Surface plasmon resonance studies on the electrochemical doping/dedoping processes of anions on polyaniline-modified electrode

The combination of in situ surface plasmon resonance (SPR) with electrochemistry was used to investigate the electrochemical doping/dedoping processes of anions on a polyaniline (PAn)-modified electrode. Electrochemical SPR characteristics of the PAn film before and after doping/dedoping were revealed. The redox transformation between the insulating leucoemeraldine, and the conductive emeraldine, corresponding to the doping/dedoping of anion, can lead to very distinct changes in both the resonance minimum angle and the shape of SPR curve. This is ascribed to the swelling/shrinking effect, and the change of the PAn film in the imaginary part of the dielectric constant resulted from the transition of the film conductivity. In situ recording the time evolution of reflectance change at a fixed angle permits the continuous monitoring of the kinetic processes of doping/dedoping anions. The size and the charge of anions, the film thickness, as well as the concentration of anions are shown to strongly influence the rate of ingress/egress of anions. The time differential of SPR kinetic curves can be well applied in the detecting electroinactive anion by flow injection analysis. The approach has higher sensitivity and reproducibility compared with other kinetic measurements, such as those obtained by amperometry.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Monitoring of organochlorine pesticides using PFU csystems in Yunnan lakes and rivers, China

Polyurethane foam unit (PFU) systems were collected from 11 lakes and three rivers in the Yunnan Plateau, China and, the PFU extrusion liquids, were analyzed for organochlorine pesticides (OCPs) by gas chromatography with electron capture detection (GCECD). The concentrations of pp'-DDE, HCB and HCHs were undetectable to 1.86 mu g l(-1) (mean 0.27 mu g l(-1)), undetectable to 0.72 mu g l(-1) (mean 0.11 mu g l(-1)), and 0.24-21.95 mu g l(-1) (mean 7.39 mu g l(-1)) respectively in lakes; and those in rivers were undetectable to 0.23 mu g l(-1) (mean 0.08 mu g l(-1)), 0.68-2.93 mu g l(-1) (mean 1.70 mu g l(-1)), and 2.71-37.56 mu g l(-1) (mean 17.01 mu g l(-1)) respectively. Notably, some residue levels of OCPs exceeded the US National Recommended Water Quality Criteria, implying Yunnan has levels of OCPs potentially harmful to human health. Further, the contamination by OCPs showed an obvious spatial distribution pattern. Amongst the lakes, Dianchi, Xingyun, Lugu and Yangzonghai had the highest OCP levels dominated by beta-HCH, whereas among rivers, Nujiang and Lancang Rivers had the highest contents of OCPs dominated by alpha-HCH. This demonstrates that HCHs are the predominant contaminants and some point sources of HCHs may still exist in Yunnan. The pollution levels in Yunnan were compared with other studies, suggesting the PFU method is suitable for long-term on-line monitoring of trace OCPs in aquatic ecosystems. Therefore, continuous studies monitoring OCPs in lakes and rivers are needed to further understand the future trend of contamination. (c) 2006 Elsevier Ltd. All rights reserved.