Synthesis of bis(amine anhydride)s for novel high T(g)s and organosoluble poly(amine imide)s by palladium-catalyzed amination of 4-chlorophthalide anhydride

Two novel bis(amine anhydride)s, NN-bis(3,4-dicarboxyphenyl)aniline dianhydride (I) and N,N-bis(3,4-dicarboxyphenyl)-p-tert-butylaniline (II), were synthesized from the palladium-catalyzed amination reaction of N-methyl-protected 4-chlorophthalic anhydride with arylamines, followed by alkaline hydrolysis of the intermediate bis(amine-phthalimide)s and subsequent dehydration of the resulting tetraacids. The X-ray structures of anhydride I and II were determined. The obtained dianhydride monomers were reacted with various aromatic diamines to produce a series of novel polyimides. Because of the incorporation of bulky, propeller-shaped triphenylamine units along the polymer backbone, all polyimides exhibited good solubility in many aprotic solvents while maintaining their high thermal properties. These polymers had glass transition temperatures in the range of 298-408 degrees C. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 525 degrees C in nitrogen.The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 95-164 MPa, 8.8-15.7%, and 1.3-2.2 GPa, respectively.

Electrostatic interaction hybrids from water-borne conductive polyaniline and inorganic precursor containing carboxyl group

Electrostatic interaction conductive hybrids were prepared in water/ethanol solution by the sol-gel process from inorganic sol containing carboxyl group and water-borne conductive polyaniline (cPANI). The electrostatic interaction hybrids film displayed 1-2 orders of magnitude higher electrical conductivity in comparison with common hybrids film, showing remarkable conductivity stability against water soaking. Most strikingly, it displayed ideal electrochemical activity even in a solution with pH = 14, which enlarged the conducting polyaniline application window to strong alkaline media.

Tunable synthesis, growth mechanism, and magnetic properties of La0.5Ba0.5MnO3

La0.5Ba0.5MnO3 products with novel flowerlike, microcube, and nanocube structures were successfully synthesized by a simple hydrothermal route by controlling the alkalinity of the reaction solutions. The synthesized products were systematically studied by X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The results showed that the formation of the flowerlike structures with a layer assembly experienced a nucleation-aggregation-crystallization growth process, while the cubic structures experienced a nucleation-crystallization growth process due to the effect of different alkalinity in the reaction solutions. The higher alkalinity also led to a decrease in the size in the cubic structures. Suitable temperature and pressure were demonstrated to be crucial to the formation of the flowerlike structures by carrying out further control experiments. The measurement of the magnetic properties of three samples obtained at different alkaline conditions indicated that the size of the La0.5Ba0.5MnO3 products had an obvious influence on their properties; however, the dependence of the properties upon the morphology of the La0.5Ba0.5MnO3 products was minor.

Templated synthesis of composite rings using core-shell toroids

In difference to compact objects of a similar size, toroidal structures have some distinguishing properties that originate from their open inner cavity and closed circuit. Here, a general facile methodology is developed to prepare composite rings with varied compositions on a large scale by using core-shell toroids assembled from tri-block copolymers of poly(4-vinyl pyridine) (PVP)/polystyrene (PS)/PVP. Taking advantage of the complexation ability of the PVP shell, varied components that range from polymers, inorganic materials, metals and their compounds, as well as pre-formed nanoparticles are introduced to the toroidal structures to form composite nanostructures. Metal ions can be adsorbed by PVP through complexation. After in situ reduction, a large number of metal-based functional materials can be prepared. PVP is alkaline, and thus capable of catalyzing the sol-gel process to generate an inorganic shell. Furthermore, pre-formed nanoparticles can also be absorbed by the shell through specific interactions. The PS core is not infiltrative during synthesis, and hollow rings can be derived after the polymer templates are removed.

The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of camphorsulfonic acid

Polyaniline-camphorsulfonic acid (PAN-CSA) composite film on platinum electrode surface has been synthesized via the electrochemical polymerization of aniline in the presence of camphorsulfonic acid (CSA). It was found that the doping of polyaniline (PAN) with CSA extends the electroactivity of PAN in neutral and even in alkaline media. The PAN-CSA composite film coated platinum electrodes are shown to be good electrocatalytic surfaces for the oxidation of ascorbic acid (AA) in phosphate buffer solution (PBS) of pH 7.0. The anodic peak potential of AA shifts from 0.63 V at the bare platinum electrode to 0.34 V at the PAN-CSA composite modified platinum electrode with a greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5-50 mM using cyclic voltammetry. The kinetics of the catalytic reaction are investigated using rotating disk electrode voltammetry and chronoamperometry. The results are explained using the theory of electrocatalytic reactions at chemically modified electrodes. The PAN-CSA composite on the electrode surface shows good reproducibility and stability.

