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.

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Facilitated ion transfer reactions of 20 amino acids with di.benzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, Ile, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (beta(0)), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization.

Electrochemical recognition of alkali metal ions at the micro-water 1,2-dichloroethane interface using a calix[4]arene derivative

In this paper, a calix[4]arene derivative, 5,11,17,23-butyl-25,26,27,28-tetra-(ethanoxycarbonyl)-methoxy-calix[4]arene (L), is investigated as a host to recognize alkali metal ions (Li+, Na+, K+, Rb+ and Cs+) at the interface between two immiscible electrolyte solutions (ITIES). Well-defined cyclic voltammograms are obtained at the micro- and nano-water \ 1,2-dichloroethane (W \ DCE) interfaces supported at micro- and nano-pipets.

The structural transition of DNA-Tris(1,10-phenanthroline) cobalt(III) complexes in ethanol-water solution

The interaction of DNA with Tris(1,10-phenanthroline) cobalt(III) was studied by means of atomic force microscopy. Changes in the morphologies of DNA complex in the presence of ethanol may well indicate the crucial role of electrostatic force in causing DNA condensation. With the increase of the concentration of ethanol, electrostatic interaction is enhanced corresponding to a lower dielectric constant. Counterions condense along the sugar phosphate backbone of DNA when e is lowered and the phosphate charge density can thus be neutralized to the level of DNA condensation. Electroanalytical measurement of DNA condensed with Co(phen)(3)(3+) in ethanol solution indicated that intercalating reaction remains existing. According to both the microscopic and spectroscopic results, it can be found that no secondary structure transition occurs upon DNA condensing. B-A conformation transition takes place at more than 60% ethanol solution.

Alkali metal ions transfer across a water/1,2-dichloroethane interface facilitated by a novel monoaza-B15C5 derivative

In this paper, a novel monoaza-B15C5 derivative, N-(2-tosylamino)-isopentyl-monoaza-15-crown-5 (L), is used as an ionophore to facilitate alkali metal cations transfer across a water/1,2-dichloroethane (W/DCE) interface. Well-defined voltammetric behaviors are observed at the polarized W/DCE interfaces supported at micro- and nano-pipets except Cs+. The diffusion coefficient of this ionophore in the DCE phase is calculated to be equal to (3.3+/-0.2) x 10(-6) cm(2) s(-1). The experimental results indicate that a 1:1 (metal: ionophore) complex is formed at the interface with a TIC/TID mechanism. The selectivity of this ionophore towards alkali ions follows the sequence Na+ > Li+ > K+ > Rb+ > Cs+. The logarithm of the association constants (log beta(1)(0)) of the LiL+, NaL+, KL+ and RbL+ complexes in the DCE phase are calculated to be 10.6, 11.6, 9.0 and 7.1, respectively. The kinetic parameters are determined by steady-state voltammograms using nanopipets. The standard rate constants (k(0)) for Li+, Na+, K+ and Rb+ transfers facilitated by L are 0.54+/-0.05, 0.63+/-0.09, 0.51+/-0.04 and 0.46+/-0.06 cm s(-1), respectively. The pH values of aqueous solution have little effect on the electrochemical behaviors of these facilitated processes. The results predicate that this new type of ionophore might be useful to fabricate electrochemical sensor of sodium ion.

The application of the MPB4 theory to the interface between between two immiscible electrolyte solutions .4. The differential capacitance of the water/nitrobenzene interface in the presence of 2:2 electrolyte

We have developed a new theoretical model based on the MPB4 theory to calculate the differential capacitance of the interface of 0.05mol/L MgSO4 in water and 0.1mol/L TBATPB in nitrobenzene. Our results coincide with the experimental values very well. It indicates that our model may describe well the structure of ITIES not only in the presence of 1:1 electrolyte but also in the presence of 2:2 electrolyte.

