Ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. CP/salt complexes showed conductivity up to 10(-5)Scm(-1) at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

The synthesis and thermotropic liquid crystalline behavior of the novel poly(aryl ether ketone)s containing chloro-side group

The novel poly(aryl ether ketone)s containing chloro-side group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and chlorohydroquinone with either 4,4'-difluorobenzophenone(BP/CH/DF) or 1,4-bis(p-fluorobenzoyl)benzene (BP/CH/BF) and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. The thermotropic liquid crystalline behavior was observed in the copolymers containing 50 and 70% biphenol. Melting transition (Tm) and isotropization transition (Ti) both appeared in the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline state. The novel poly(aryl ether ketone)s had relatively higher glass transition temperature (Tg) in the range of 168 similar to 200 degrees C and lower melting temperature (Tm) in the range of 290 similar to 340 degrees C. The thermal stability (Td) was in the range of 430 similar to 490 degrees C.

Studies on water-swellable elastomers .2. Thermal properties and crystalline behavior of amphiphilic graft copolymers with poly(ethylene glycol) side chains

The thermal properties and crystalline structure of the amphiphilic graft copolymers CR-g-PEG600, CR-g-PEG2000, and CR-g-PEG6000 using chloroprene rubber (CR) as the hydrophobic backbone and poly(ethylene glycol) (PEG) with different molecular weights as the hydrophilic side chains were studied by DSC and WAXD. The results showed that a distinct phase-separated structure existed in CR-g-PEGs because of the incompatibility between the backbone segments and the side-chain segments. For all the polymers studied, T-m2, which is the melting point of PEG crystalline domains in CR-g-PEG, decreased compared to that of the corresponding pure PEG and varied little with PEG content. For CR-g-PEG600 and CR-g-PEG2000, T-m1, which is the melting point of the CR crystalline domains, increased with increasing PEG content when the PEG content was not high enough, and at constant PEG content, the longer were the PEG side chains the higher was the T-m1. The crystallite size L-011 of CR in CR-g-PEGs increased compared to that of the pure CR and decreased with increasing PEG content. (C) 1997 John Wiley & Sons, Inc.

Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Lithium ion conducting polymer electrolytes based on alternating maleic anhydride copolymer with oligo-oxyethylene side chains

A comb polymer with oligo-oxyethylene side chains of the type -(CH2CB2O)(12)CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer and poly (ethylene glycol) methyl ether. The polymer can dissolve LiClO4 salt to form homogeneous amorphous polymer electrolyte. The ac ion conduction was measured using the complex impedance method, and conductivities were investigated as functions of temperatures and salt concentration. The complexes were first found to have two classes of glass transition which increase with increasing salt content, The optimum conductivity attained at 25 degrees C is in the order of 5.50 x 10(-6)Scm(-1). IR spectroscopy was used to study the cation-polymer interaction.

Synthesis and thermal transitional properties of side-chain liquid crystalline polyacrylates containing para-nitroazobenzene as mesogenic groups

The synthesis and characterization of side-chain liquid crystalline (LC) polyacrylates containing para-nitroazobenzene (Pn) as mesogenic groups were described. Homopolymers with 3 and 4 carbon atoms in the spacers were non-LC polymers; for homopolymers with 6 carbon atoms in the spacer, nematic LC behavior was observed. Copolymers with acrylic acid as one component exhibited an S-Ad phase according to the WAXD results which showed the d/l of 1.4-1.54 for the copolymers with 3, 4, and 6 carbon atoms in the spacers. Considering the molecular structure as well as the WAXD results of the copolymers, the possible molecular arrangement in the smectic Sad phase was proposed, in which the smectic layers were composed of the antiparallel mesogens and the antiparallel arrangement was considered to be enhanced due to the H bond between - COOH and - NO2. The stress-induced orientational phenomena of Pn in the LC states was also discussed. (C) 1996 John Wiley & Sons, Inc.

A novel structure analysis method for lanthanide complex - None paramagnetic shift tri-lanthanide mixture method

A new structure analysis method for lanthanide complexes was proposed, that is, none paramagnetic shift tri-lanthanide mixture method, It was found that the paramagnetic induced shift could be cancelled by mixing three kinds of paramagnetic lanthanide ions in appropriate proportion. As a result, the chelating sites would he seen simplely from the half widths and the relative distances between lanthanide ion and the ligand nucleus could be calculated from the relaxation time (T-1) or the half width. Care should be addressed that the analysis method is suitable for the systems in which intramolecular arrangements and intermolecular ligand exchanges are relatively fasten NMR time scale used.

