Study of the electrochemical behaviour of amphetamine and its derivatives in aqueous solution

The polarographic behaviour of amphetamine-type drugs in acid and alkaline solutions was investigated. Differential pulse polarography (DPP) with a dropping mercury electrode (DME) was used to monitor these drugs in aqueous solution. DPP and cyclic voltammetry (CV) were also utilised to study the electrode process of some 2-phenylethylamines derivatised with 4-N,N-dimethylaminobenzaldehyde (Ehrlich’s reagent) and 2,4-dinitrofluorobenzene, known as Sanger’s reagent, respectively. Received: 19 March 1998 / Revised: 17 September 1998 / Accepted: 21 September 1998     

Study of the electrochemical behaviour of metaclazepam in aqueous media and its determination in biological fluids

Summary The polarographic behaviour of metaclazepam in Britton Robinson universal buffer has been investigated by the following techniques: DC tast and differential pulse polarography, cyclic voltammetry, microcoulometry and adsorptive stripping voltammetry. The compound is polarographically active over the entire pH-range, showing a single well-defined wave. This has been characterized as being a 2e^– diffusion-controlled wave in acid media. The reduction step is due to the C=N group. The drug is also surface-active and the adsorption at the electrode is higher in alkaline than in acid media. A stripping method for the determination of this psychotropic drug at the sub-micromolar and nanomolar concentration levels is described. Adsorptive accumulation for 300 s followed by differential pulse measurement in Britton Robinson buffer at pH 9.1 can be used for the determination of metaclazepam in urine with an accuracy and precision of 2% and 3%, respectively. The detection limit was 0.55 ng per ml of urine (adsorptive accumulation at –0.60 V for 300 s).     

Amphiphilic cholesteryl-bearing carboxymethylcellulose derivatives: self-assembly and rheological behaviour in aqueous solution

The self-assembly of amphiphilic cholesteryl-bearing carboxymethylcellulose derivatives (CCMCs) from individual molecules to self-aggregates, in addition to their rheological behaviour in aqueous solution were investigated. The conformations of the individual CCMC individual molecules and self-aggregates, and the microstructures of CCMC self-aggregates were characterized using the static and dynamic light scattering analyses, and the steady fluorescence technology. The results showed that the individual CCMC chains became compact, and aqueous NaCl solution changed from an approximate θ solvent to a bad one when the number of hydrophobic cholesteryl groups increased. The CCMC self-aggregates exhibited as compact spheres. The microstructural characterization indicated that one CCMC self-aggregate consisted of multiple individual CCMC molecules and hydrophobic microdomains, and multiple cholesteryl groups self-associated into one hydrophobic microdomain. The atomic force microscopy images of CCMC self-aggregates in phase mode showed that the multiple interior hydrophobic phase separation regions were surrounded by hydrophilic polysaccharide chains, providing an evidence for multiple hydrophobic microdomains in one self-aggregate. The rheological analysis proved that the CCMC self-aggregates were a microgel, in which the associations of cholesteryl groups provided multiple cross-linking points in the polymer network. The microgel solutions displayed a unique thixotropy and a shear thinning behaviour.     

Water-induced fluorescence quenching of aniline and its derivatives in aqueous solution

Nonradiative deactivation processes of excited aniline and its derivatives in aqueous solution were investigated by steady-state and time-resolved fluorescence measurements to reveal characteristic solvent effects of water on the relaxation processes of excited organic molecules. The magnitude of nonradiative rate (k_nr) of excited aniline derivatives increased significantly in water compared to that in organic solvents (cyclohexane, ethanol, and acetonitrile). The fluorescence lifetime measurements in organic solvent/H₂O mixed solvents suggested that the fluorescence quenching in water was not due to exciplex formation but due to interactions with a water cluster. From temperature effect experiments on the fluorescence lifetime and quantum yield of aniline, N-methylaniline, and N,N-dimethylaniline, the apparent activation energies for the nonradiative deactivation rate in water were determined as 21, 30, and 41 kJ mol^-1, respectively. Upon substitution of hydrogen atoms in the aromatic ring of aniline derivatives for deuterium atoms resulted in normal deuterium isotope effect in cyclohexane, i.e. k_nr decreased by deuterium substitution, while in water the same deuterium substitution led to an increase in k_nr (the inverse isotope effect). The inverse isotope effects implied that a direct internal conversion to vibrationally higher excited states in the electronically ground state is not a dominant mechanism but the transition to a close-lying energy level, e.g. the relaxation to charge transfer to solvent (ctts) state, would be associated with the quenching mechanism in water.     

