title: Evaluation of in-channel amperometric detection using a dual-channel microchip electrophoresis device and a two-electrode potentiostat for reverse polarity separations.
abstract: In-channel amperometric detection combined with dual-channel microchip electrophoresis is evaluated using a two-electrode isolated potentiostat for reverse polarity separations. The device consists of two separate channels with the working and reference electrodes placed at identical positions relative to the end of the channel, enabling noise subtraction. In previous reports of this configuration, normal polarity and a three-electrode detection system were used. In the two-electrode detection system described here, the electrode in the reference channel acts as both the counter and reference. The effect of electrode placement in the channels on noise and detector response was investigated using nitrite, tyrosine, and hydrogen peroxide as model compounds. The effects of electrode material and size and type of reference electrode on noise and the potential shift of hydrodynamic voltammograms for the model compounds were determined. In addition, the performance of two- and three-electrode configurations using Pt and Ag/AgCl reference electrodes was compared. Although the signal was attenuated with the Pt reference, the noise was also significantly reduced. It was found that lower LOD were obtained for all three compounds with the dual-channel configuration compared to single-channel, in-channel detection. The dual-channel method was then used for the detection of nitrite in a dermal microdialysis sample obtained from a sheep following nitroglycerin administration.
authors.affiliation: Ralph N. Adams Institute for Bioanalytical Chemistry, University of Kansas, Lawrence, KS, USA; Institute of Chemistry and Biotechnology, Federal University of Alagoas, UFAL, Maceió, AL, Brazil.
authors.forename: Diogenes
authors.initials: D
authors.lastname: Meneses
authors.forename: Dulan B
authors.initials: DB
authors.lastname: Gunasekara
authors.forename: Pann
authors.initials: P
authors.lastname: Pichetsurnthorn
authors.forename: José A F
authors.initials: JA
authors.lastname: da Silva
authors.forename: Fabiane C
authors.initials: FC
authors.lastname: de Abreu
authors.forename: Susan M
authors.initials: SM
authors.lastname: Lunte
mesh_terms: D055664:Electrochemical Techniques / Q000295:instrumentation* / Q000379:methods; D004566:Electrodes; D046209:Electrophoresis, Microchip / Q000295:instrumentation* / Q000379:methods; D004867:Equipment Design; D057230:Limit of Detection; D017551:Microdialysis; D009573:Nitrites
chemical_list: D009573:Nitrites
keywords: Dual-channel; Electrically isolated potentiostat; In-channel electrochemical detection; Microchip electrophoresis; Noise