LANTHANIDE-INDUCED SHIFT AND RELAXATION RATE STUDIES OF THE AQUEOUS COMPLEXATION OF CITRATE

The aqueous complexation of lanthanide ions with citrate in pH 7.4 solution has been investigated with use of the lanthanide-induced shift and paramagnetic relaxation rate enhancement methods. The results show that citrate coordinates via hydroxyl and central carboxylate groups with lanthanide ions and forms 1:2 (Ln/cit) isostructural complexes through the lanthanide series. A new possible coordination geometry deduced from our experimental data is suggested and discussed.

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.

CONFORMATION OF PHENYL RINGS IN THE HELICAL CHAIN POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The conformation of phenyl rings in the side groups of the helical chain polymer poly(tripenyl-methyl methacrylate) (1) in solution was studied by spectroscopic methods. According to the Raman spectrum the phenyl rings of 1 and triphenylmethyl methacrylate in solution have the same depolarization ratio at 1002 cm-1. The electronic spectra (ultraviolet and fluorescence) of 1 are similar to those of model substances, except for the "red shift" of the spectra of about 5 nm. It was concluded that the phenyl rings can rotate around the phenyl-C bond.

In vitro selected peptides bind with thymidylate synthase mRNA and inhibit its translation

Thymidylate synthase (TS), an essential enzyme for catalyzing the biosynthesis of thymidylate, is a critical therapeutic target in cancer therapy. Recent studies have shown that TS functions as an RNA-binding protein by interacting with two different sequences on its own mRNA, thus, repressing translational efficiency. In this study, peptides binding TS RNA with high affinity were isolated using mRNA display from a large peptide library (>10(13) different sequences). The randomized library was subjected up to twelve rounds of in vitro selection and amplification. Comparing the amino acid composition of the selected peptides (12th round, R12) with those from the initial random library (round zero, R0), the basic and aromatic residues in the selected peptides were enriched significantly, suggesting that these peptide regions might be important in the peptide-TS mRNA interaction. Categorizing the amino acids at each random position based on their physicochemical properties and comparing the distributions with those of the initial random pool, an obvious basic charge characteristic was found at positions 1, 12, 17 and 18, suggesting that basic side chains participate in RNA binding. Secondary structure prediction showed that the selected peptides of R12 pool represented a helical propensity compared with R0 pool, and the regions were rich in basic residues. The electrophoretic gel mobility shift and in vitro translation assays showed that the peptides selected using mRNA display could bind TS RNA specifically and inhibit the translation of TS mRNA. Our results suggested that the identified peptides could be used as new TS inhibitors and developed to a novel class of anticancer agents.

Diet shift of upland buzzards (Buteo hemilasius): evidence from stable carbon isotope ratios

We measured the stable carbon isotope ratios for muscle of the upland buzzards (Buteo hemilasius), plateau pika (Ochotoma curzoniae), root vole (Microtus oeconomus), plateau zokor (Myospalax fontanierii) and passerine bird species at the Haibei Alpine Meadow Ecosystem Research Station (HAMERS), and provided diet information of upland buzzards with the measurement of stable carbon isotopes in tissues of these consumers. The results showed that δ~(13)C values of small mammals and passerine bird species ranged from -25.57‰ to -25.78‰ (n = 12), and from -24.81‰ to -22.51% (n = 43), respectively, δ~(13)C values of the upland buzzards ranged from -22.60‰ to -23.10‰ when food was not available. The difference in δ~(13)C values (2.88‰±0.31‰) between upland buzzards and small mammals was much larger than the differences reported previously, 1‰-2‰, and showed significant difference, while 1.31‰±0.34‰ between upland buzzard and passerine bird species did not differ from the previously reported trophic fractionation difference of 1‰-2‰. Estimation of trophic position indicated that upland buzzards stand at trophic position 4.23, far from that of small mammals, i.e., upland buzzards scarcely captured small mammals as food at the duration of food shortage. According to isotope mass balance model, small mammals contributed 7.89% to 35.04% of carbon to the food source of the upland buzzards, while passerine bird species contributed 64.96% to 92.11%. Upland buzzards turned to passerine bird species as food during times of shortage of small mammals. δ~(13)C value, a useful indicator of diet, indicates that the upland buzzards feed mainly on passerine bird species rather than small mammals due to "you are what you eat" when small mammal preys are becoming scarce.

