATAAA and a polyA tail, and an open reading frame (ORF) encoding a polypeptide of 509 amino acids with a putative signal peptide of 22 amino acids. The deduced amino acid sequence of CfKZSPI contained 12 tandem Kazal domains with high similarity to other Kazal-type SPIs. The temporal expression of CfKZSPI in hemocytes after Vibrio anguillorum challenge was recorded by quantitative real-time RT-PCR. The relative mRNA expression level of CfKZSPI was up-regulated and reached 43.6-fold at 3 h post-challenge. After a decrease at 6 h, the expression Level increased again and reached 207.8-fold at 12 h post-challenge. The 12th Kazal domain of CfKZSPI was recombined into pET-32a(+) and expressed in Escherichia coli Rosetta-gami (DE3) to investigate its inhibitory activity. The purified recombinant protein (rCf KZSPI-1 2) showed significant inhibitory activity against trypsin but no activity against thrombin. When the molar ratio of inhibitor to trypsin reached 1:1, almost 90% of the enzyme activity could be inhibited, which suggested that one molecule of rCfKZSPI-12 was able to inhibit one molecule of trypsin. Kinetics analysis with Dixon plot showed that the inhibition constant (K-i) of rCfKZSPI-12 to trypsin was 173 nmol L-1. These results indicated that CfKZSPI was a novel Kazal-type SPI with significant inhibitory activity against trypsin, and was suspected to be involved in scallop immune response. (c) 2008 Elsevier Ltd. All rights reserved.

Nutrients in the Changjiang River

N, P and SiO3-Si in the Changjiang mainstream and its major tributaries and lakes were investigated in the dry season from November to December, 1997, and in the flood season in August and October, 1998. An even distribution of SiO3-Si was found along the Changjiang River. However, the concentrations of total nitrogen, total dissolved nitrogen, dissolved inorganic nitrogen, nitrate and total phosphorus, total particulate phosphorus increased notably in the upper reaches, which reflected an increasing impact from human activities. Those concentrations in the middle and lower reaches of the Changjiang River were relatively constant. Dissolved N was the major form of N and the particulate P was the major form of P in the Changjiang River. The molar ratio of dissolved N to dissolved P was extremely high (192.5-317.5), while that of the particulate form was low (5.6-37.7). High N/P ratio reflected a significant input of anthropogenic N such as N from precipitation and N lost from water and soil etc. Dissolved N and P was in a quasi-equilibrium state in the process from precipitate to the river. In the turbid river water, light limitation, rather than P limitation, seemed more likely to be a controlling factor for the growth of phytoplankton. A positive linear correlationship between the concentration of dissolved N and the river's runoff was found, mainly in the upper reaches, which was related to the non-point sources of N. Over the past decades, N concentration has greatly increased, but the change of P concentration was not as significant as N. The nutrient fluxes of the Changjiang mainstream and tributaries were estimated, and the result showed that the nutrient fluxes were mainly controlled by the runoff, of which more than a half came from the tributaries. These investigations carried out before water storage of the Three Gorges Dam will supply a scientific base for studying the influences of the Three Gorges Dam on the ecology and environment of the Changjiang River and its estuary.

Nutrient compositions of cultured Thalassiosira rotula and Skeletonema costatum from the Jiaozhou Bay in China

Carbon, nitrogen, phosphorus, silicon composition of cultured two different sized phytoplankton common species of Thalassiosira rotula and Skeletonema costatum from the Jiaozhou Bay were measured. Carbon, nitrogen, phosphorus, silicon contents in cell were. obvious higher in T. rotula than in S. costatum, but the percents of nitrogen, phosphorus, silicon contents in cell dry mass in T. rotula were lower than those in S. costatum. The dry mass concentrations of nitrogen,phosphorus,silicon in S. costatum were much higher than those in T. rotula, particularly silicon, the former was 6.4 times of the latter, showing that S. costatum could more assimilate these elements. Especially, S. costatum had competitive dominance for assimilating silicon, which is beneficial to its becoming a major dominant species in relative short silicon of the Jiaozhou Bay. There were some differences in numerical value of nutrient ratios both laboratory-cultured phytoplankton and different sized suspended particulates (mainly phytoplankton) in the Jiaozhou Bay, which was caused by the changes of environment. High contents of carbon, nitrogon and relative low phosporus,silicon, high molar ratio of nitrogen to phosphorus (far higher than Redfield value) and low ratio of silicon to phosphorus and silicon to nitrogen (far lower than Redfield values) in the two diatoms and different sized suspended particulates were consistent with those in the seawater. Relative short silicon in the seawater and phytoplankton showed that silicon was possibly affectting phytoplankton growth in the Jiaozhou Bay.