CHARACTERIZATION OF A POTASSIUM-PROMOTED COBALT MOLYBDENUM ALUMINA WATER-GAS SHIFT CATALYST

A series of potassium-promoted CoMo/Al2O3 has been investigated by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR). CoMoO4 was found in the CoMo/Al2O3 catalyst by XRD and is destroyed by the presence of potassium. The reducibility of molybdenum is enhanced by potassium in the CoMoK/Al2O3 catalyst and is easier to reduce to Mo(IV) during sulfidation. In the oxidic state catalyst cobalt is increased on the surface by the addition of potassium. After sulfidation this phenomena disappeared, the distribution of cobalt remains at a constant level and is unaffected by the potassium content. The addition of potassium leads to a monotonical decrease of the molybdenum dispersion with the impregnating amount of potassium in the oxidic state catalyst but is more complicated after sulfidation. Potassium is well dispersed on the surface in both the oxidic and sulfided state. The activity in the water-gas shift reaction was correlated with the potassium content of CoMoK/Al2O3.

WATER-SOLUBLE AND AMPHIPHILIC POLYMERS .6. A STUDY ON THE SURFACE-COMPOSITION OF CAST FILMS OF PST/PMAA AND PEO-PST-PEO BLOCK POLYMERS BY XPS

Thin films of PSt/PMAA and PEO-PSt-PEO block polymers were deposited on a polystyrene substrate by solution adsorption (with or without solvent treatment), and the film surfaces were characterized by means of XPS. Direct solvent - casting of PEO-PSt-PEO from benzene solutions resulted in PSt-rich surfaces, whereas PMAA richer surfaces were obtained for PSt/PMAA films cast from DMF solutions. Moreover, solvent treatment after casting had profound effect on the film surface composition. Treatment with water markedly increased the surface concentration of polar PEO segments. In the case of PSt-PMAA block polymers, the PSt content on the surface increased in the order of water < ethanol < cyclohexane < petroleum ether, the last-named giving films with almost pure PSt surface. It is well worth noticing that the bulk composition had little to do with the surface composition for both PSt/PMAA and PEO-PSt-PEO block polymers within the composition range investigated when subsequent solvent treatment was applied.

Three-stage transformation of chlorophyll transient fluorescence pattern under sustained dehydration and the discovery of critical water content in seaweeds

The chlorophyll fluorescence kinetics of marine red alga Grateloupia turutunt Yamada, green alga Ulva pertusa Kjellm and brown alga Laminaria japonica Aresch during natural sustained dehydration were monitored and investigated. The pulse amplified modulation (PAM) system was used to analyze the distinct fluorescence parameters during thallus dehydration. Results proved that the fluorescence kinetics of different seaweed all showed three patterns of transformation with sustained water loss. These were: 1) peak kinetic pattern (at the early stage of dehydration fluorescence enhanced and quenched subsequently, representing a normal physiological state). 2) plateau kinetic pattern (with sustained water loss fluorescence enhanced continuously but quenching became slower, finally reaching its maximum). 3) Platform kinetic pattern (fluorescence fell and the shape of kinetic curve was similar to plateau kinetic pattern). A critical water content (CWC) could be found and defined as the percentage of water content just prior to the fluorescence drop and to be a significant physiological index for evaluation of plant drought tolerance. Once thallus water content became lower than this value the normal peak pattern can not be recovered even through rehydration, indicating an irreversible damage to the thylakoid membrane. The CWC value corresponding to different marine species were varied and negatively correlated with their desiccation tolerance, for example. Laminaria japonica had the highest CWC value (around 90%) and the lowest dehydration tolerance of the three. In addition, a fluorescence "burst" was found only in red algae during rehydration. The different fluorescence parameters F-o, F-v and F-v, F-m were measured and compared during water loss. Both F-o and F-v increased in the first stage of dehydration but F-v/F-m. kept almost constant. So the immediate response of in vivo chlorophyll fluorescence to dehydration was an enhancement. Later with sustained dehydration F-o increased continuously while F-v decreased and tended to become smaller and smaller. The major changes in fluorescence (including fluorescence drop during dehydration and the burst during rehydration) were all attributed to the change in F-o instead of F-v This significance of F-o indicates that it is necessary to do more research on F-o as well as on its relationship with the state of thylakoid membrane.

