Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Extraction and separation of rare earths from chloride medium with mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester and sec-nonylphenoxy acetic acid

BACKGROUND: 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, H(2)A(2)) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec-nonylphenoxy acetic acid (CA100, H2B2) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied.

Solvent extraction study of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid with Cyanex301 or Cyanex302

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

Solvent extraction of rare earths from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and sec-octylphenoxyacetic acid

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

Preparation and characterization of poly(piperazineamide) composite nanofiltration membrane by interfacial polymerization of 3,3 ',5,5 '-biphenyl tetraacyl chloride and piperazine

Most nanofiltration (NF) membranes are composite and have a polyamide thin film prepared by interfacial polymerization. Their performances mainly correlate the structure of the thin film and monomers used for its preparation. In this work, a novel thin-film composite (TFC) nanofiltration membrane was successfully prepared from 3,3',5,5'-biphenyl tetraacyl chloride (mm-BTEC) and piperazine (PIP) through interfacial polymerization. Attenuated reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS) were used to characterize the chemical composition of the membrane surface. The membrane performance was optimized by studying preparation parameters including monomer concentration, reaction time, and pH of aqueous phase.

A quantitative HPLC method for determining lactide content using hydrolytic kinetics

A new method for quantitative analysis of lactide has been developed by applying chemical kinetics to a HPLC system. The most important advance is its practical approach to the quantification of analytes that are unstable in the HPLC mobile phase. In HPLC analysis, anhydrous mobile phases cannot separate lactide from impurities, and only mixtures of water and organic solvent can achieve effective separation. By selecting conditions for testing and studying the kinetics of lactide hydrolysis, extensive experiments revealed that lactide degradation can be treated as a pseudo-first-order reaction under the given HPLC conditions, and lactide content or purity can be quantitatively determined. This method is practical for measuring the purity of the intermediate lactide in polylactic acid (PLA) production and the lactide content in PLA.

Efficient preparation of silver nanoplates assisted by non-polar solvents

In the paper, we report an efficient method to prepare high yield (up to 97%) of silver nanoplates. Synthesis of silver nanoplates was carried Out in a binary solvent system of N,N-dimethylformamide (DMF) and toluene, in which DMF served as the reductant and polyvinylpyrrolidone (PVP) as the capping agent. By increasing the ratio of toluene to DMF to 7:6, silver nanoplates can be Successfully synthesized; otherwise other shaped nanoparticles would be the major products. The nanoplate sample was characterized by TEM, HRTEM, SAED, XRD, AFM and UV-visible spectroscopy, proving the high nanoplate purity of this sample. The influence of toluene content, other solvents, AgNO3 concentration, preparation temperature and chloride ions was also examined, which suggests that the function of nonpolar solvents in this system is to enhance the PVP coverage on silver surface and, furthermore, to facilitate the preferential adsorption of PVP on two (I I I) facets of silver nanoplates.

Incorporation of Nanoparticles into Polyelectrolyte Multilayers via Counterion Exchange and in situ Reduction

We report a general method for incorporation of nanoparticles into polyelectrolyte multilayer (PEM) thin films by utilizing the excess charges and associated counterions present in the PEMs. Silver ions were introduced directly into multilayers assembled from poly(diallyldimethylammonium chloride) (PDDA) and poly(styrene sulfonate) (PSS), (PDDA/PSS)(n), by a rapid ion exchange process, which were then converted into silver nanoparticles via in situ reduction to create composite thin films. The size and the content of the nanoparticles in the film call be tuned by adjusting the ionic strength in the polyelectrolyte solutions used for the assembly. Spatial control over the distribution of the nanoparticles in the PEM was achieved via the use of multilayer heterostructure containing PDDA/PSS bilayer blocks assembled at different salt concentrations. Because excess charges and counterions are always present in any PEM, this approach can be applied to fabricate a wide variety of composite thin Films based on electrostatic self-assembly.

N,N,N ',N '-Tetramethylchloroformamidinium Chloride-Mediated Cyclizations of beta-Oxo Amides: Facile and Divergent One-Pot Synthesis of Substituted 2H-Pyrans, 4H-Pyrans and Pyridin-2(1H)-ones

An efficient and divergent one-pot synthesis of substituted 2H-pyrans, 4H-pyrans and pyridin-2(1H)-ones from beta-oxo amides based on the selection of the reaction conditions is reported. Mediated by N,N,N',N'-tetramethylchloroformamidinium chloride, beta-oxo amides underwent intermolecular cyclizations in the presence of triethylamine at room temperature to give substituted 2H-pyrans in high yields, which could be converted into substituted 4H-pyrans in the presence of sodium hydroxide in ethanol at room temperature, or into substituted pyridin-2(1H)-ones under reflux.

Biochemical effects of gadolinium chloride in rats liver and kidney studied by H-1 NMR metabolomics

The biochemical effects of gadolinium chloride were studied using high-resolution H-1 nuclear magnetic resonance (NMR) spectroscopy to investigate the biochemical composition of tissue (liver and kidney) aqueous extracts obtained from control and gadolinium chloride (GdCl3) (10 and 50 mg/kg body weight, intraperitoneal injection. i.p.) treated rats. Tissue samples were collected at 48, 96 and 168 h p.d. after exposure to GdCl3, and extracted using methanol/chloroform solvent system. H-1 NMR spectra of tissue extracts were analyzed by pattern recognition using principal components analysis. The liver damages caused by GdCl3 were characterized by increased succinate and decreased glycogen level and elevated lactate, alanine and betaine concentration in liver. Furthermore, the increase of creatine and lactate, and decrease of glutamate, alanine, phosphocholine, glycophosphocholine (GPC), betaine, myo-inositol and trimethylamine N-oxide (TMAO) levels in kidney illustrated kidney disturbance induced by GdCl3.

