The nature of the interaction between polyaniline and 2,5-dimercapto-1,3,4-thiadiazole in electrochemical redox processes

The interaction between polyaniline (PAn) and 2,5-dimercapto-1,3,4-thiadiazole (DMcT) was investigated by means of cyclic voltammetry and UV-visible spectroscopy. The results show that the polymerization-depolymerization reaction of DMcT or its dilithium salt Li(2)DMcT is a kinetically quasi-reversible process. PAn exhibits very weak electrochemical activity in neutral propylene carbonate. After doping with protonic acid, such as hydrochloric acid or maleic acid etc., however, it shows an extensively enhanced electroactivity. For the complex system, PAn-DMcT or PAn-Li(2)DMcT, polyaniline has no catalytic activity for the electrochemical polymerization-depolymerization reaction of DMcT or DMcT(2-). Instead, the enhancement of the electrochemical redox activity of PAn-DMcT system compared with that of PAn, DMcT, Li(2)DMcT, and PAn-Li(2)DMcT comes from the protonic doping of PAn by DMcT.

Novel highly selective anion chemosensors based on 2,5-bis(2-hydroxyphenyl)-1,3,4-oxadiazole

2-(2-Hydroxyphenyl)-5-phenyl-1,3,4-oxadiazole 1 and 2,5-bis(2-hydroxyphenyl)-1,3,4-oxadiazole 2 were used as anion fluorescent and colorimetric chemosensors with high selectivity for H2PO4- and F- over Cl-, while 2 can even distinguish H2PO4- from F-. (C) 2002 Elsevier Science Ltd. All rights reserved.

Investigation of the electrocatalytic effect of polyaniline on the redox reaction of 2,5-dimercapto-1,3,4-thiadiazole by cyclic voltammetry

Electrochemical polymerized polyaniline(PAn) film electrode was used to investigate the electrocatalytic effect of PAn on the electrochemical redox reaction of 2,5-dimercapto-1,3,4-thiadiazole (DMcT), PAn film electrode was electrochemically treated or immersed in DMcT solution before it was scanned in 1.0 mol/L HCl electrolyte. The cyclic voltammograms of PAn film electrode in 1.0 mol/L HCl solution changed with the above treatment, implying the electrocatalytic effect of PAn on the redox reaction of DMcT, The formation of electron-donor-acceptor adducts through the interaction between thiol or disulfide groups of DMcT and amine or imine groups of PAn during the treatment was probably the reason of the catalysis, The electrochemical properties of the adduct were different from those of PAn and DMcT, The adduct possessed a higher electrochemical activity and a better electrochemical reversibility than DMcT or PAn used alone.

聚苯胺对2,5-二巯基-1,3,4-噻二唑氧化还原反应的电化学催化作用的循环伏安研究

研究了聚苯胺 ( PAn)膜电极在 2 ,5-二巯基 -1 ,3 ,4 -噻二唑 ( DMc T)溶液中电化学处理或浸泡后的循环伏安 ( CV)曲线的变化规律 .实验结果表明 ,PAn膜电极在 DMc T溶液中进行电化学处理或浸泡过程可使DMc T进入 PAn膜内部与 PAn形成复合物 .PAn对 DMc T的电化学催化作用可能和二者之间形成的电子给体 -受体复合物有关 .该复合物的电化学氧化还原特性不同于 PAn和 DMc T,其氧化还原反应速率和可逆性均优于 DMc T

Soluble 2,5-dimercapto-1,3,4-thiadiazole/poly(o-toluidine) electroactive composite

A poly(o-toluidine) (POT)/2,5-dimercapto-1,3,4-thiadiazole (DMcT) composite was prepared. When POT and DMcT are mixed in a proper solvent, POT in a medium-oxidation state is reduced, and DMcT in turn is oxidized to its soluble dimer when the molar ratio of DMcT to POT is higher than 0.5. Therefore, the composite was soluble in organic solvents such as tetrahydrofuran (THF), dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP) and exhibited very high electroactivity, two orders of magnitude higher than that of pure POT and three orders of magnitude higher than that of pure DMcT. Molecular-level contact between POT and DMcT is the reason for the improved catalytic effect of POT on DMcT, compared to that of polyaniline on DMcT. (C) 1999 The Electrochemical Society. S0013-4651(98)08-059-8. All rights reserved.

Catena-Poly[[[tetra-mu(2)-aqua-heptaaqua-(mu(2)-benzene-1,3,5-tricarboxylato)-mu(3)-hydroxido-trinickel(II)sodium]-mu(4)-benzene-1,3,5-tricarboxylato]sesqui-hydrate]

The title coordination polymer, {[Ni3Na(OH)(C9H3O6)(2)( H2O)(11)] center dot 1.5H(2)O}(n), is built up from three independent Ni-II ions and one Na-I cation bridged by benzene-2,4,6-tricarboxylate ( BTC) ligands and water molecules. Three Ni-II ions are bridged by three bidentate carboxylate groups of three BTC ligands, two aqua ligands and one OH- unit, to form a trinuclear metal cluster. The Na-I cation is bonded to the Ni-II cluster by two bridging water molecules. One of the three BTC ligands bridges neighbouring clusters into one-dimensional chains, which are further connected through a complex hydrogen-bonding scheme, forming a three-dimensional suprastructure. The title complex is isomorphous with the previously reported Co-II complex.