Benthic foraminiferal distribution in surface sediments along continental slope of the southern Okinawa Trough: dependance on water masses and food supply

Benthic foraminiferal analysis of 29 samples in surface sediments from the southern Okinawa Trough is carried out. The results indicate that benthic foraminiferal abundance decreases rapidly with increasing water depth. Percentage frequencies of agglutinated foraminifera further confirm the modem shallow carbonate lysocline in the southern Okinawa Trough. From continental shelf edge to the bottom of Okinawa Trough, benthic foraminiferal fauna in the surface sediments can be divided into 5 assemblages: (1) Continental shelf break assemblage, dominated by Cibicides pseudoungerianus, corresponds to subsurface water mass of the Kuroshio Current; (2) upper continental slope assemblage, dominated by Cassidulina carinata, Globocassidulina subglobosa, corresponds to intermediate water mass of the Kuroshio Current; (3) intermediate continental slope assemblage, dominated by Uvigerina hispida, corresponds to the Okinawa Trough deep water mass above the carbonate lysocline; (4), lower continental slope - trough bottom assemblage, dominated by Pullenia bulloides, Epistominella exigua and Cibicidoides hyalinus, corresponds to deep water mass of the Okinawa Trough; and (5) trough bottom agglutinated assemblage, dominated by Rhabdammina spp., Bathysiphon flavidus, corresponds to I strongly dissolved environment of the trough bottom. The benthic foraminiferal fauna in the southern Okinawa Trough are controlled jointly by water masses and food supply. Water temperature, oxygen concentration and carbonate dissolution of the water masses are important controlling factors especially for the continental shelf break and trough bottom assemblages. The food supply also plays an important role in these benthic foraminiferal assemblages along the western slope. of the Okinawa Trough. Both the abundance and the 5 assemblages of benthic foraminifera correspond well to the organic matter supply along the continental slope and a lateral transport of TSM (total suspended matter) and POC (particulate organic carbon) from the shelf break to the deep water is also an important food supply for benthic fauna in this region.

Origin and Pathway of Equatorial 13 degrees C Water in the Pacific Identified by a Simulated Passive Tracer and Its Adjoint

The origin and pathway of the thermostad water in the eastern equatorial Pacific Ocean, often referred to as the equatorial 13 degrees C Water, are investigated using a simulated passive tracer and its adjoint, based on circulation estimates of a global general circulation model. Results demonstrate that the source region of the 13 degrees C Water lies well outside the tropics. In the South Pacific, some 13 degrees C Water is formed northeast of New Zealand, confirming an earlier hypothesis on the water's origin. The South Pacific origin of the 13 degrees C Water is also related to the formation of the Eastern Subtropical Mode Water (ESTMW) and the Sub-Antarctic Mode Water (SAMW). The portion of the ESTMW and SAMW that eventually enters the density range of the 13 degrees C Water (25.8 < sigma(theta) < 26.6 kg m(-3)) does so largely by mixing. Water formed in the subtropics enters the equatorial region predominantly through the western boundary, while its interior transport is relatively small. The fresher North Pacific ESTMW and Central Mode Water (CMW) are also important sources of the 13 degrees C Water. The ratio of the southern versus the northern origins of the water mass is about 2 to 1 and tends to increase with time elapsed from its origin. Of the total volume of initially tracer-tagged water in the eastern equatorial Pacific, approximately 47.5% originates from depths above sigma(theta) = 25.8 kg m(-3) and 34.6% from depths below sigma(theta) = 26.6 kg m(-3), indicative of a dramatic impact of mixing on the route of subtropical water to becoming the 13 degrees C Water. Still only a small portion of the water formed in the subtropics reaches the equatorial region, because most of the water is trapped and recirculates in the subtropical gyre.

