New proton exchange membranes based on poly (vinyl alcohol) for DMFCs

A series of new composite proton exchange membranes for direct methanol fuel cells (DMFCs) based on poly (vinyl alcohol) (PVA), phosphotungstic acid (PWA) and silica were prepared. The highest proton conductivity (a) of these membranes is 0.017 S/cm at ambient temperature. The methanol permeability (D) of these composite membranes ranges from 10(-7) to 10(-8) cm(2)/S. From the ratios of sigma/D, it was found that the optimal weight composition of the PVA/PWA/SiO2 membrane is PVA/PWA/SiO2=0.40:0.40:0.20 wt. Infrared (IR) spectrographic measurements indicate that the Keggin structure characteristics of the PW12O403- anion is present in the composite membranes. Cyclic voltammetry shows that the electrochemical stability window of the complex membrane is from -0.5 to 1.5 V vs. Ag/AgCl electrode. The results of differential scanning calorimetry (DSC) show that silica can improve the thermal stability of the complexes and the single Tg of the membrane indicates that the membrane is homogeneous. The complexes behave as X-ray amorphous.

Novel hole-transporting materials based on 1,4-bis(carbazolyl)benzene for organic light-emitting devices

Novel hole-transporting molecules containing 1,4-bis(carbazolyl)benzene as a central unit and different numbers of diphenylamine moieties as the peripheral groups have been synthesized and characterized. These compounds are thermally stable with high glass transition temperatures of 141-157 degreesC and exhibit chemically reversible redox processes. Their amorphous state stability and hole transport properties can be significantly improved by increasing the number of diphenylamine moieties in the outer part and by controlling the symmetry of the carbazole-based molecules. These compounds can be used as good hole-tran sporting materials for organic electroluminescent (EL) devices. The device performance based on tri- and tetra-substituted carbazole derivatives is comparable to that of a typical 4,4'-bis[N-(1-naphthyl)-N-phenylamino] biphenyl (NPB)-based device.

A room-temperature ionic-liquid-templated proton-conducting gelatinous electrolyte

Novel proton-conducting gelatinous electrolytes templated by room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF(4)) have been prepared in methylsisesquioxane backbone containing H3PO4, and the influences of the RTIL on the structure, morphology, thermal stability, and electrochemical properties of the gelatinous electrolytes have been examined. X-ray diffraction and scanning electron microscopy proved that BMImBF(4) acted as structure-directing template during the sol-gel process of methyl-trimethoxysilane. X-ray photoelectron spectra and infrared spectroscopy demonstrated that the hydrogen-bonding was formed between BMImBF(4) and H3PO4. The electrolytes had good thermal stability up to 300 degreesC and showed superior mechanical and electrochemical properties. A room-temperature conductivity of 1.2 x 10(-3) S cm(-1) was obtained for the electrolyte at the molar ratio of RTIL/Si/H3PO4 0.3/1/1, and its electrochemical window was up to 1.5 V.

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.

The direct synthesis of wholly aromatic poly(p-phenylene)s bearing sulfobenzoyl side groups as proton exchange membranes

Sulfonated poly(p-phenylene)s (SPPs) containing sulfonic acid groups in their side chains had been directly synthesized by Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and 2,5-dichlorobenzophenone. The synthesized copolymers possessed high molecular weights revealed by their high viscosity, and the formation of tough and flexible membranes by casting from DMAc solution. The copolymers exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. Transmission electron microscopic (TEM) analysis revealed that these side-chain type SPP membranes have a microphase-separated structure composed of hydrophilic side-chain domains and hydrophobic polyphenylene main chain domains. The proton conductivities of copolymer membranes increased with the increase of IEC and temperature, reaching values above 3.4 x 10(-1) S/cm at 120 degrees C, which are almost 2-3 times higher than that of Nafion 117 at the same measurement conditions. Consequently, these materials proved to be promising as proton exchange membranes.

Well defined carbazole-based hole-transporting amorphous molecular materials

Monodisperse carbazole-based oligomers have been synthesized via C-N bonds formation by the modified Ullmann reaction. The full characterization of their structure is presented. These derivatives are highly thermally stable amorphous compounds with glass transition temperatures of 167-171 degrees C and thermal decomposition temperatures of ca. 400 degrees C. Amorphous films of the materials were fabricated and their hole-transporting properties were tested in a light emitting device with Alq(3) as an electroluminescent and electron-transporting material.

Carbazole-based hole-transporting materials for electroluminescent devices

Two kinds of carbazole-based molecules connected with diphenylamine and carbazole are synthesized by modified Ullmann reaction. Comparative study on their thermal stability, redox behavior, hole injection and transport properties are present. The results demonstrate that the carbazole-based molecules are very promising hole-transporting materials for electroluminescent devices.

