Study of the conductivity and side chain mobility of a comb-like polymer electrolyte using the dynamic mechanical method

Using poly(styrene-co-maleic anhydride) as a backbone and poly(ethylene glycol) methyl ether (PEGME) with different molecular weights as side chains, three comb-like polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the polymer electrolytes possess two glass transitions: alpha -transition and beta -transition, and the temperature dependence of the ionic conductivity shows WLF (Williams-Landel-Ferry) behavior. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T-beta as reference temperature. The values of the WLF parameters (C-1 and C-2) were obtained and were found to be almost independent of the length of the PEGME side chain and the content of Li salt. By reference to T-0 = 50 degreesC. the relation between log tau (c) and c was found to be linear. The master curves are displaced progressively to higher frequencies as the molecular weight of the side chain is increased. The relation between log tau (n) and the molecular weight of the side chain is also linear. (C) 2001 Elsevier Science B.V. All rights reserved.

Effect of hydrogen bonds on optical nonlinearities of inorganic crystals

This work probes the role of hydrogen bonds (such as O-H ... O and N-H ... O) in some inorganic nonlinear optical (NLO) crystals, such as HIO3, NH4H2PO4 (ADP), K[B5O6(OH)(4)] . 2H(2)O (KB5) and K2La(NO3)(5) . 2H(2)O (KLN), from the chemical bond standpoint. Second order NLO behaviors of these four typical inorganic crystals have been quantitatively studied, results show hydrogen bonds play a very important role in NLO contributions to the total nonlinearity. Conclusions derived here concerning the effect of hydrogen bonds on optical nonlinearities of inorganic crystals have important implications with regard to the utilization of hydrogen bonds in the structural design of inorganic NLO crystals. (C) 1999 Elsevier Science B.V. All rights reserved.

Solvent extraction of scandium(III) by Cyanex 923 and Cyanex 925

The extraction equilibria of Sc(III), Zr(IV), Ti(IV), Th(IV), Fe(III) and Lu(III) from sulphuric or hydrochloric acid media by Cyanex 923 (mixture of straight chain alkylated phosphine oxides) and Cyanex 925 (mixture of branched chain alkylated phosphine oxides) were studied at various aqueous acidities. The extractant Cyanex 923 demonstrated better scandium loading and selectivity for TI(IV). Fe(III) and Lu(III) than Cyanex 925. The effects of extractant concentration on the extractions of sulphuric acid and Sc(III) by Cyanex 923 were examined. The stoichiometries of the extraction reactions were postulated based on slope analysis. The experimental results indicate that Cyanex 923 can be employed to recover scandium directly from the hydrolytic mother solution arising from TiO2 production via the sulphate process. The parameters studied were scandium loading capacity, phase ratio, concentrations of Ti(IV) scrubbing and Sc(III) stripping agents. A new solvent extraction technology of scandium recovery was developed. The purity of the final Sc(III) product is above 95% with a yield > 94%. (C) 1998 Elsevier Science B.V.

Matrix-assisted laser desorption/ionization of ginsenosides

Molecular weight of 8 ginsenosides and the component of total saponions in American ginseng have been determined by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The average error of the molecular weight of each ginsenoside was found less than 0.05%. The results demonstrate that MALDI-MS is a very simple and useful method to measure the molecular weight of some high polar, thermal unstable small molecules with high sensitivity and reproducibility.

Theoretical investigation of LaC3n+ (n = 0, 1, 2) clusters by density functional theory

LaC3n+ (n = 0, 1, 2) clusters have been studied using B3LYP (Becke 3-parameter-Lee-Yang-Parr) density functional method. The basis set is Dunning/ Huzinaga valence double zeta for carbon and [2s2p2d] for lanthanum, denoted LANL1DZ. Four isomers are presented for each cluster; two of them are edge binding isomers with C-2 upsilon symmetry, the other two are Linear chains with C-infinity upsilon symmetry. Meanwhile, two spin states for each isomer, that is, singlet and triplet for LaC3+, doublet and quartet for LaC3 and LaC32+, respectively, are also considered. Geometries, vibrational frequencies, infrared intensities, and other quantities are reported and discussed. The results indicate that at some spin states; the C-2 upsilon symmetry isomers are the dominant structures, while for the other spin states, linear isomers are energetically favored. (C) 1998 John Wiley & Sons, Inc.