乙撑二氧噻吩在中性水溶液中的电化学聚合及行为研究

本文研究了乙撑二氧噻吩在中性水溶液中的电化学聚合过程以及聚乙撑二氧噻吩膜的电化学行为, 利用光电子能谱和红外光谱等方法对聚合物膜进行了表征, 研究表明在中性水溶液中制成的聚乙撑二氧噻吩膜修饰电极具有较好的电化学行为和稳定性。     

Photochemical behaviour of halophenols in aqueous solution

The mechanism of photolysis by direct absorption of chloro-, bromo-and fluorophenols (XPhOH with X=Cl, Br or F) is much more dependent on the position of the halogen than on its nature. In all cases, the first step is a heterolytic C-X scission with release of the halogenated acid HX. 3-XPhOH is almost specifically converted into resorcinol. The anionic form of 2-XPhOH is transformed with a rather high quantum yield into cyclopentadiene carboxylic acids. By nanosecond laser-flash photolysis the first transient detected is a ketene which is converted into fulvene-6, 6 diol and then into the cyclopentadiene carboxylic acids. The phototransformation is about 10 times less efficient from the neutral form and not so specific. The irradiation of 4-XPhOH leads to the formation of a carbene which is the first detected transient. According to the experimental conditions, this transient reacts with oxygen producing a benzoquinone-O-oxide and subsequentlyp-benzoquinone, with water leading to hydroquinone or with another molecule of halophenol producing a halogenodihydroxybiphenyl. It was also observed that 4-chlororesorcinol behaves as both 4-ClPhOH and 2-ClPhOH. Chlorohydroquinone does not react as monohalophenols, the main photoproducts are hydroquinone and chlorobenzoquinone. This reaction is consistent with a radical mechanism. The transformation of halophenols can be sensitized by phenol and in most cases by hydroquinone. The half-life of the triplet state of hydroquinone was evaluated at 0.9μs and the intersystem crossing yield at 0.39. The sensitization of 3-FPhOH was observed with phenol but not with hydroquinone leading to the conclusion that the energy level of its triplet state lies in the range 310–350 kJ mol⁻¹. It is lower than 310 kJ for the other halophenols studied here.     

Study on the aggregation and electrochemical properties of Rose Bengal in aqueous solution of cyclodextrins

The interactions of Rose Bengal (RB) with alpha-cyclodextrin (alpha-CD), hydroxypropyl-beta-cyclodextrin (HP-beta-CD), hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD), heptakis(2,3,6-tri-O-methyll)-beta-cyclodextrin (TM-beta-CD) were studied in aqueous solutions of 0.1 M KClO(4) and 0.1 M LiClO(4) by vis absorption, fluorescence spectroscopy as well as electrochemical measurements at 298 K. The spectrophometric results indicate that RB is included in all beta- and gamma-CDs forming complexes with a stoichiometry 1:1 whose stability is slightly higher in KClO(4) than in LiClO(4) solutions. The complex stability constants determined for salt-containing CD solutions are lower than those for water solutions. The complexation of RB with beta- and gamma-CD and the differences between the complexes obtained in the presence of the two salts were confirmed by an electrochemical study.     

Polyaniline doped with modified gold nanoparticles and its electrochemical properties in neutral aqueous solution

Doping polyaniline with COO(-)-modified gold nanoparticles by forming stable layer-by-layer multilayer films can shift its electroactivity to neutral pH. The films can electrocatalyze the oxidation of NADH and offer potential applications in other fields, e.g., optoelectronics or biosensing.     