Pollinator shift and reproductive performance of the qinghai-tibetan plateau endemic and endangered Swertia przewalskii (Gentianaceae)

Reproductive failure results in many plant species becoming endangered. However, little is known of how and to what extent pollinator shifts affect reproductive performance of endangered species as a result of the artificial introduction of alien insects. In this study we examined breeding systems, visitor species, visiting frequency and seed set coefficients of Swertia przewalskii in two years that had different dominant pollinator species (native vs. alien). Flowers of this species were protandrous and herkogamous and insects were needed for the production of seeds. The stigmatic receptivity of this species was shorter than for other gentians. No significant difference in seed set coefficient was found for hand-pollinated plants between the two years, indicating that pollinator shift only had a minor effect on this plant's breeding system. The commonest pollinators in 2002 were native bumblebees, alien honeybees and occasional solitary bees, however, only alien honeybees were observed in 2004. The flower visitation rate in both years was relatively high, although the total visit frequency decreased significantly in 2004. The control flowers without any treatment produced significantly fewer seed sets in 2004 than in 2002. In the past decade the seed production of this species may have partly decreased due to pollination by alien honeybees, however, we suggest that they might have acted as alternative pollinators ensuring seed production of S. przewalskii when native pollinators were unavailable. The main reason that this plant is endangered is probably the result of habitat destruction, but changes in land use, namely intensified agricultural practice and unfavorable animal husbandry have also contributed to its decline. We recommend that in-situ conservation, including the establishment of a protected area, is the best way to preserve this species effectively.

中低纬度变化磁场的暴时特征研究

Magnetic storm is a kind of severe disturbances in the whole solar-earth electromagnetic space. It has significant effects on communication, electric power, oil transport pipe and human activities in space. Therefore, magnetic storms are worth for applications systems, not only being a favorable issue for scientists. In this paper, the spatial and temporal distributions of the magnetic fields produced by the magnetosphere-ionosphere current systems during storms are studied. Four parts are included in this paper decomposion of different disturbances with different origins, topological structure of the ring current, the asymmetric characteristics of the ring current, and the statistic peculiarities of the day-to-day variability (DTD) of Sq. 1 The decomposition of magnetic disturbances at mid-low latitudes and its evolutions during storms Transient variations in the geomagnetic field recorded at mid-low latitudes mainly include the storm-time variation (Dst), solar quiet daily variation (Sq) and disturbance daily variation (SD). With the data of the geomagnetic meridian chain observatories in China, 25 storms during the period of 1997 to 1999 have been analyzed. According to the features of different variations, a method of “three-steps decomposition” is developed by using the method of Natural Orthogonal Components (NOC), Correlation Analysis and Fourier Analysis to separate those three components in turn. The results show that, the first eigenmode by the MNOC clearly describing the special distribution and temporal evolution of storm-time variation, in addition, Correlation Analysis and Fourier Analysis offer a useful method to extract the Sq and SD variations. The latitudinal shift of the Sq current focus seems to be the principal reason of the day-to-day variaitons in the daily range of Sq. The magnitude of SD reaches a maximum during the main phase, and then gradually decreases. 2 The topology structure of the ring current during storms Both the mechanism of the ring current and the geomagnetic data suggest that the central plane of the ring current is declining to the geomagnetic equator plane with a tilt angle δ. Using the H and Z component data at two stations in a meridian chain, we deduce a new parameter describing the invariable peculiarity of different storms. Then the δ angle is calculated by using the data from a meridian chain and tested with the ERC model. Finally the deduced tilt angles are used to modify Dst index. 3 The asymmetric characteristics of the ring current during storms The variations of the geomagnetic field at mid-low latitudes show a significant dawn-dusk asymmetry, resulting from the superposition of the fields from the symmetric ring current and the partial ring current. On the basis of the data from the 20°E, 30°E meridian chains and 30°N latitudinal chain, the dawn-dusk asymmetry is investigated by using three methods, namely, statistic analysis, ring current model calculation and typical event analysis. This characteristic implies the asymmetry of the spatial distribution of the ring current. In addition, during the main phase after the sudden commencement (SC), H field increases and reaches maximum around noontime, implying the effect of the Chapman-Ferraro current. 4 The statistic characteristics of the day-to-day variability and its mechanism The day-to-day variability of the geomagnetic Sq field is studied by using the magnetic data from a meridian chain of magnetometers along 120° E longitude. The method of NOC is applied to separate the Sq variation from complicated disturbances. The first eigenmode with the largest eigenvalue represents fairly well the Sq variation with a conspicuous day-to-day variability in the daily range. For the stations on the same north- or south-side of the Sq current system focus, the day-to-day variations show a positive correlation. In contrast, for the stations on the different sides of the Sq focus, they show a negative correlation, suggesting an important role of latitudinal shift of the Sq current system focus to the day-to-day variability of the Sq daily range. The Sq daily range is correlated with the magnetic indices Ap and Dst in a peculiar way: on some severe disturbed days, noticeably enhancements of the Sq are observed, implying increases of the ionospheric conductivities and/or tidal wind velocities; on other severe disturbed days, however, dramatically reduced Sq variations occur, suggesting dominant effects of the ‘disturbance dynamo’ process.