裸玻碳电极伏安测定甲氰咪胍

提出了裸ＧＣＥ不需任何处理测定甲氰咪胍的方法．浓度在３×１０－７～６×１０－５ｇ／ｍＬ范围内与峰电流呈线性关系，ＲＳＤ为２．２％（ｎ＝１０）．，回收率为９６％～１０２％．该方法操作简便快速，大多数金属离子和多种有机生化物质不干扰测定，方法用于片剂和加标尿样中甲氰咪胍的测定与药典方法对照，获得满意结果，并对电极反应进行了初步探讨.

人参皂苷的基质辅助激光解吸质谱研究

利用MALDI-TOFMS测定了八种人参皂苷的分子量,并分析了西洋参总皂苷的组成.同时,进行了灵敏度实验,并探讨了基质及碱金属离子的影响,证明该方法灵敏度高,重复性好,结果准确.是测定极性小分子分子量的有效方法.

生理条件下稀土及钙、锌离子与L-羟脯氨酸配位作用的研究

生理条件下稀土及钙、锌离子与Ｌ－羟脯氨酸配位作用的研究＊高峰＊＊牛春吉孟淑兰倪嘉缵（中国科学院长春应用化学研究所稀土化学和物理开放实验室长春１３００２２）金天柱王瑞瑶王祥云（北京大学稀土材料化学和应用国家重点实验室北京１００８７１）关键词稀土钙锌Ｌ－…

Study of ion solvation and ion association in polymer gel electrolyte with polyethylene oxide-co-polypropylene oxide as a plasticizer

Using a molal conductance method, ion solvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)-LiClO4 gel electrolytes with amorphous ethylene oxide-co-propylene oxide (EO-co-PO, <(M)over bar (n)>, = 1750) as the plasticizer were investigated. It was found that the fraction of solute existing as single ions (alpha(i)) and ion pairs (alpha(p)) decreases, while that of triple ions (alpha(t)) increases linearly with increasing salt concentration. The dependence of these fractions on molecular weight of plasticizer was also examined. It was shown that alpha(i) and alpha(t) increase and alpha(p) decreases with increasing molecular weight. The result of temperature dependence of these fractions was very interesting: when the temperature is lower than 55 degrees C, alpha(i) increases while alpha(p) and alpha(t) decrease with increasing temperature; however, when the temperature is higher than 55 degrees C, the reverse is true.

SOLVENT-EXTRACTION OF SC(III), ZR(IV), TH(IV), FE(III), AND LU(III) WITH THIOSUBSTITUTED ORGANOPHOSPHINIC ACID EXTRACTANTS

The solvent extraction of Sc(III), Zr(IV), Th(IV), Fe(III) and Lu(III) with Cyanex 302 (bis(2,4,4-trimethylpentyl)monothiophosphinic acid) and Cyanex 301 ( bis(2,4,4-trimethylpentyl) dithiophosphinic acid) in n-hexane from acidic aqueous solutions has been investigated systematically. The effect of equilibrium aqueous acidity on the extraction with these reagents was studied. The separation of Th(IV), Fe(III) and Lu(III) from Sc(III), or the separation of other metals from Lu(III) with Cyanex 302, can be achieved by controlling the aqueous acidity. However, Cyanex 301 exhibited a poor selectivity for the above metals, except for Lu(III). The extraction of these metals with Cyanex 272, Cyanex 302 and Cyanex 301 has been compared. The stripping percentages of Sc(III) for Cyanex 302 and Cyanex 301 in a single stage are near 78% and 75% with 3.5 mol/L and 5.8 mol/L sulphuric acid solutions, respectively. The effects of extractant concentration and temperature on the extraction of Sc(III) were investigated. The stoichiometry of the extraction of Sc(III) with Cyanex 302 was determined. The role of different components of Cyanex 302 in the extraction of Sc(III) was discussed.

