Copolypeptide-doped polyaniline nanofibers for electrochemical detection of ultratrace trinitrotoluene

This paper demonstrates a new electrochemical method for the detection of ultratrace amount of 2,4,6-trinitrotoluene (TNT) with synthetic copolypeptide-doped polyaniline nanofibers. The copolypeptide, comprising of glutamic acid (Glu) and lysine (Lys) units, is in situ doped into polyaniline through the protonation of the imine nitrogen atoms of polyaniline by the free carboxylic groups of Glu segments, resulting in the formation of polyaniline nanofibers of emeraldine salt. The free amino groups of Lys segments at the surface of nanofibers provide the receptor sites of TNT through the formation of charge-transfer complex between the electron-rich amino groups and the electron-deficient aromatic rings. Adsorptive stripping voltammetry results demonstrate that the poly(Glu-Lys)-doped nanofibers confined onto glassy carbon electrodes exhibit a remarkable enriching effect and thus sensitive electrochemical response to TNT with a linear dynamic range of 0.5-10 μM and a detection limit down to 100 nM. Moreover, other kinds of nitro compounds show different redox behaviors from TNT at the doped nanofibers, and thus do not interfere with the electrochemical detection of TNT. This study essentially offers a new and simple method for electrochemical detection of ultratrace TNT.     

Stability and electrochemical properties of full-conjugated self-assembled films based on polyaniline and its acid-substituted derivates

<正>The stability of full-conjugated self-assembled(SA) multilayer films based on partially doped polyaniline(PANI) as a polycation and poly(o-aminobenzoic acid)(PCAN),poly(aniline-2-sulfonic acid)(PSAN) as polyanions is investigated in alkali aqueous solutions.The self-assembled PANI-PCAN films keep their stability within 24 h in 1 mol/L NaOH solution,-the PANI-PSAN films,however,maintain the stability for 20 min in the same condition because the solubility of PSAN in alkali solutions is much higher than that of PCAN.The electrochemical properties of the SA films are determined, and the film-CdS composites formed in situ are also reported.     

Viscoelastic phenomena during electrochemical deposition of polyaniline films

Electrochemical quartz crystal microbalance (EQCM) and crystal admittance measurements were used to study the potentiodynamic electrodeposition of polyaniline films. Variations in peak admittance provided the distinction between acoustically thin and acoustically thick films. In the former instance, the Sauerbrey equation was used to interpret the EQCM frequency shift in gravimetric terms. In the latter case, admittance spectra were interpreted viscoelastically to yield shear storage and loss moduli. Variations in storage modulus with potential (within a given deposition cycle) and with number of deposition cycles (at a given potential) were small, covering the range 1.1–1.6 × 10⁷ dyn cm⁻². Variations in loss modulus were much more dramatic, increasing from very low levels typical of a simple fluid to values similar to the storage modulus. More subtle variations of both components within a single potential cycle were highlighted using a novel differential format. This revealed two peaks, correlating with the first film redox process and with further film oxidation/polymerization. Contribution to the International Workshop on Electrochemistry of Electroactive Materials (WEEM-2006), Repino, Russia, 24–29 June 2006.     

Thin-layered MoS2/polyaniline nanocomposite for highly sensitive electrochemical detection of chloramphenicol

In this study, we synthesized molybdenum disulfide/polyaniline (MoS₂/PANI) nanocomposite via in situ polymerization of aniline in the presence of thin-layered MoS₂. The as-prepared MoS₂/PANI nanocomposite obtained an improved electrochemical performance due to the physisorption interaction between aromatic aniline and the basal plane of MoS₂. Furthermore, we constructed a new kind of electrochemical sensor based on MoS₂/PANI nanocomposite for the detection of chloramphenicol, which showed an excellent performance. The sensor has a high sensitivity and wide detection range from 1×10^-7 mol/L to 1×10^-4 mol/L, with a low detection limit of 6.9×10^-8 mol/L.     

A study on the influence of anionic surfactants on electrochemical degradation of polyaniline

The influence of anionic surfactants on the electrochemical degradation of polyaniline (PANI), deposited by electro-polymerization onto platinum electrodes, was investigated in an aqueous medium by means of cyclic voltammetry. The degradation rate was found to be greatly dependent on the pH of the solution. The electrochemical degradation of PANI/dodecylsulfate and PANI/dodecylbenzenesulfonate films was compared with that of a PANI/hydrochloride film. The degradation rate in the two former cases decreased by some 50% compared to the PANI/hydrochloride film in aqueous solution at pH = 2. The results were confirmed with theoretical calculations performed on the evaluation of head group charge of surfactants, the distance of anions from PANI positive sites and the shielding of anions on PANI positive sites.     