Study of the electrochemical behaviour of a carbon steel electrode in sodium sulfate aqueous solutions using electrochemical impedance spectroscopy

The study of a plain carbon steel (AISI 1020) in Na₂SO₄ aqueous solutions at different concentrations was carried out by electrochemical impedance spectroscopy (EIS) in order to determine the corrosion mechanism and to obtain representative corrosion rates of the system. EIS was used to measure corrosion current densities at high concentrations in the range 0.1–1 wt% Na₂SO₄, but in the low concentration range, from 0.001 to 0.01 wt%, a scattered Nyquist plot was obtained. Other electrochemical techniques, such as polarization resistance (PR), Tafel plots and electrochemical noise (EN), were also used in this analysis. The charge transfer resistance was determined and compared with the PR and noise resistance. Electronic Publication     

铝在氢氧化钠溶液中的电化学行为研究

铝是地壳中含量丰富的元素 ,分布广泛 ,由于其具有价格低、能量密度高、导电性良好及无毒性等优点 ,因而是阳极材料的首选物质 ,铝电池的研究也已经成为近年来研究开发的热点课题之一[1～ 3] 。探讨铝在强碱性溶液中的溶解机理 ,对铝电池的研究和开发将具有一定的理论指导意义。1　实验部分1 1　仪器与试剂ＢＡＳ 1 0 0Ａ电化学系统 (美国ＢＡＳ仪器公司 ) ;ＣＳ5 0 1型恒温槽 ;工作电极为直径是 0 .3ｍｍ的铂圆盘电极 ,参比电极是标准甘汞电极 (ＳＣＥ)。铝( 99.99% ) (天津化学试剂厂 ) ,氢氧化钠为分析纯(上海化学试剂厂 ) ,水为二次蒸…     

The influence of aniline and its derivatives on the corrosion behaviour of copper in acid solution

The inhibiting action of aniline and its derivatives on the corrosion of copper in hydrochloric acid has been investigated, with emphasis on the role of substituents. With this purpose five different anilines were selected: aniline, p-chloro aniline, p-nitro aniline, p-methoxy and p-methyl aniline. The electrochemical and gravimetric results, obtained in the absence and presence of different concentrations of inhibitors, revealed that aniline reduces the corrosion of copper, with a critical concentration of 10^–2 M. Furthermore, the interaction energy calculated as G_ads gave a value of 4.2 kcal mol^–1 indicating physisorption of the organic compound at the copper surface. The results have also shown that substituents, either electron donors (–CH₃, –OCH₃) or, electron acceptors (–NO₂, –Cl) in para position, decrease the inhibition action of aniline. A theoretical study using molecular mechanic and ab initio Hartree Fock methods, to model the adsorption of aniline on copper (100) showed results in good agreement with the experimental data. Aniline adsorbs parallel to the copper surface, showing no preference for a specific adsorption site. On the other hand, from ab initio Hartree Fock calculations, an adsorption energy between 2 kcal/mol and 5 kcal/mol is obtained, which is close to the experimental value, confirming that the adsorption of aniline on the metal substrate is rather weak. In view of these results, the orientation of the aniline molecule with respect to the copper surface is considered to be the dominant effect.     

Photochemical polymerization of thiophene derivatives in aqueous solution

A novel method of photochemical polymerization of thiophene derivatives in aqueous solution catalyzed by potassium dichromate and initiated by illumination is described.     

Study of the behaviour of amino acids in aqueous solution by time-domain NMR and high-resolution NMR

The study of protein hydration by time-domain NMR is complicated by the great number of interactions involved, resulting from the presence of several amino acids and the possible modifications produced by the various structures. Moreover, a good comprehension of the molecular interactions of the simple amino acids in solution is essential to elucidate the mechanism of the biological functions of proteins. Measurements of transverse relaxation rates of the protons of water (R(2) = 1/T(2)) in aqueous solutions of amino acids such as L-glycine, L-asparagine, L-arginine and L-tryptophan were carried out in order to study the effects of chemical exchange and molecular diffusion on the amplitude of R(2). The values of R(2) measured by the Carr-Purcell-Meiboom-Gill (CPMG) sequence were studied while varying the solution pH and the parameters of the CPMG sequence. The dependence of R(2) on pH and tau (inter-pulse delay between the first and the second pulses of the CPMG sequence) is interpreted in terms of chemical exchange between the protons of water and those of the labile amino acid groups. This interpretation was confirmed by the analysis of the proton spectra acquired using a 300 MHz NMR spectrometer.     

