Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.

Sulfonated polyimides bearing benzimidazole groups for proton exchange membranes

A series of sulfonated polymides containing benzimidazole groups were synthesized using 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS) as the sulfonated diamine, and 2-(3',5-diaminophenyl)benzimidazole (a) or 6,4'-diamino-2-phenylbenzimidazole (b) as the nonsulfortated diamine. The electrolyte properties of the synthesized polyimides Ia-x, Ib-x, x refers to molar percentage of the sulfonated diamine) were investigated and compared with those of polyimides (Ic-x) from BTDA, ODADS, and m-phenylenediamine (c). All synthesized polyimides possessed high molecular weights revealed by their high viscosity, and formation of tough and flexible membranes. Polyintides with benzimidazole groups exhibited much better swelling capacity than those without benzimiclazole groups. This was attributed to the strong interchain interaction through basic benzimidazole functions and sulfonic acid groups. The sulfortated polyimides that are incorporated with 1, 1',8,8'-binaphthalimide exhibited better hydrolytic stability than that with 1,4,5,8-naphthalimide. Polyimide membranes with good water stability as well as high proton conductivity were developed. Polyimide membrane (Ia - 90), for example, did not lose mechanical properties after being soaked in boiling water for tOOO h, while its proton conductivity was still at a high level (compared to that of Nafion 117).

Electrostatic assembly of polyaniline and platinum-poly(amidoamine) dendrimers hybrid nanocomposite multilayer, and its electrocatalysis towards CO and O-2

The electrostatic layer-by-layer assembly method was successfully used in a multilayer buildup of polyaniline (PANT) and platinum nanocrystals encapsulated in the carboxyl-terminated poly(amidoamine) dendrimers (generation 4.5 G4.5COOH) (Pt-G4.5COOH NPs) on solid substrates. Multilayer growth was monitored by ultraviolet-visible (UV-vis) absorption spectroscopy. The AFM observation revealed a molecularly smooth (PANI/Pt-G4.5COOH NPs) multilayer film which is rougher and thicker than the multilayer of PANT and G4.5COOH (G4.5COOH/PANI)(m). The PANI/Pt-G4.5COOH NPs multilayers show a fast surface-confined electron-exchange process at the Au electrode in an acid solution, and remains stable, reversible and electroactive, even in neutral solution. Furthermore, the multilayers show a strong elect rocatalytic response towards CO oxidation and O-2 reduction, and the catalytic capability can be easily tuned by the control of multilayer thickness.

Self-assembly of polypeptide-containing ABC-type triblock copolymers in aqueous solution and its pH dependence

Self-assembling of novel biodegradable ABC-type triblock copolymer poly(ethylene glycol)-poly(L-lactide)-poly(L-glutamic acid) (PEG-PLLA-PLGA) is studied. In aqueous media, it self-assembles into a spherical micelle with the hydrophobic PLLA segment in the core and the two hydrophilic segments PEG and PLGA in the shell. With the lengths of PEG and PLLA blocks fixed, the diameter of the micelles depends on the length of the PLGA block and on the volume ratio of H2O/dimethylformamide (DMF) in the media. When the PLGA block is long enough, morphology of the self-assembly is pH-dependent. It assembles into the spherical micelle in aqueous media at pH 4.5 and into the connected rod at or below pH 3.2. The critical micelle concentration (cmc) of the copolymer changes accordingly with decreasing solution pH. Both aggregation states can convert to each other at the proper pH value. This reversibility is ascribed to the dissociation and neutralization of the COOH groups in the LGA residues. When the PLGA block is short compared to the PEG or PLLA block, it assembles only into the spherical micelle at various pH values.

High-pressure sintering study of a novel hard material (W0.5Al0.5)C-0.5 without binder metal

A novel hard material of (W0.5Al0.5)C-0.5 has been successfully sintered under high-pressure (4.5 GPa). The influence of sintering time and temperature on the microstructure, Vickers microhardness and density of the as-prepared specimens are well described. Interestingly, sintering temperature has an amazing influence on the hardness, density and microstructure of the specimen while the sintering time does not. It is found that the most suitable sintering condition from our work is 1600 degrees C and 10 min under pressure of 4.5 GPa. The hardness and relative density of the as-prepared sample can reach 2340 kg mm(-2) and 98.62%, respectively. The cell parameters of the sintered specimen is found to be little smaller than that of the powder, which we propose is related to the high pressure.