Substrate assisted electrochemical deposition of patterned cobalt thin films

The patterned Co layers deposited on the scratched Cu surfaces were investigated with the use of the scanning electron microscopy. Patterned cobalt thin films were electrochemically deposited from the cobalt sulfate bath at room temperature. Pattering of cobalt was carried out by simple means of substrate scratching. Gentle scratching induces a direct pattering of cobalt from vertical to horizontal. The prepared pattered films were characterized for their structural, surface morphological and compositional properties by means of X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. X-ray diffraction studies reveal that the films are of cobalt. From the SEM images fabrication of patterns of cobalt is apparent. This work demonstrates a novel approach for obtaining patterned cobalt for many technological applications.     

Thermal and structural stability of composite systems based on polyaniline deposited on porous polyethylene films

Conducting composite systems containing polyaniline layers produced on the surface and inside the pores of polyethylene support have been prepared. Microporous polyethylene films were obtained by melt extrusion with subsequent annealing, uniaxial extension, and thermal fixation. Polyaniline layers were formed by in-situ polymerization of aniline onto polyethylene porous support placed into the aqueous reaction mixture. Structural and chemical transformations upon heating of these systems in air in free state and in vacuum under load have been investigated by thermo-mechanical tests, IR spectrometry, and electron microscopy. Changes in mechanical properties of composites after heating have been analyzed. Composite systems have been found to demonstrate a considerably lower shrinkage upon heating than microporous polyethylene substrates. It has been discovered that the composites preserve mechanical integrity on heating up to temperatures much higher than the polyethylene melting point. It is concluded that thermo-mechanical behaviour of the composites is determined by the space-continuous phase of polyaniline on the surface and in the bulk of polyethylene support.     

Light scattering of bisphenol-A polycarbonate in the amorphous state and at the beginning of thermal crystallization

Summary Depolarized light scattering of amorphous polycarbonate (PC) is angular independent. The amount of scattering did not give any evidence for the existence of a liquid crystal type of phase, consisting of regions with a strong orientation correlation between chain segments. Annealing of PC belowT _g does not affect its scattering behaviour. Therefore, observed changes in physical properties such as the mechanical behaviour cannot be interpreted by an appreciable increase of intermolecular orientation correlation. If PC is heated at 190 °C for several days, an angular dependent scattering component appears. This component arises from the formation of spherulites with a sheaf-like structure.With 4 figures and 1 table     

Determination of mercury by electrochemical cold vapor generation atomic fluorescence spectrometry using polyaniline modified graphite electrode as cathode

An electrochemical cold vapor generation system with polyaniline modified graphite electrode as cathode material was developed for Hg (II) determination by coupling with atomic fluorescence spectrometry. This electrochemical cold vapor generation system with polyaniline/graphite electrode exhibited higher sensitivity; excellent stability and lower memory effect compared with graphite electrode electrochemical cold vapor generation system. The relative standard deviation was 2.7% for eleven consecutive measurements of 2 ng mL^− 1 Hg (II) standard solution and the mercury limit of detection for the sample blank solution was 1.3 рg mL^− 1 (3σ). The accuracy of the method was evaluated through analysis of the reference materials GBW09101 (Human hair) and GBW 08517 (Laminaria Japonica Aresch) and the proposed method was successfully applied to the analysis of human hairs.     

Light scattering in colloidal solution of magnetite in electric and magnetic fields

Light scattering by magnetite particles in kerosene under the simultaneous action of crossed electric and magnetic fields was studied. Decreasing of variation of light scattering intensity at some values of electric and magnetic fields have been found. Values of fields at which a minimum of light scattering intensity occur depend on the angle between laser beam and the plane of crossed fields.     

Light scattering in binary and ternary (polymer) solutions with specific interactions

Concentration dependence of basic light-scattering quantities in three binary low-molecular and two ternary polymer solutions was studied. Depolarization ratio alone may serve as a sensitive measure of presence of specific interactions. Experimental data of anisotropic scattering in low-molecular mixtures were in harmony with the idea that the parameters determining molecular orientation should be considered as continuous probability variables; in the case of polymer solutions specific interactions do not influence the anisotropic scattering.The presence of specific interactions with the formation of a minimum on the course of isotropic scattering is characterized. Transition from one solution structure to another with a local maximum on the course of composition light scattering is indicated.     

