Cyclic voltammetry of solid diphenylamine crystals immobilized on an electrode surface and in the presence of an aqueous solution

Diphenylamine solid crystals have been mechanically attached to platinum or gold electrodes by four different methods and investigated by cyclic voltammetry in the presence of aqueous acidic media. It is demonstrated that the oxidative dimerization and polymerization (observed in non-aqueous solutions or mixed solvent systems) can also be accomplished by using diphenylamine microcrystals in contact with the electrode metal in the presence of aqueous solutions. Formation of a thin polymer layer has been observed even in the areas of the electrode that were not in direct contact with the diphenylamine microparticles. This finding can be explained by surface diffusion of the organic molecules or by oversaturation of the solution close to the diphenylamine microcrystals. A gradual growth of the voltammetric peaks characteristic of the polymer has been observed, while the irreversible wave due to the formation of cation radicals and their dimerization has shown a stationary behaviour. The redox transformation of the oligomeric compound formed at the surface is accompanied by a clear colour change: at pH 0 the colourless reduced form is converted to the bright-blue (violet) oxidized form. Electronic Publication     

Thin-film electrochemical sensor for diphenylamine detection using molecularly imprinted polymers

This work reports on the development of a new voltammetric sensor for diphenylamine based on the use of a miniaturized gold electrode modified with a molecularly imprinted polymer recognition element. Molecularly imprinted particles were synthesized ex situ and further entrapped into a poly(3,4-ethylenedioxythiophene) polymer membrane, which was electropolymerized on the surface of the gold electrode. The thickness of the polymer layer was optimized in order to get an adequate diffusion of the target analyte and in turn to achieve an adequate charge transfer at the electrode surface. The resulting modified electrodes showed a selective response to diphenylamine and a high sensitivity compared with the bare gold electrode and the electrode modified with poly(3,4-ethylenedioxythiophene) and non-imprinted polymer particles. The sensor showed a linear range from 4.95 to 115 μM diphenylamine, a limit of detection of 3.9 μM and a good selectivity in the presence of other structurally related molecules. This sensor was successfully applied to the quantification of diphenylamine in spiked apple juice samples.     

Synthesis, optical, electrochemical, and thermal studies on triazole-based dendrimers with diphenylamine as surface group

Fréchet-type dendrimers with hole-transporting diphenylamine as surface group and electron-transporting triazole moiety as building block have been synthesized by convergent synthetic strategy through ‘click chemistry’ methodology. First generation dendrimer exhibits longer relaxation time, higher quantum yield in the fluorescence spectrum, and better thermal stability than the zero and second generation dendrimers. CV studies showed irreversible reduction potential and the formation of radical cation due to diphenylamine moiety.     

Hypocrellin A与二苄胺和N-甲基苄胺的光化学反应

为了探讨HypocrellinA (HA)与胺基衍生物反应的自由基形成机制 ,我们采用ESR谱分别研究了HA与二苄胺 (DBA)和N 甲基苄胺 (NMBA)的光化学反应 .在含胺类物质和溶解氧的溶剂系统下 ,可见光照射HA激发成HA ,然后将溶解氧转变成1O2 ,1O2 诱导DBA或NMBA的氯仿溶液都能产生半醌自由基和氮氧自由基 .氮氧自由基的信号强度随光照时间的增加而减弱 ,而半醌自由基的信号强度随光照时间的增加而增强 ,氮氧自由基的含量与光照产生的半醌自由基成反比 .在除氧条件下 ,光照含HA和DBA的氯仿溶液体系时 ,半醌自由基是主要的自由基 .结果表明 ,在有氧的氯仿溶液中 ,HA诱导胺类物质生成HA半醌自由基