pH-dependent conformational changes of ferricytochrome c induced by electrode surface microstructure

pH-dependent processes of bovine heart ferricytochrome c have been investigated by electronic absorption and circular dichroism (CD) spectra at functionalized single-wall carbon 'nanotubes (SWNTs) modified glass carbon electrode (SWNTs/ GCE) using a long optical path thin layer cell. These methods enabled the pH-dependent conformational changes arising from the heme structure change to be monitored. The spectra obtained at functionalized SWNTs/GCE reflect electrode surface microstructure-dependent changes for pH-induced protein conformation, pK(a) of alkaline transition and structural microenvironment of the ferricytochrome c heme. pH-dependent conformational distribution curves of ferricytochrome c obtained by analysis of in situ CD spectra using singular value decomposition least square (SVDLS) method show that the functionalized SWNTs can retain native conformational stability of ferricytochrome c during alkaline transition.

Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate)

The crystallization and melting behavior of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) (PHBV) and a 30/70 (w/w) PHBV/poly(propylene carbonate) (PPC) blend was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR). The transesterification reaction between PHBV and PPC was detected in the melt-blending process. The interaction between the two macromolecules was confirmed by means of FTIR analysis. During the crystallization process from the melt, the crystallization temperature of the PHBV/PPC blend decreased about 8 degreesC, the melting temperature was depressed by 4 degreesC, and the degree of crystallinity of PHBV in the blend decreased about 9.4%; this was calculated through a comparison of the DSC heating traces for the blend and pure PHBV. These results indicated that imperfect crystals of formed, crystallization was inhibited, and the crystallization ability of PHBV was weakened in the blend. The equilibrium melting temperatures of PHBV and the 30/70 PHBV/PPC blend isothermally crystallized were 187.1 and 179 degreesC, respectively.

Specific determination of As(V) by an acid phosphatase-polyphenol oxidase biosensor

An original amperometric biosensor based on the simultaneous entrapment of acid phosphatase (AcP) and polyphenol oxidase (PPO) into anionic clays (layered double hydroxides) was developed for the specific detection of As(V). The functioning principle of the bienzyme electrode consisted of the successive hydrolysis of phenyl phosphate into phenol by AcP, followed by the oxidation of phenol into o-quinone by PPO. The phenyl phosphate concentration was, thus, monitored by potentiostating the biosensor at -0.2 V vs Ag/AgCl to detect amperometrically the generated quinone. The detection of As(V) was based on its inhibitory effect on AcP activity toward the hydrolysis of phenyl phosphate into phenol. The As(V) can be specifically determined in pH 6.0 acetate buffer without any interferences of As(III) or phosphate, the detection limit being 2 nM or 0.15 ppb after an incubation step for 20 min.

Micellization and reversible pH-sensitive phase transfer of the hyperbranched multiarm PEI-PBLG copolymer

A novel, hyperbranched, amphiphilic multiarm biodegradable polyethylenimine-poly(gamma-benZyl-L-gluta- mate) (PEI-PBLG) copolymer was prepared by the ring-opening polymerization of gamma-benzyl-L-glutamate-N-car-boxyanhydride (BLG-NCA) with hyperbranched PEI as a macroinitiator. The copolymer could self-assemble into core-shell micelles in aqueous solution with highly hydrophobic micelle cores. As the PBLG content was increased, the size of the micelles increased and the critical micelle concentration (CMC) decreased. The surface of the micelles had a positive potential. The cationic micelles were capable of complexing with plasmid DNA (pDNA), which could be released subsequently by treatment with polyanions. The PEI-PBLG copolymer formed unimolecular micelles in chloroform solution. ne pH-sensitive phase-transfer behavior exhibited two critical pH points for triggering the encapsulation and release of guest molecules. Both the encapsulation and release processes were rapid and reversible. Under strong acidic or alkaline conditions, the release process became partially or completely irreversible.

Sudies on non-isothermal melt crystallization kinetics in PET/PEN/DBS blends

Macrokinetic models, namly the modified Avrami, Ozawa and Zibicki models, were applied to study the non-isothermal melt crystallization process of PET/PEN/DBS blends by DSC measurement. The modified Avrami model was found to describe the experimental data fairly well. With the cooling rates in the range from 5 to 20 K/min, Ozawa model could be well used to describe the early stages of crystallization. However, Ozawa model did not fit the polymer blends during the late stages of crystallization, because it ignored the influence of secondary crystallization. The crystallization ability of the blends decreases with increasing the DBS content from analysis by using Ziabicki kinetic model, which is similar to the results based on calculation of the effective energy barrier of the blends.