Novel redox species polyaniline derivative-Au/Pt as sensing platform for label-free electrochemical immunoassay of carbohydrate antigen 199

A novel electrochemical redox-active nanocomposite was synthesized by a one-pot method using N,N′-diphenyl-p-phenylediamine as monomer, and HAuCl₄ and K₂PtCl₄ as co-oxidizing agents. The as-prepared poly(N,N′-diphenyl-p-phenylediamine)-Au/Pt exhibited admirable electrochemical redox activity at 0.15 V, excellent H₂O₂ electrocatalytic ability and favorable electron transfer ability. Based on these, the evaluation of the composite as sensing substrate for label-free electrochemical immunosensing to the sensitive detection of carbohydrate antigen 199 was described. This technique proved to be a prospective detection tool with a wide liner range from 0.001 U mL⁻¹ to 40 U mL⁻¹, and a low detection limit of 2.3 × 10⁻⁴ U mL⁻¹ (S/N = 3). In addition, this method was used for the analysis of human serum sample, and good agreement was obtained between the values and those of enzyme-linked immunosorbent assay, implying the potential application in clinical research. Importantly, the strategy of the present substrate could be extended to other polymer-based nanocomposites such as polypyrrole derivatives or polythiophene derivatives, and this could be of great significance for the electrochemical immunoassay.     

Conformational transition in polyaniline films - Spectroscopic and conductivity studies of ageing

Polyaniline films were produced in situ at room temperature from aniline hydrochloride oxidized with ammonium peroxydisulfate on glass surfaces immersed in an aqueous reaction mixture. A notable change in the character of the time dependence of resistivity at fixed temperature was observed when the temperature of ageing exceeded 85 °C. The ageing was much faster above this limit. This observation is reflected in the FTIR spectroscopic measurements on the aged protonated, as well as deprotonated, samples. The FTIR spectral variation may be explained by a conformational transition of the polymer chain at about 85 °C. The fact that a similar transition has been found with deprotonated samples indicates that this feature is an inherent property of polyaniline, and is not caused by the acid component of the PANI salt.     

Column switching high-performance liquid chromatography with two channels electrochemical detection for high-sensitive determination of isoflavones

Column switching HPLC with electrochemical detection (HPLC-ED), which consists of one pre-column and two electrochemical detectors subsequent to each analytical column, called HPLC-2ED, has been developed for determining isoflavones (daidzin, genistin, daidzein, and genistein) with high sensitivity. In the present HPLC-2ED, the eluted daidzin and genistin from the pre-column were separated on an analytical column using a methanol–water–phosphoric acid mixture (30:70:0.5) as the mobile phase (MP), and daidzein and genistein were separated on another analytical column using a methanol–water–phosphoric acid mixture (50:50:0.5). The way of the elute flow from the pre-column was changed by rotating the switching valve at 17 min. The difference in retention times of genistein between isocratic HPLC-ED and HPLC-2ED was 52.2 min. The detection limit (S/N = 3) per column injection (5 μL) of genistein was 0.5 pg. The sensitivity by the present method is superior to that of previously reported gradient HPLC-ED for the determination of isoflavones.     

Layer-by-layer composite films of polyaniline and vanadium pentoxide sol gels studied by electrochemical surface plasmon spectroscopy

Electroactive multilayer films of polyaniline (PAni) and vanadium pentoxide (V₂O₅) sol-gels were prepared on gold surfaces by means of the layer-by-layer (LBL) method. The stepwise buildup and the optoelectrochemical behaviour of the composite films were investigated in-situ by electrochemical surface plasmon spectroscopy (ESPS). A thickness increment of 2.3 nm per deposited bilayer was obtained by modelling the surface plasmon spectra. The composite multilayer films display charging-discharging characteristics similar to a bare vanadium pentoxide xerogel network along with an optoelectrochemical response which is dominated by the conducting polymer component. Electrochemical impedance spectroscopy (EIS) experiments confirm the findings from ESPS with regard to the presence of different conductive states of the composite.     

Dynamics of thin polymer films: Recent insights from incoherent neutron scattering

Incoherent neutron scattering is presented as a powerful tool for interpreting changes in molecular dynamics as a function of film thickness for a range of polymers. Motions on approximately nanosecond and faster timescales are quantified in terms of a mean-square atomic displacement (〈u²〉) from the Debye–Waller factor. Thin-film confinement generally leads to a reduction of 〈u²〉 in comparison with the bulk material, and this effect becomes especially pronounced when the film thickness approaches the unperturbed dimensions of the macromolecule. Generally, there is a suppression (never an enhancement) of 〈u²〉 at temperatures T above the bulk calorimetric glass-transition temperature (T_g). Below T_g, the reduction in the magnitude of 〈u²〉 depends on the polymer and the length scales being probed. Polymers with extensive segmental or local mobility in the glass are particularly susceptible to reductions of 〈u²〉 with confinement, especially at the Q vectors probing these longer length scales, whereas materials lacking these sub-T_g motions are relatively insensitive. Moreover, a reduced 〈u²〉 value correlates with reduced mobility at long time and spatial scales, as measured by diffusion in these thin polymer films. Finally, this reduced thin-film mobility is not reliably predicted by thermodynamic assessments of an apparent T_g, as measured by discontinuities or kinks in the T dependence of the thermal expansion, specific volume, index of refraction, specific heat, and so forth. These measurements illustrate that 〈u²〉 is a powerful and predictive tool for understanding dynamic changes in thin polymer films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3218–3234, 2004     

