SYNTHESIS AND PROPERTIES OF SULFONATED POLY（ARYLENE ETHER） CONTAINING TRIPHENYL METHANE MOIETIES FROM ISOCYNATE MASKED BISPHENOL

A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.     

Vergleichende Messungen des Zeta-Potentials von Faserstoffen durch Elektroosmose und Strömungsstrom/Strömungspotential

An apparatus for the determination of zetapotential is described, which allows measurement of both streaming potential and streaming current as well as electroosmosis with one and the same fiber diaphragm with various electrodes (calomel, Ag/AgCl, palladium). Measurements with glass fibers, fibers of polyacrylonitrile and of polyester, and with cellulose pulp show that identical values for the electrokinetic parameters are obtained independent of voltage applied during electroosmosis resp. pressure difference during streaming measurements. This allows the conclusion that the zetapotential in dilute electrolyte solution is here an unequivocally determinable figure.

Herrn Prof. Dr.R. C. Schulz mit den herzlichsten Glückwünschen zum 65. Geburtstag gewidmet.     

Theoretical analysis of the performance of a model supercapacitor consisting of metal oxide nano-particles

The factors influencing the electrochemical behaviour of a supercapacitor have been partly examined in this work. The effects of so-called intrinsic parameters, i.e. exchange current density, unit cell length and double layer (DL) capacitance; as well as the so-called application parameters, i.e. cell current, on the cell potential discharge time have been considered. The contributions of each type of capacitors, DL capacitor and faradaic supercapacitor under various states of operation and material have been analyzed, and the competing (compensating) effects of the two types of capacitors as regards to the discharge and power characteristics manifested by current–potential and energy–power (Ragone plots) are elucidated.     

化学位移估算研究ATP构象随溶液pH值的变化

利用Johnson和Bovey的理论和方法计算了不同扭曲角χ(O4′－C1′－N9－C4)的ATP(5′-三磷酸腺苷)分子中糖环质子H1′和H2′由于环流效应引起的化学位移.H1′的化学位移与扭曲角χ有较强的依赖关系,反映了ATP在溶液中细微的构象变化.将计算结果与实验结果比较,证明在本文讨论的pH值范围(1～10)内,Mg2＋加入后,ATP的扭曲角χ在230～360°范围内变化.随溶液的pH值减小,ATP分子的构象由trans 构象通过-gauche构象转变为cis构象. 从而证明在酸性条件下, ATP倾向于以cis构象存在,而在碱性条件下trans构象更为稳定,从另一方面支持了在酸性条件下N1参与配位而在碱性条件下N7参与配位的结论.在讨论中也考虑了由pH变化所引起的环流强度的变化.     

ENTROPIC CONTRIBUTION TO THE INTERACTION PARAMETER xIN THE POLYMER／OLIGOMER SYSTEM： A LATTICE CLUSTER THEORY CONSIDERATION

Entropic contribution to the interaction parameter xeff in the model incompressible polymer/oligomer system is calculated by the lattice cluster theory (LCT). It is found that in the oligomer solvent, there exists a wide concentration range that the non-combinatorial “entropic interaction” term xeff φ1φ2 perceptibly counteracts the mean field combinary entropy ΔSMF. With the increase of the solvent size, both xeff and the ratio xefc φ1φ2/ΔSMF first reach their maximum and finally become trivially to zero. It is worth noting that no any demixing was found in the current calculation. This makes the controversial idea “entropically driven demixing” even elusive. However, we propose that further work on compressible polymer solution with structured monomer will witness the demixing owning to an increased configurational correlation.     

A unified orbital model of delocalised and localised currents in monocycles, from annulenes to azabora-heterocycles

Why are some (4n+2)π systems aromatic, and some not? The ipsocentric approach to the calculation of the current density induced in a molecule by an external magnetic field predicts a four‐electron diatropic (aromatic) ring current for (4n+2)π carbocycles and a two‐electron paratropic (antiaromatic) current for (4n)π carbocycles. With the inclusion of an electronegativity parameter, an ipsocentric frontier‐orbital model also predicts the transition from delocalised currents in carbocycles to nitrogen‐localised currents in alternating azabora‐heterocycles, which rationalises the differences in (magnetic) aromaticity between these isoelectronic π‐conjugated systems. Ab initio valence‐bond calculations confirm the localisation predicted by the naïve model, and coupled‐Hartree–Fock calculations give current‐density maps that exhibit the predicted delocalised‐to‐localised/carbocycle–heterocycle transition.     

有限线性扩散区域内EC＇反应催化电流

有限线性扩散区域内ＥＣ＇反应催化电流吴志斌，董绍俊，吴浩青（同济大学化学系，上海，２０００９２）（中国科学院长春应用化学研究所）（复旦大学化学系）关键词有限线性扩散空间，ＥＣ＇反应，催化电流化学修饰电极等有关膜电极及薄层池的电极过程动力学问题均涉及到...     

基于定向纳米碳管气体放电的气敏传感器研究

介绍了一种基于定向纳米碳管的气敏传感器,以生长定向纳米碳管的氧化铝模板作为阳极,铝板作为阴极,利用纳米碳管的尖端发射效应,在较低的电压下使气体产生放电现象。通过对纳米碳管在气体中击穿电压和放电电流的测量,实现对气体的定性定量检测。同时纳米碳管气敏传感器还具有体积小、灵敏度高、稳定性好、响应速度快、在常温常压下即可进行检测等优点,具有较好的应用前景。     

Analytical,structural and electrical characterization of SiGe layers by electron microbeam techniques

k-ratios of Ge-L and Si-K measured at different beam energies allow to evaluate simultaneously composition and thickness of SiGe layers on a Si substrate. A simple technique applying backscattered electrons also enables estimation of composition of bulk SiGe and of composition and thickness of relatively thick (200 nm) SiGe layers on Si. Electron channeling patterns of pseudomorphic SiGe/Si structures and of pure Si substrate show no significant differences whereas in relaxed structures a smearing of the pattern with increasing density of misfit dislocations is observed. Under particular conditions the technique of the electron beam induced current permits imaging of recombination-active misfit dislocations with a spatial resolution around 0.2 m. Moreover, a repulsion of holes due to the valence-band offset in a n-Si/SiGe heterostructure was detected.     

Gas chromatographic determination of organolead compounds with an alternating current plasma detector

The performance of the gas chromatography/alternating current plasma detector as a selective detector for organolead compounds is investigated. The helium make-up flow rate and the spatial position from which the lead emission is viewed, have an effect on the detector response. The detection limit for tetrabutyl lead was established as 130 pg/s and the lead selectivity ratio was found to exceed 13,800. Some applications of organolead determination in complex matrices were also studied in order to demonstrate the selectivity and sensitivity of the alternating current plasma detector.