双聚焦偏移速度估计与可分表示叠前弹性反演

In exploration seismology, the geologic target of oil and gas reservoir in complex medium request the high accuracy image of the structure and lithology of the medium. So the study of the prestack image and the elastic inversion of seismic wave in the complex medium come to the leading edge. The seismic response measured at the surface carries two fundamental pieces of information: the propagation effects of the medium and the reflections from the different layer boundaries in the medium. The propagation represent the low-wavenumber component of the medium, it is so-called the trend or macro layering, whereas the reflections represent the high-wavenumber component of the medium, it is called the detailed or fine layering. The result of migration velocity analysis is the resolution of the low-wavenumber component of the medium, but the prestack elastic inversion provided the resolution of the high-wavvenumber component the medium. In the dissertation, the two aspects about the migration velocity estimation and the elastic inversion have been studied.Firstly, any migration velocity analysis methods must include two basic elements: the criterion that tell us how to know whether the model parameters are correct and the updating that tell us how to update the model parameters when they are incorrect, which are effected on the properties and efficiency of the velocity estimation method. In the dissertation, a migration velocity analysis method based on the CFP technology has been presented in which the strategy of the top-down layer stripping approach are adapted to avoid the difficult of the selecting reduce .The proposed method has a advantage that the travel time errors obtained from the DTS panel are defined directly in time which is the difference with the method based on common image gather in which the residual curvature measured in depth should be converted to travel time errors.In the proposed migration velocity analysis method, the four aspects have been improved as follow:? The new parameterization of velocity model is provided in which the boundaries of layers are interpolated with the cubic spline of the control location and the velocity with a layer may change along with lateral position but the value is calculated as a segmented linear function of the velocity of the lateral control points. The proposed parameterization is suitable to updating procedure.? The analytical formulas to represent the travel time errors and the model parameters updates in the t-p domain are derived under local lateral homogeneous. The velocity estimations are iteratively computed as parametric inversion. The zero differential time shift in the DTS panel for each layer show the convergence of the velocity estimation.? The method of building initial model using the priori information is provided to improve the efficiency of velocity analysis. In the proposed method, Picking interesting events in the stacked section to define the boundaries of the layers and the results of conventional velocity analysis are used to define the velocity value of the layers? An interactive integrate software environment with the migration velocity analysis and prestack migration is built.The proposed method is firstly used to the synthetic data. The results of velocity estimation show both properties and efficiency of the velocity estimation are very good.The proposed method is also used to the field data which is the marine data set. In this example, the prestack and poststack depth migration of the data are completed using the different velocity models built with different method. The comparison between them shows that the model from the proposed method is better and improves obviously the quality of migration.In terms of the theoretical method of expressing a multi-variable function by products of single-variable functions which is suggested by Song Jian (2001), the separable expression of one-way wave operator has been studied. A optimization approximation with separable expression of the one-way wave operator is presented which easily deal with the lateral change of velocity in space and wave number domain respectively and has good approach accuracy. A new prestack depth migration algorithm based on the optimization approximation separable expression is developed and used to testing the results of velocity estimation.Secondly, according to the theory of the seismic wave reflection and transmission, the change of the amplitude via the incident angle is related to the elasticity of medium in the subsurface two-side. In the conventional inversion with poststack datum, only the information of the reflection operator at the zero incident angles can be used. If the more robust resolutions are requested, the amplitudes of all incident angles should be used.A natural separable expression of the reflection/transmission operator is represented, which is the sum of the products of two group functions. One group function vary with phase space whereas other group function is related to elastic parameters of the medium and geological structure.By employing the natural separable expression of the reflection/transmission operator, the method of seismic wave modeling with the one-way wave equation is developed to model the primary reflected waves, it is adapt to a certain extent heterogeneous media and confirms the accuracy of AVA of the reflections when the incident angle is less than 45'. The computational efficiency of the scheme is greatly high.The natural separable expression of the reflection/transmission operator is also used to construct prestack elastic inversion algorithm. Being different from the AVO analysis and inversion in which the angle gathers formed during the prstack migration are used, the proposed algorithm construct a linear equations during the prestack migration by the separable expression of the reflection/transmission operator. The unknowns of the linear equations are related to the elasticity of the medium, so the resolutions of them provided the elastic information of the medium.The proposed method of inversion is the same as AVO inversion in , the difference between them is only the method processing the amplitude via the incident angle and computational domain.