Characterization and electrochemical deposition of natural melanin thin films

Melanin is an important class of biological pigments because of its distinct chemical and physical properties. The electrochemical deposition of natural melanin thin films was studied using two different techniques; constant potential and cyclic voltammetry along with a deposition time of five hours. The thin films deposited electrochemically on a fluorine-doped tin oxide conductive glass substrate using the constant potential method, exhibited faster growth rate and better adhesion to the fluorine-doped tin oxide working electrodes than those deposited using the cyclic voltammetry method. The thin films deposited on the fluorine-doped tin oxide conductor glass using the constant potential method were also more homogeneous than those deposited via the cyclic voltammetry technique. The increase of film thickness is related to the increase of electrochemical deposition time. Interestingly, the electrochemical deposition using the constant potential method had the advantage of consuming less electric charge. The physical and chemical structures of the melanin thin films were characterized using ultraviolet–visible absorption spectroscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction analysis. The ultraviolet–visible absorption spectra showed the correlation between the variation of deposition rates of melanin and the type of electrochemical technique employed as well as the thickness of the film. The average thickness of the film is 500 nm which absorb 40% of light in both type of films. The atomic force microscopy images illustrated the homogeneous deposition of the melanin molecules on the fluorine-doped tin oxide conductive glass substrate, indicating that the thickness of the thin films can be controlled. We estimated an average grain size of 14.093 Å. The ease of preparing such thin films of organic materials can open new avenues towards the use of soft conductors, in contrast to the complex preparation of industrial semiconductors.     

Doping of polyaniline films with organic sulfonic acids in aqueous media and the effect of water on these doped films

Polyaniline (PANI) films in the form of emeraldine salt (ES) doped with aqueous organic sulfonic acids such as camphorsulfonic acid (CSA), p-toluenesulfonic acid (p-TSA) and dodecylbenzenesulfonic acid (DBSA) were studied. The ES films were obtained by treating the PANI in the form of emeraldine base (EB) with the aqueous solution of the acids. The dopant weight fraction (w), which is related to the mass gain during the redoping of EB, was in situ determined using a quartz crystal microbalance (QCM). The behaviour of PANI doping with different acids indicates that the uptake shows a slow diffusion process. The kinetics of the doping reaction is dominated by Fickian diffusion kinetics. The diffusion coefficients (D) of the dopant ions into the PANI chains were determined and were found to vary within the range of (1.6-18) × 10⁻¹⁵ cm² s⁻¹. Moreover, the effect of water on these doped ES films was studied. The starting point is the fact that PANI-coated the electrode of QCM shows significant frequency shifts on exposure to water. The changes in the frequency as a function of treatment time in water were quantitatively measured. The response of the device suggests that the mass decrease under water exposure is due to dopant ions release. The latter films were dedoped by exposure to ammonia solution to obtain the EB film form. A further decrease in the mass of the films was observed. The percentage of the mass loss due to water exposure is found to be less than w determined during the dedoping process.     

Remarkably enhanced capacitance of ordered polyaniline nanowires tailored by stepwise electrochemical deposition

A stepwise deposition method was employed to create ordered polyaniline (PANI) nanowires with remarkably enhanced capacitance. Cyclic voltammetry, AC impedance, and galvanostatic charge/discharge cycling were employed to investigate the electrochemical performance of the PANI electrodes. The PANI-deposited electrode exhibits much higher capacitance than those prepared by one-step deposition method, which were mainly contributed from the unique nano structure of PANI and the increased biological, economical, and technical surface areas. The superior capacitive behaviors of the nano PANI electrodes show great potential in preparation of high efficient electrochemical capacitors or rechargeable batteries.     

Aspects of polyaniline electrodeposition on aluminium

Electrodeposition of polyaniline (PAni) from acid solutions on spontaneous passivating electrodes such as Al is not so obvious as on active metals (Fe and Ni). The methods that can result in deposition are: (1) surface pre-treatment with a chelating agent (alizarin) to block the hydrogen evolution reaction on aluminium and (2) a suitable monomer concentration (critical monomer concentration) to decrease the polymerisation induction time. The oxidation of aluminium to thick porous film limits the growth kinetics of PAni during deposition by cyclic voltammetry. We found that after reducing hydrogen evolution by surface chelation, for film growing in 0.5 M H₂SO₄ a concentration of 0.4 M aniline is required.