基质辅助激光解吸电离飞行时间质谱表征细胞色素C

A matrix-assisted laser desorption ionization time-of-flight mass spectrometry(MALDI-TOF—MS) technique was used for analysis of moleculear weight of cytochrome C.The effects of three kinds of matrix,such as 2,5-dihydroxybenzoic acid(DHB),a-cyano-4-hydroxycinnamic acid(a-CHC) and sinapinic acid(SA),were used to compared and a suitable a-CHC was found.Experimental data showed that this method was properable to analysis of the congeneric biochemical samples.

Synthesis, reactive mechanism and thermal stability of W1-xAlxC (x=0.33, 0.5, 0.75, 0.86) nanocrystalline

W1-xAlxC (x = 0.33, 0.50, 0.75, 0.86) solid solutions have been synthesized directly by ball-milling tungsten powder, aluminum powder and activated carbon. The structural development of W0.5Al0.5C phase with the milling times up to 160 h has been followed using X-ray diffraction. X-ray photoelectron spectra demonstrate that Al atom takes the place of W. High temperature annealing experiment reveals that Al is stable in hexagonal structure to 1873 K. Transmission electron microscopy image shows that the grain size of the prepared powders is about 5 nm.

Synthesis, crystal structure, and thermal property of a novel supramolecular assembly: (NH42810424)(CHNO) O-[H(V)O(]2H)4(10)28(2), constructed from decavanadate and caffeine

A novel 3D supramolecular assembly constructed from decavanadate and caffeine building blocks, (NH4)(2)(C8H10N4O2)(4)[H4V10O28].2H(2)O (1), has been synthesized in aqueous solution and characterized by elemental analysis, IR, H-1 NMR, V-51 NMR, TG-DTA, and single crystal X-Ray diffraction. The compound 1 crystallizes in monoclinic system, space group P2(1)/n, a = 15.801(1) Angstrom, b = 12.914(1) Angstrom, c = 15.913(2) Angstrom, beta = 113.55degrees, V = 2976.4 (5) Angstrom(3), Z = 2, R = 0.0498 with 6818 reflections. Water molecules, ammonium ions, and caffeine act as "cement" linking the polyanions into 1D chain along the c-axis by hydrogen bonding. In compound 1, extensive hydrogen-bond contacts and strong pi-pi interactions lead to an ordered 3D supramolecular framework. TG-DTA curves indicate that the weight loss of the complex can be divided into three stages.

Extraction mechanism of La3+ from hydrochloric acid solution using Cyanex 302

The solvent extraction of La3+ from hydrochloric acid solutions was investigated using his (2, 4, 4-trimethylpentyl) monothiophosphinic acid (Cyanex 302, HL) as an extractant. The effect of equilibrium of aqueous acidity on extraction of La3+ using Cyanex 302 In different diluents was discussed. The effects of extractant concentration and chloride ion on the extraction reaction were also studied. Stoichiometry of the extraction reactions and the nature of metal complexes formed were determined using slope analysis technique and IR measurement.

Extraction of zinc(II) and cadmium(II) by using mixtures of primary amine N1923 and organophosphorus acids

The extraction of zinc(II) and cadmium(II) from a chloride medium by mixtures of primary amine N1923 and organophosphorus acids [di-(2-ethylhexyl)-phosphoric acid, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH/EHP), isopropyl phosphonic acid 1-hexyl-4-ethyloctyl ester, bis(2,4,4-trimethylpentyl) phosphinic acid, bis(2,4,4-trimethylpentyl) monothiophosphinic acid, and bis(2,4,4-trimethylpentyl) dithiophosphinic acid] has been studied in the present paper. Results show that only the mixtures of N1923 + HEH/EHP and N1923 + Cyanex272 have synergistic effects on zinc(II), but the other mixtures have no evident synergistic effects. All six mixtures have no evident synergistic effects on cadmium(H). A possible explanation of the different extraction abilities is given based on the structure of the extractants. Furthermore, the possibilities of separating zinc(II) and cadmium(II) with these mixtures are investigated according to the extractabilities. It is possible to separate Zn2+ from bulk cadmium with N1923 and HEH/EHP mixtures and separate Cd2+ from bulk zinc with N1923 and Cyanex301 mixtures.