Synthesis and characterization of hyperbranched aromatic poly(ester-imide)s

The synthesis and characterization of hyperbranched aromatic poly(ester-imide)s are described. A variety of AB(2) monomers, N-[3- or 4-bis(4-acetoxyphenyl)toluoyl]-4-carboxyl-phthalimide and N-{3- or 4-[1,1-bis(4-acetooxyphenyl)]ethylphenyl}-4-carboxy phthalimides were prepared starting from condensation of nitrobenzaldehydes or nitroacetophenones with phenol and used for synthesis of hyperbranched poly(ester-imide)s containing terminal acetyl groups by transesterification reaction. These hyperbranched poly(ester-imide)s were produced with weight-average molecular weight of up to 6.87 g/mol. Analysis of H-1 NMR and C-13 NMR spectroscopy revealed the structure of the four hyperbranched poly(ester-imide)s. These hyperbranched poly(ester-imide)s exhibited excellent solubility in a variety of solvents such as N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran and showed glass-transition temperatures between 217 and 255 degreesC. The thermogravimetric analytic measurement revealed the decomposition temperature at 10% weight-loss temperature (T-d(10)) ranging from 365 to 416 degreesC in nitrogen.

Preparation of divalent rare earth ions in air by aliovalent substitution and spectroscopic properties of Ln(2+)

When alkaline earth ions in borates, phosphates or borophosphates [SrB4O7, SrB6O10, BaB8O13, MBPO5 (M=Ca,Sr)] are substituted partially and aliovalently by trivalent rare earth ions such as Sm3+, Eu3+, these rare earth ions can be reduced to divalent state by the produced negative charge vacancy V-M". The matrices must have appropriate structure containing a rigid three-dimensional network of tetragonal AO(4) groups (A=B,P). These groups can surround and isolate the produced divalent RE2+ ions from the reaction with oxygen. Therefore, this reduction reaction can be carried out even in air at high temperature. The produced divalent rare earth ions can be detected by luminescence and XANES methods and their spectroscopic properties are discussed.

Liquid-phase hydrogenation of furfural to tetrahydrofurfuryl alcohol catalyzed by polymer resin supported palladium catalysts

Three kinds of polymer resin supported Pd catalysts were prepared by mixing PdCl2, with alkaline styrene anion exchange resins[D392 -NH2, D382, -NHCH3, D301R, -NH(CH3)(2)], strongly alkaline styrene anion exchanged resin [201 X 7DVB, -NH+ (CH3)(3)] and alkaline epoxy exchange resin (701, -NH2), and hydrogenating in liquid phase at 1.013 X 10(5) Pa. The hydrogenation of furfural was studied under the reaction conditions such as solvent, temperature. Pd content in the supported catalyst and the amount of the catalyst. The yield of hydrogenation reaction of furfural markedly increased to 100% and the selectivity to tetrahydrofurfuryl alcohol increased to over 98% by polymer (alkaline styrene anion exchange resins D392, -NH2, D382, -NHCH3) supported palladium catalysts comparing with the yield over 70% and selectivity over 97% by palladium catalyst, in 50% alcohol-50% water or pure water solution at 1.013 X 10(5) Pa. The relationship between hydrogenation and the structures of functional group in the supporting resin was examined by XPS method.

Chemiluminescence determination of trace ascorbic acid with chromium (VI)-H2O2-luminol system

A new chemiluminescence(CL) system for the determination of ascorbic acid has been established. By the fast reduction reaction between chromium(VI) and ascorbic acid, chromium(M was generated to react with luminol and hydrogen peroxide in alkaline aqueous solution and hydrogen peroxide to produce CL. The CL emission intensity was correlated with ascorbic acid concentration in the range 8.0 x 10(-9) to 1.6 x 10(-4) mol/L, and the detection limit was 8.0 x 10(-9) mol/L ascorbic acid. The relative standard deviation (n = 11) for 1.0 x 10(-6) mol/L ascorbic acid is 0.9%. The method has been applied to the determination of ascorbic acid in vitamin C tablets with satisfactory results.

Preparation of borates doped with divalent rare earth ions (RE2+) in air and spectroscopy of divalent rare earth ions (RE2+ = Sm, Eu, Tm, Yb)

The spectroscopic feature of divalent Sm2+, Eu2+, Tm2+ and Yb2+ is discussed in this paper. Especially the spectroscopic properties of some berates containing tetrahedral BO4 group such as SrB4O7, SrB6O10 and BaB8O13 doped with these divalent ions are reported. When the divalent alkaline earth ion in these berates is replaced partially by the above trivalent rare earth ion, the charge carried in the produced defects can be used as reductant to reduce the doped rare earth ion into divalent state at high temperature even in air. Therefore, a convenient and safe method is provided to prepared phosphors doped with these divalent rare earths.