Growth kinetics of 1-2 mm and 3-4 mm colonies of Nostoc sphaeroides (Cyanophyta) in outdoor culture

Nostoc sphaeroides Kutzing was cultivated in paddlewheel-driven raceway ponds and the growth kinetics of 1-2 mm and 3-4 mm colonies of N. sphaeroides was studied. The biomass productivities in 2.5 m(2) raceway ponds inoculated with 1-2 mm and 3-4 mm colonies were 5.2 and 0.25 g dry wt m(-2) stop d(-1), respectively. Furthermore, differently sized colonies showed different relative water content, total soluble carbohydrates, chlorophyll a content and density of filaments. This is the first report on mass culture of N. sphaeroides under outdoor conditions.

Supramolecular architectures, photophysics, and electroluminescence of 1,3,4-oxadiazole-based iridium(III) complexes: From mu-dichloro bridged dimer to mononuclear complexes

One mu-dichloro bridged diiridium complex and three mononuclear iridium(III) complexes based on the 1,3,4-oxadiazole derivatives as cyclometalated ligands and acetylacetonate (acac) or dithiolates O,O'-diethyldithiophosphate (Et(2)dtp) or N,N'-diethyldithiocarbamate (Et(2)dtc) as ancillary ligands have been synthesized and systematically studied by X-ray diffraction analysis. The results reveal that three mononuclear complexes all adopt distorted octahedral coordination geometry around the iridium center by two chelating ligands with cis-C-C and trans-N-N dispositions, which have the same coordination mode as the diiridium dimer. The dinuclear complex crystallizes in the monoclinic system and space group C2/c, whereas three mononuclear iridium complexes are all triclinic system and space group P(1) over bar. In the stacking structure of the dimer, one-dimensional tape-like chains along the b-axis are formed by hydrogen bondings, which are strengthened by pi stacking interactions between phenyl rings of 1,3,4-oxadiazole ligands. Then these chains assemble a three-dimensional alternating peak and valley fused wave-shape structure. In each stacking structure of three mononuclear complexes, two molecules form a dimer by the C-H center dot center dot center dot O hydrogen bondings, and these dimers are connected by pi stacking interactions along the b-axis, constructing a zigzag chain.

Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

以1-苯基-3-甲基-4-苯甲酰基代吡唑酮[5]萃取稀土和钍铀钛锆及其在分析化学中的某些应用

本文研究了以PMBP-苯萃取稀土和钍、铀、钛、锆的萃取行为。测定了La、Ce、Pr、Nd、Sm、Gd、Dy、Yb、Y、U(Ⅵ)、Ti、Th和Zr的pH_(1/2)值,计算了它们的萃取平衡常数。并介绍了近十年来作者将此萃取剂应用于铀、钍、稀土、鋰、钢铁合金及岩石中痕量稀土、钍和钙的分离和测定方面的工作。实践证明,PMOP合成简便、价格低廉、萃取能力较强,是比TTA更为优越的萃取剂。

Novel, highly efficient blue-emitting heteroleptic iridium(III) complexes based on fluorinated 1,3,4-oxadiazole: tuning to blue by dithiolate ancillary ligands

Novel blue-emitting phosphorescent iridium(III) complexes with fluorinated 1,3,4-oxadiazole derivatives as cyclometalated ligands and dithiolates as ancillary ligands have been synthesized and fully characterized; highly efficient OLEDs have been achieved using these complexes in the light-blue to blueemitting region.

1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5与中性磷(膦)萃取剂协同萃取镧B

研究了 1 苯基 3 甲基 4 苯甲酰基 -吡唑酮 5 (HPMBP)和中性有机磷 (膦 )类萃取剂Cyanex 4 71X(TIBPS ,B)在硝酸介质中对稀土元素La 的萃取 ,用斜率法和恒摩尔法探讨了萃取机理 ,确定了萃合物的组成为La(NO3 ) 2 ·PMBP·B ,计算了萃取平衡常数。比较了HPMBP与Cyanex 4 71X、Cyanex 92 1、Cyanex 92 3、Cyanex 92 5、DEH/EHP、P35 0及TBP的单独及混合体系萃取La 的性能 ,结果表明 :所有混合体系对La 均有协同效应 ,其中HPMBP与Cyanex 92 3、Cyanex 92 1、Cyanex 92 5的混合体系是萃取La 的有效体系。

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮萃取~(46)Sc的研究

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(PMBP)做萃取剂,氯仿和环己烷为稀释剂,观察了在HCl溶液46Sc的溶剂萃取行为。实验结果表明,从10-3~10-2mol/L的HCl溶液中用PMBP-氯仿(或环己烷)能有效地萃取46Sc,萃取率可达95%以上。另外,对PMBP从HCl溶液中萃取46Sc和234Th的结果也做了比较,结果表明,通过控制水溶液中HCl的浓度,能实现234Th与46Sc的分离。