Numerical modeling of water wave interaction with a soft mud bed

A vertical 2-D numerical model is presented for simulating the interaction between water waves and a soft mud bed. Taking into account nonlinear rheology, a semi-empirical rheological model is applied to this water-mud model, reflecting the combined visco-elasto-plastic properties of soft mud under such oscillatory external forces as water waves. In order to increase the resolution of the flow in the neighborhood of both sides of the inter-surface, a logarithmic grid in the vertical direction is employed for numerical treatment. Model verifications are given through comparisons between the calculated and the measured mud mass transport velocities as well as wave height changes.

Origins and pathways of the subsurface and intermediate water masses of the Indonesian Throughflow derived from historical and Argo data

On the basis of Argo data and historic temperature/salinity data from the World Ocean Database 2001 (WOD01 origins and spreading pathways of the subsurface and intermediate water masses in the Indonesian Throughflow (ITF) region were discussed by analyzing distributions of salinity on representative isopycnal layers. Results were shown that, Subsurface water mostly comes from the North Pacific Ocean while the intermediate water originates from both the North and South Pacific Ocean, even possibly from the Indian Ocean. Spreading through tire Sulawesi Sea, the Makassar Strait, and the Flores Sea, the North Pacific subsurface water and the North Pacific Intermediate water dominate the western part of the Indonesian Archipelago. Furthermore its the depth increases, the features of the North Pacific sourced water masses become more obvious. In the eastern part of the waters, high salinity South Pacific subsurface water is blocked by a strong salinity front between Halmahera and New Guinea. Intermediate water in the eastern interior region owns salinity higher than the North Pacific intermediate water and the antarctic intermediate water (AAIW), possibly coming from the vertical mixing between subsurface water and the AAIW from the Pacific Ocean, and possibly coming front the northward extending of the AAIW front the Indian Ocean as well.

Summer reproduction of the planktonic copepod Calanus sinicus in the Yellow Sea: influences of high surface temperature and cold bottom water

We have observed that Calanus sinicus retreated from neritic areas in the Yellow Sea and concentrated in the Yellow Sea Cold Bottom Water (YSCBW) area in summer. To investigate the summer reproductive strategy of C. sinicus in this situation, effects of high temperature on reproduction and hatching, as well as geographical variation of in situ egg production rate, were studied by onboard incubation in August 2001. Diel vertical migration (DVM) of females was investigated within and outside the YSCBW, respectively. Onboard incubation at 27 degrees C (i.e. surface temperature) resulted in lower fecundities than that at 9.8 and 12 degrees C (i.e. bottom temperature inside and outside the YSCBW) together with decreased hatching rates and increased naupliar malformation. Egg production was more active at stations outside the YSCBW than inside, where chlorophyll-a concentration was also relatively low. Females inside the YSCBW underwent DVM although they rarely entered the surface layer, but DVM was not observed outside the YSCBW. We conclude that surface temperature in summer has deleterious effects on C. sinicus egg production and hatching, and that it cannot reproduce successfully over the whole area. Inside the YSCBW, egg production is depressed by low food availability, while females outside suffer from high temperatures because of strong vertical mixing.

Morphology and Molecular Phylogeny of Trimyema koreanum n. sp., a Ciliate from the Hypersaline Water of a Solar Saltern

A new ciliate, Trimyema koreanum n. sp., isolated from hypersaline water (salinity of 293 parts per thousand) from a solar saltern in Korea, was investigated using live observation, protargol impregnation, and gene sequencing. Trimyema koreanum is about 30 x 13 mu m in vivo, has usually 23 longitudinal ciliary rows forming two distinct ciliary girdles visible both in vivo and in protargol impregnation. A third indistinct ciliary girdle as well as a girdle of mucocysts is distinguishable only in impregnated cells. We suggest T. koreanum as a new species, differing from the most similar species, T. marinum, by the presence of two distinct ciliary girdles (T. marinum usually has six ciliary girdles clearly visible in living cells and three anterior spirals that encircle the cell completely). Although the number of known 18S rRNA sequences in the genus Trimyema was limited, the Trimyema group including T. koreanum forms a strong clade. The phylogenetic position confirms that the isolate belongs to the genus Trimyema and is different from previously sequenced species. Trimyema koreanum is able to consume both prokaryotes and small eukaryotes (specifically, the alga Dunaliella sp.).