Polymer light-emitting diodes based on a bipolar transporting luminescent polymer

A soluble electroluminescent polymer containing hole-deficient triphenylamine and electron-deficient oxadiazole units in the main chains has been designed and studied. The design is based on the consideration that the triphenylamine group possesses good hole-transporting property and the oxadiazole unit is known to be of electron-transporting character. Because of the good bipolar transporting performance, the brightness and electroluminescent efficiency are significantly improved and the turn-on voltage is reduced compared with a similar polymer without the electron-deficient oxadiazole units in the main chains. For a device with configuration ITO/PEDOT/polymer/CsF/Al, a maximum brightness of 3600 cd m(-2) and a maximum luminescent efficiency of 0.65 cd A(-1) (quantum efficiency of 0.3%) were obtained in the polymer with oxadiazole units, about 15 times brighter and 15 times more efficient than the corresponding polymer without oxadiazole units.

Blue organic light-emitting diodes based on an oxadiazole-containing organic molecule exhibiting excited state intramolecular proton transfer

A blue organic light-emitting device based on an emissive layer of 2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazole (HOXD), which exhibits excited state intramolecular proton transfer (ESIPT), was presented. The device had a luminance efficiency of 0.8 cd/A and a maximum brightness of 870 cd/m(2). Our studies indicate that some EL may originate from the triplet excitation state of the enol form of HOXD.

Evaluation of bioeffects of a long-term administering ChangLe on rat by proton NMR method and biochemical examination

High resolution H-1 nuclear magnetic resonance ( NMR) spectroscopy has been employed to assess long-term toxicological effects of ChangLe (a kind of rare earth complex applied in agriculture). Male Wistar rats were administrated orally with ChangLe at doses of 0, 0.1, 0.2, 2.0, 10 and 20 mg/kg body weight daily, respectively, for 6 months. Urine was collected at-day 30, 60, go and serum samples were taken after 6 months. Many low-molecular weight metabolites were identified by H-1 NMR spectra of rat urine. A decrease in citrate and an increase in ketone bodies, creatinine, DMA, DMG, TMAO, and taurine in the urine of the rats. receiving high doses were found by H-1 NMR spectra. These may mean that high-dosage of ChangLe impairs the specific region of liver and kidney, such as renal tubule and mitochondria. The decrease in citrate and the increase in succinate and alpha-ketoglutarate were attributed to a combination of the inhibition of certain citric acid enzymes, renal tubular acidosis and the abnormal fatty acid catabolism. The information of the renal capillary necrosis could be derived from the increase in DMIA, DMG and TMAO. The increase in taurine was due to hepatic mitochondria dysfunction. The conclusions were supported by the results of biochemical measure. merits and enzymatic assay.

Blue organic light-emitting devices with an oxadiazole-containing emitting layer exhibiting excited state intramolecular proton transfer

We report a blue organic light-emitting device having an emissive layer of 2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazole (HOXD), that exhibits excited state intramolecular proton transfer (ESIPT). The device had a luminance efficiency of 0.8 cd/A and a maximum brightness of 870 cd/m(2). Electroluminescence spectra revealed a dominating peak at 450 nm and two additional peaks at 480 and 515 nm with a full width at half maximum of 50 nm. Our studies indicate that some EL may originate from the triplet excitation state of the enol form of HOXD.

Synthesis of novel nitrogen- and sulfur-containing conjugated polymers used as hole-transporting materials for organic light-emitting diodes

Two series of highly soluble novel nitrogen- and sulfur-containing conjugated polymers were synthesized via an acid-induced self-polycondensation of functional monomers with methyl sulfinyl and aromatic groups. The well-defined structures of synthesized polymers were confirmed by their NMR and IR spectra. The highest occupied molecular orbital energy values for these materials, estimated by cyclic voltammetry, showed a broad range of values from about 5.0 to 5.2 eV used as hole-transport layers (HTL) in two-layer light-emitting diodes ITO/HTL/Alq(3)/Mg:Ag [ITO = indium tin oxide, and Alq(3) = tris(8-quinolinato) aluminum]. The typical turn-on voltage of these diodes was about 4-5 V. The maximum brightness of the device was about 3440 cd/m(2) at 20 V. The maximum efficiency was estimated to be 0.15 1m/W at 10 V.

Effect of rare earth element on the metabolism in rats by high resolution proton nuclear magnetic resonance spectroscopy

The high-field nuclear magnetic resonance (NMR) spectra can be used for the rapid multicomponent analysis in small amounts of biological fluids. In this paper, the effect of La (NO3)(3) on the rats' metabolism in urine was investigated by H-1 NMR analysis. The experimental groups of wistar rats were injected intraperitoneally with La(NO3)(3) at doses of 0.2, 2.0, 10 and 20mg/kg body weight. The remarkable variation of low molecular weight metabolites in urine has been identified by H-1 NMR spectra, in which dimethylamine, N, N-dimethylglycine, urea, alpha -ketoglutarate, trimethylamine N-oxide, succinate, citrate and amino acids have been suggested as NMR markers for renal damage and ethanol, lactate, taurine as the markers for liver damage. This work may assess its possible use in the early detection of biochemical changes associated with Rare Earth induced kidney and liver dysfunction.