大鼠精索静脉曲张对睾丸氧自由基和LPO浓度的影响

应用成年Ｗｉｓｔａｒ大鼠制作精索静脉曲张动物模型，术后３月，处死动物取出睾丸。以电子自旋共振（ＥＳＲ）法测试睾丸组织的氧自由基相对自旋浓度，ＴＢＡ法和化学发光法分别检测过氧化脂质（ＬＰＯ）含量、超氧化物歧化酶（ＳＯＤ）水平。实验结果表明，精索静脉曲张组（ＶＧ）左、右睾丸氧自由基自旋浓度明显高于假手术对照组（ＣＧ）（Ｐ＜Ｏ．０５）；ＶＧ双睾ＬＰＯ含量显著高于ＣＧ（Ｐ＜０．０１）；睾丸氧自由基相对自旋浓度和ＬＰＯ含量呈明显正相关（ｒ＝０．５４，Ｐ＜０．０５）；．ＶＧ双睾ＳＯＤ水平均显著低于ＣＧ（Ｐ＜０．０１）。上述结果提示：精索静脉曲张大鼠睾丸组织中含有大量的氧自由基和ＬＰＯ，损伤睾丸细胞及其各级生物膜，会导致睾丸生精功能紊乱造成不育，而睾丸氧自由基清除障碍可能是氧自由基浓度增高继之ＬＰＯ含量增多的重要机制之一。

INVESTIGATION OF THE ELECTROCHEMICAL-BEHAVIOR OF TRYPTOPHAN BY IN-SITU CIRCULAR DICHROIC SPECTROELECTROCHEMISTRY

The electrochemical redox processes of tryptophan were studied by in situ circular dichroic (CD) spectroelectrochemistry with a long optical path length thin-layer cell. The oxidation of tryptophan at low concentrations in basic aqueous solution is a two-electron irreversible electrochemical process which results from an irreversible subsequent chemical reaction. A method of treatment of CD spectral data for the irreversible electrochemical reaction is suggested, from which the values E(p/2) = 0.46 V, alphan(alpha) = 0.313 and k0 = 2.4 x 10(-4) cm s-1 (the standard heterogeneous reaction rate constant for tryptophan oxidation) were obtained.

ENHANCED AMPEROMETRIC DETECTOR FOR LOCAL-ANESTHETICS IN LIQUID-CHROMATOGRAPHY WITH METAL-OXIDE DISPERSED GLASSY-CARBON ELECTRODES

Chemically modified electrodes (CMEs) prepared by the dispersion of metal oxide particles on a glassy carbon (GC) substrate greatly enhance the voltammetric response and amperometric detection of local anesthetics following liquid chromatography (LC). The enhancement is more pronounced with the GC electrodes dispersed by the metal oxides of higher oxidation states (+3, +4) and for the species exhibiting relatively slow electrode kinetics under given conditions. With an applied potential of 1.2 V (vs. SCE), LC amperometric detection of the analytes at the alpha-alumina modified GC surface gives detection limits 2-5 times lower than those obtained at the bare electrode. The metal oxide-dispersed electrodes display significant improvement in sensitivity, and selectivity and indicate excellent preparation reproducibility and performance stability.

以铁氰化钾为介体的苹果酸脱氢酶电极的研制

通过化学交联法将苹果酸脱氢酶 (MDH) 固定在玻碳电极表面(d=0.5cm),使用 N-甲基吩嗪甲基硫酸盐 (PMS) 和铁氰化钾为介体,间接地测定酶促反应中生成的还原辅酶 I(NADH).工作电位+350mV (vs.Ag/AgCl),L-苹果酸测定的线性范围为 25μmol/L—300μmol/L,响应时间小于60s,电极的使用寿命可达10d.并对电极的选择和重现性进行了讨论.

电导法测定稀土冠醚配合物的稳定常数

用电导法研究了无水乙腈溶液中稀土高氯酸盐与DB·18-C-6、3,3-二甲基16-C-5(Me_2·16-C-5)、16-C-5的配位反应,以及1:9(V/V)H_2O-CH_3CN体系中稀土高氯酸盐与Me_2·16-C-6的配位行为,计算了1:1配合物的稳定常数。在无水乙腈中稀土与16-C-5的稳定常数大于稀土与Me_2·16-C-5的。加入少量水后,对轻稀土lgK值减小;重稀土则lgK值增大。