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Detection of dopamine in the presence of excess ascorbic acid at physiological concentrations through redox cycling at an unmodified microelectrode array

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Abstract

The electrochemical behavior of dopamine was examined under redox cycling conditions in the presence and absence of a high concentration of the interferent ascorbic acid at a coplanar, microelectrode array where the area of the generator electrodes was larger than that of the collector electrodes. Redox cycling converts a redox species between its oxidized and reduced forms by application of suitable potentials on a set of closely located generator and collector electrodes. It allows signal amplification and discrimination between species that undergo reversible and irreversible electron transfer. Microfabrication was used to produce 18 individually addressable, 4-μm-wide gold band electrodes, 2 mm long, contained in an array having an interelectrode spacing of 4 μm. Because the array electrodes are individually addressable, each can be selectively biased to produce an overall optimal electrochemical response. Four adjacent microbands were shorted together to serve as the collector, and were flanked on each side by seven microbands shorted as the generator (a ratio of 1:3.5 of electroactive area, respectively). This configuration achieved a detection limit of 0.454 ± 0.026 μM dopamine at the collector in the presence of 100 μM ascorbic acid in artificial cerebrospinal fluid buffer, concentrations that are consistent with physiological levels. Enhancement by surface modification of the microelectrode array to achieve this detection limit was unnecessary. The results suggest that the redox cycling method may be suitable for in vivo quantification of transients and basal levels of dopamine in the brain without background subtraction.

Microelectrode array chip design and assignment of electrodes used for determination of dopamine (DA) in the presence of large excess of ascorbic acid (AA) by redox cycling. Analytes (DA and AA) are oxidized at the generator electrodes to form dopamine-o-quinone (DAQ) and dehydroascorbic acid (AAo) which diffuse to the nearest collector electrodes. DA is selectively detected at the collector electrodes, because DAQ can be reduced there, but AAo hydrolyzes to a nonelectroactive form prior to arrival

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Acknowledgments

Funding was provided in part by the National Science Foundation (CHE-0719097) and the Arkansas Biosciences Institute, the major research component of the Arkansas Tobacco Settlement Proceeds Act of 2000. We thank Errol Porter for advice on microfabrication. The use of the High Density Electronics Center microfabrication facilities is also acknowledged. We express our appreciation to Adrian Michael of the University of Pittsburgh for insightful discussions about applications. T.S. Hollingsworth is acknowledged for assistance in preparing this manuscript.

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  1. Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, AR, 72701, USA

    Anupama Aggarwal, Mengjia Hu & Ingrid Fritsch

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  1. Anupama Aggarwal
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Published in the topical collection Bioelectroanalysis with guest editors Nicolas Plumeré, Magdalena Gebala, and Wolfgang Schuhmann.

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Aggarwal, A., Hu, M. & Fritsch, I. Detection of dopamine in the presence of excess ascorbic acid at physiological concentrations through redox cycling at an unmodified microelectrode array. Anal Bioanal Chem 405, 3859–3869 (2013). https://doi.org/10.1007/s00216-013-6738-z

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