Influence of Zn content on the microstructure and mechanical properties of extruded Mg-5Y-4Gd-0.4Zr alloy

Microstructures and mechanical properties of the Mg-5Y-4Gd-xZn-0.4Zr alloys have been investigated. These results show that the Mg-5Y-4Gd-0.5Zn-0.4Zr alloy in the peak-aged condition exhibits the highest tensile strength, and the values of the ultimate tensile strength and yield tensile strength are 370 and 300 MPa, respectively. It is suggested that addition of 0.5% Zn has a great effect on age hardening response. The long periodic stacking structure has been found in these Zn-containing alloys, and the volume fraction of this phase increases with increasing Zn addition. This phase plays an important role in improvement of the mechanical properties, especially for the elongations. The beta' phase precipitates during the ageing process are responsible for the improvement of the mechanical properties of the alloys in the peak-aged condition.

Soluble neodymium chloride 2-ethylhexanol complex as a highly active catalyst for controlled isoprene polymerization

Soluble NdCl3 center dot 3EHOH (2-ethyl hexanol) in hexane combined with AlEt3 is highly active for isoprene polymerization in hexane. The NdCl3 center dot 3EHOH/AlEt3 has higher activity than the typical binary catalyst NdCl3 center dot 3(i)PrOH (isopropanol)/AlEt3 and ternary catalyst NdV3 (neodymium versatate)/AlEt2Cl/Al(i-Bu)(2)H. The molecular weight of polyisoprenes can be controlled by variation of [Nd], [Al]/[Nd] ratio and polymerization temperature and time. The NdCl3 center dot 3EHOH/AlEt3 catalyst polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 96%), high molecular weight (ca. 10(5)) and relatively narr ow molecular weight distributions (M-w/M-n = 2.0-2.8) simultaneously. More importantly, some living polymerization characteristics were demonstrated: (a) absence of chain termination; (b) linear correlation between M-n and polymer yield; (c) increment of molecular weight in the 'seeding' polymerization. Though some deviation from the typical living polymerization such as molecular weight distribution is not narrow enough and the line of M-n and polymer yield does not extrapolate to zero, controlled polymerization with the current catalyst can still be concluded.

Studies on the content variation of chemical constituents during the combination of ginseng with veratrum nigrum by ESI-MS and HPLC-ESI-MS

To study the content variation of ginsenosides and alkaloids during combination of ginseng with veratrum nigrum, the ginsenosides and alkaloids in the decoction of ginseng with veratrum nigrum were analyzed and compared by high performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) and electrospray ionization-mass spectrometry (ESI-MS). In the compatible decoction, eight ginsenosides and eight alkaloids. were detected, and the contents of six ginsenosides were found to be reduced, on the contrary, the contents of six alkaloids were increased. During combination of ginseng with veratrum nigrum, the contents of ginsenosides were reduced and those of the toxic alkaloids were increased. From the chemical point of view, the traditional theory is right that ginseng and veratrum nigrum are incompatible with each other.

Study on the synthesis and performance of hydrogels with ionic monomers and montmorillonite

Two series of the nanocomposite hydrogels were synthesized by in-situ solution polymerization. One pre-gel solution was obtained by directly dispersing the montmorillonite (MMT) powder into aqueous monomer solution and the other pre-gel solution was obtained by mixing monomer aqueous solution and the dispersion of MMT. The structure and performance of two series of hydrogels in dry state were studied by XRD, Raman spectroscopy, TEM and Al-27 MAS NMR. Compressing test results showed that the gel strength of the hydrogels prepared by the latter method was much higher than that by the former method. When acryloyloxyethyl trimethyl ammonium chloride (DAC) was introduced into the system, hydrogels with excellent nanostructure could be synthesized. The result of Al-27 MAS NMR suggested that the chemical environment of aluminum in MMT was changed by the introduction of DAC due to the interaction between the groups of DAC and MMT layers. Thus, the combination of copolymerizing with strong polar monomers and using the dispersion of MMT were the effective ways to obtain tranocomposite hydrogel of MMT and ionic monomers. The nanostructure of the hydrogel improved the gel strength, while the swelling ratio of the hydrogel depended on synergic effects of multifunctional groups.

Polyamide thin film composite membranes prepared from 3,4',5-biphenyl triacyl chloride, 3,3',5,5'-biphenyl tetraacyl chloride and m-phenylenediamine

Two novel of tri- and tetra-functional biphenyl acid chloride: 3,4',5-biphenyl triacyl chloride (BTRC) and 3,3',5,5'-biphenyl tetraacyl chloride (BTEC), were synthesized, and used as new monomers for the preparations of the thin film composite (TFC) reverse osmosis (RO) membranes. The TFC RO membranes were prepared on a polysulfone supporting film through interfacial polymerization with the two new monomers and m-phenylenediamine (MPD). The membranes were characterized for the permeation properties, chemical composition, d-space between polymer chains, hydrophilicity, membrane morphology including top surface and cross-section. Permeation experiment was employed to evaluate the membranes performance including salt rejection and water flux. The surface structure and chemical composition of membranes were analyzed by attenuated total reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS). The results revealed that the active layer of membranes was composed of highly cross-linked aromatic polyamide with the functional acylamide (-CONH-) bonds. The TFC membranes prepared from biphenyl acid chloride exhibit higher salt rejection compared with that prepared from trimesoyl chloride (TMC) at the expanse of some flux.