Kinetics of extraction and stripping of y(III) by Cyanex 272 as an acidic extractant using a constant interfacial cell with laminar flow

The extraction and stripping kinetics of yttrium(III) with bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, HA) dissolved in heptane as an acid extractant have been investigated by constant interfacial cell with laminar flow. The experimental hydrodynamic conditions have been chosen so that the contribution of diffusion to the measured rate of reaction is minimized. The plot of interfacial area on the rate has shown a linear relationship, which makes the interface the most probable local for the chemical reactions. At the same time, the extraction thermodynamic and kinetic methods are compared to determine the equilibrium extraction constant. A rate equation and the rate-determining step of the extraction and stripping of yttrium(III) have also been obtained, respectively.

Sulfonated poly(arylene-co-naphthalimide)s synthesized by copolymerization of primarily sulfonated monomer and fluorinated naphthalimide dichlorides as novel polymers for proton exchange membranes

A novel sulfonated aromatic dichloride monomer was successfully prepared by the reaction of 2, 5-dichlorobenzophenone with fuming sulfuric acid. Copolymerization of this monomer in the form of sodium salt (1) with N-(4-chloro-2-trifluoromethylphenyl)-5-chloro-1,8-naphthalimide (2) or bis(N-(4-chloro-2-trifluoromethylphenyl)1,4,5,8-naphthalimide (3) generated two series of novel poly(arylene-co-naphthalimide) s I-x and II-x where x represents the content of the sulfonated monomer. The synthesized copolymers with the -SO3H group in the side chains possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymers exhibited excellent stability toward water and oxidation due to the introduction of the hydrophobic CF3 groups. The sulfonated copolyimides that incorporated with 1,8-naphthalimide (I-x) exhibited better hydrolytic and oxidative stabilities than those with 1,4,5,8-naphthalimide. Copolymer I-50 membrane endured for more than 83 h in Fenton's reagent at room temperature. The mechanical properties of I-50 membrane kept almost unchanged after immersing membrane in boiling water for 196 h. The proton conductivities of copolymer films increased with increasing IEC and temperature, reaching values above 6.8 x 10(-1) S/cm at 80 degrees C.

Polypeptide modification of multiwalled carbon nanotubes by a graft-from approach

Covalent surface functionalization of carbon nanotubes with polypeptides is promising for possible medical applications. This work presents a graft-from approach to perform the polypeptide modification of multiwalled carbon nanotubes (MWTNs). The raw MWNTs are first amine-functionalized. The amine-functionalized MWNTs are then used as the initiator to initiate the ring-opening polymerization of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG- NCA), to results in the polypeptide-grafted MWNTs. FT-IR, XPS, and TGA data demonstrate that the functionalization is successful. The TEM images of the products show that the thickness of the polypeptide shell of the PBLG-MWNT is about 4.5-22 nm. Using the facile route developed here, carbon nanotubes functionalized with other types of polypeptides can be easily fabricated using the corresponding NCAs.

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.

The extraction of rare earths using mixtures of acidic phosphorus-based reagents or their thio-analogues

The solvent extraction of rare earths from chloride solution has been investigated using mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, P507) and organophosphorus acids [di-(2-ethylhexyl)phosphoric acid (HDEHP, P204), isopropylphosphonic acid 1-hexyl-4-ethylocryl ester (HHEOIPP), bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272), bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302), and bis(2,4,4-trimethypentyl)dithiophosphinic acid (Cyanex 301)]. Results show that the extractability of the selected extractants for rare earths decreases in the order: HEHEHP/HDEHP > HEHEHP/Cyanex 301 > HEHEHP/HHEOIPP > HEHEHP/Cyanex 302 > HEHEHP/Cyanex 272. A possible explanation of the different extractabilities is given based on the structure of the extractants. Furthermore, the possibilities of the separation of adjacent rare earths with these mixtures were investigated according to the extractabilities; the results show the possibility of separating the rare earths.