Application of Graphite-Epoxy Composite Electrodes in Differential Pulse Anodic Stripping Voltammetry of Heavy Metals

An analytical study on the use of graphite-epoxy composite (GEC) electrodes for differential pulse anodic stripping voltammetry (DPASV) of heavy metals is presented. This study is accompanied by microscopic observations of the electrode surface before and after the stripping step in comparison to glassy carbon electrode. GEC electrodes show much better accumulation properties and consequently acceptable behaviour which makes them suitable as working electrodes in the DPASV of heavy metals. Lead determination in real water samples in a batch system as well as some preliminary results in a flow-through system are presented. The detection limits in batch measurements were 100ppb for Cd, 10pb for lead and 50ppb for copper. The detection limit for lead in the flow-through system was similar to that in the batch. The results obtained show that these low cost and easy to prepare materials can be of interest in future research concerning stripping techniques of heavy metals and other analytes.     

Determination of Pb and Cu by Anodic Stripping Voltammetry Using Glassy Carbon Electrodes Modified with Mercury or Mercury-Nafion Films

 Two different approaches for the modification of glassy carbon electrodes using a mercury film and mercury-nafion are compared. The mixture of mercury(II) chloride solution with a nafion solution diluted in ethanol is used to coat the polished glassy carbon surface. The modified working electrodes are compared when measuring Pb and Cu in real seawater samples. An optimisation of the parameters during the formation of the films was done to obtain well-defined stripping peaks. The type of inert supporting electrolyte and the pH play an important role on the sensitivity of the measurement. Results for Pb and Cu determinations show the advantages of Hg-nafion modification as an alternative method. These advantages include a shorter modification time, the avoidance of Hg solutions during the formation of the Hg film and an improved sensitivity for Pb determination. Received March 16, 1999. Revision April 24, 2000.     

Label-free voltammetric immunosensor using a nanoporous membrane based platform

A novel device and methodology for the rapid and simple label-free electrochemical detection of proteins based on screen-printed carbon electrodes (SPCEs) modified with nanoporous Al₂O₃ membranes is reported. The nanoporous membranes are functionalized with antibodies and followed by the immunorecognition event that gives rise to the pore blocking. The blockage inside the nanochannels is fast, pore size dependent and easy to be detected by measuring the decrease in the differential pulse voltammetric (DPV) peak current of the [Fe(CN₆)]^4?/3? redox specie used as indicator. The developed nanoporous membrane based device represents a simple biodetection alternative that can be extended in the future to several other immuno and DNA detection systems.     

Compact microcubic structures platform based on self-assembly Prussian blue nanoparticles with highly tuneable conductivity

Control of molecular and supramolecular properties is used to obtain a new advanced hybrid material based on Prussian blue nanoparticles (PB NPs). This hybrid material is obtained through a self-assembled Layer-by-Layer (LbL) approach combining the advantageous features of β-cyclodextrin (β-CD) polysaccharides, PB NPs and poly(allylamine hydrochloride) from electrostatic interaction between the deposited layers. Transmission electronic microscopy images suggested that PB NPs were protected by β-CD polysaccharides that prevent the aggregation phenomena. In addition, as confirmed by scanning electronic microscopy images, it was found that PB NPs are organized in microcubic supramolecular like structures via a mesoscale self-assembly process. Interestingly, the 3-bilayer {PAH/PB-CD} film exhibited a higher density of microcubic structures and a high electrochemical response with PB sites available for redox reactions at a supramolecular level. By utilizing fewer bilayers and consequently less material deposition, the formed {PAH/PB-CD} multilayer films of a tuneable conductivity can be expected to have interesting future applications for host-guest like dependent electrochemical biosensing designs.     

Nanoparticle based enhancement of electrochemical DNA hybridization signal using nanoporous electrodes

A novel nanoparticle-based enhanced methodology for the detection of ssDNA using nanoporous alumina filter membranes, containing pores of 200 nm in diameter, is reported. The blockage of the pores due to the hybridization is detected by measuring the decrease in the differential pulse voltammetric response of the [Fe(CN)(6)](4-/3-) redox indicator and using screen-printed carbon electrodes as transducing platform. Furthermore, 20 nm gold nanoparticle (AuNPs) tags are used in order to increase the sensitivity of the assay. The enhancement mechanism of DNA detection is due to an additional blocking effect induced by hybridization reaction by bringing AuNPs inside the pores. The developed methodology can be extended to other biosensing systems with interest not only for DNA but also for proteins and cells. The developed nanochannel/nanoparticle biosensing system would have enormous potential in future miniaturized designs adapted to mass production technologies such as screen-printing technology.     

Magnetic and electrokinetic manipulations on a microchip device for bead-based immunosensing applications

The combination of electrophoretic and magnetic manipulations with electrochemical detection for a versatile microfluidic and bead-based biosensing application is demonstrated. Amperometric detection is performed in an off-channel setup by means of a voltammetric cell built at the microchannel outlet and using a gold working electrode. Superparamagnetic particles are introduced and handled inside the channel by means of an external permanent magnet in combination with the electrogenerated flow which allows reproducible loading. The specific detection of phenol as electroactive alkaline phosphatase product is used in this study as proof of concept for a sensitive protein quantification. Characterizations and optimization of different parameters have been carried out in order to achieve the best detection signal. The applicability of the device has been finally demonstrated by the detection of rabbit IgG as model protein after an immunoassay performed on magnetic particles as immobilization platform. A comparison between the electrochemical detection using the developed device and the optical standard detection revealed similar performances with, however, extremely lower amount of reagent used and shorter analysis time. The developed electrophoretic- and magnetic-based chip may open the way to several other biosensing applications with interest not only for other proteins but also for DNA analysis, cell counting, and environmental control.     

Nanoparticles for the development of improved (bio)sensing systems

Nanoparticles serve as fundamental building blocks for nanobiotechnology, especially in several applications in the development of novel (bio)sensing systems. Nanoparticles can be used for modification of the surfaces of (bio)sensing transducers or as optical or electroactive labels to improve different aspects of performance, for example sensitivity, detection limit, multidetection capability, and response stability. Nanoparticles can be integrated into the transducer materials on an individual basis or inside other matrices to ensure the immobilization of recognition biomolecules and/or receptors which are the principal components of the (bio)sensing systems. Incorporation of nanoparticles into optical and electrochemical (bio)sensing systems, including their use in microfluidic based systems has the advantages of enabling the design of robust, easy to use, portable, and cost-effective devices.     

Experimental study of electrostatically stabilized colloidal particles: colloidal stability and charge reversal

We consider the interaction of colloidal spheres in the presence of mono-, di-, and trivalent ions. The colloids are stabilized by electrostatic repulsion due to surface charges. The repulsive part of the interaction potential Ψ(d) is deduced from precise measurements of the rate of slow coagulation. These "microsurface potential measurements" allow us to determine a weak repulsion in which Ψ(d) is of the order of a few k(B)T. These data are compared to ζ potential measured under similar conditions. At higher concentrations both di- and trivalent counterions accumulate at the very proximity of the particle surface leading to charge reversal. The salt concentration c(cr) at which charge reversal occurs is found to be always above the critical coagulation concentration c(ccc). The analysis of Ψ(d) and of the ζ potential demonstrates, however, that adsorption of multivalent counterions starts far below c(cr). Hence, colloid stability in the presence of di- and trivalent ions cannot be described in terms of a DLVO ansatz assuming a surface charge that is constant with regard to the ionic strength.