Size-dependent electrochemical behavior of thiol-capped CdTe nanocrystals in aqueous solution

Electrochemical studies of thiol-capped CdTe nanocrystals in aqueous solution have demonstrated several distinct oxidation and reduction peaks in the voltammograms, with the peak positions being dependent on the size of the nanocrystals. While the size dependence of the reduction and one of the oxidation potentials can be attributed to altering the energetic band positions owing to the quantum size effect, an extraordinary behavior was found for the oxidation peak observed at less positive potentials. In contrast to a prediction based on the quantum size effect, this peak moves to more negative potentials as the nanocrystals' size decreases. Moreover, the contribution of the charge associated with this peak compared to the total charge passed during the nanocrystal oxidation correlates well with the photoluminescence (PL) efficiency of individual fractions of the CdTe nanocrystals. These experimental observations allow a peak to be assigned to the oxidation of Te-related surface traps. The intra-band-gap energy level assigned to these Te-related trap states shifts toward the top of the valence band as the nanocrystal size increases, thus allowing the higher photostability of the larger nanocrystals to be explained. At a certain nanocrystal size, the trap level can even move out of the band gap.     

The triplet-state lifetime of indole derivatives in aqueous solution

An important feature of tryptophan phosphorescence, crucial for probing protein structure and dynamics, is the drastic reduction of the lifetime (tau) in fluid solutions. Initial reports of indole and derivatives showed that tau decreases from 6 s in rigid glasses to about 1 ms in aqueous solutions at ambient temperature. Recently a report by Fischer et al. questioned the validity of the millisecond lifetime, claiming that in millimolar electrolyte solutions tau is about 40 micros, similar to the 12-30 micros of earlier determinations based on flash photolysis. Longer lived phosphorescence was detected in pure water but because it exhibited an initial growing phase and an anomalously large triplet yield, the emission was attributed to an artifact arising from the slow, first-order, geminate recombination of the radical cation and electron generated by photochemistry. In this study, we reexamine both the phosphorescence lifetime and the triplet quantum yield of indole, N-acetyl tryptophanamide (NATA), N-methyl tryptophan and the tryptophan-glycine-glycine tripeptide under the same conditions adopted by Fischer et al. as well as over a wider range of electrolyte and buffering salts concentrations, pH, solvent and temperature. Throughout, the results show that the phosphorescence decay is slow and uniform down to the 12 micros resolution of the instrument, with no evidence of short-lived, 40 micros-like components. Most compelling was the similarity between the fluorescence-normalized triplet yield of indole derivatives in water and that of W59 in the protein ribonuclease T1 or of NATA in rigid glasses. Its invariance over experimental conditions that varied the production of photoproducts several fold and the characteristic susceptibility of the triplet lifetime to O2, proton and ground state quenching demonstrated that the triplet state was formed predominantly through normal intersystem crossing and that its unquenched lifetime was at least 9 ms.     

关于苯及其衍生物在盐水溶液中的活度系数的研究

摘录了25℃时苯,甲苯,邻位、间位、对位二甲苯,间位、对位二氯苯及萘在NaF,LiCL,NaBr,NEt~4Br等25种盐的水溶液中的活度系数f,它们的lgf-c~s的关系符合Setchenow盐效应公式。计算了苯及其衍生物在上述25种盐水溶液中的各种盐效应理论的k~s,主要有:1)Debye-macAulay静电理论;2)Conway-Desnoyers-Smith静电理论;3)Masterton-Lee定标粒子理论;4)McDevit-Long内压力理论;5)改进的内压力理论;6)改进的Bockris色散力理论。对各种理论值比较后可以看到改进后的内压力理论k~s值与实验k~s值较为吻合。Bockris色散力理论经改进后计算比较简单,可以判断盐效应符号,盐效应顺序也基本正确。