Most of the current techniques for detection of dopamine exploit its ease of oxidation. However, the oxidative approaches suffer from a common problem. The products of dopamine oxidation can react with ascorbic acid present in samples and regenerate dopamine again, which severely limits the accuracy of detection. In this paper, we report a nonoxidative approach to electrochemically detect dopamine with high sensitivity and selectivity. This approach takes advantage of the high performance of our newly developed poly(anilineboronic acid)/carbon nanotube composite and the excellent permselectivity of the ion-exchange polymer Nafion. The binding of dopamine to the boronic acid groups of the polymer with large affinity affects the electrochemical properties of the polyaniline backbone, which act as the transduction mechanism of this nonoxidative dopamine sensor. The unique reduction capability and high conductivity of single-stranded DNA functionalized, single-walled carbon nanotubes greatly improved the electrochemical activity of the polymer in physiological buffer, and the large surface area of the carbon nanotubes largely increased the density of the boronic acid receptors. The high sensitivity along with the improved selectivity of this sensing approach is a significant step forward toward molecular diagnosis of Parkinson's disease.

Most of the current techniques for in vivo detection of dopamine exploit the ease of oxidation of this compound. The major problem during the detection is the presence of a high concentration of ascorbic acid that is oxidized at nearly the same potential as dopamine on bare electrodes. Furthermore, the oxidation product of dopamine reacts with ascorbic acid present in samples and regenerates dopamine again, which severely limits the accuracy of the detection. Meanwhile, the product could also form a melanin-like insulating film on the electrode surface, which decreases the sensitivity of the electrode. Various surface modifications on the electrode, new materials for making the electrodes, and new electrochemical techniques have been exploited to solve these problems. Recently we developed a new electrochemical detection method that did not rely on direct oxidation of dopamine on electrodes, which may naturally solve these problems. This approach takes advantage of the high performance of our newly developed poly(anilineboronic acid)/carbon nanotube composite and the excellent permselectivity of the ion-exchange polymer Nafion. The high affinity binding of dopamine to the boronic acid groups of the polymer affects the electrochemical properties of the polyaniline backbone, which act as the basis for the transduction mechanism of this non-oxidative dopamine sensor. The unique reduction capability and high conductivity of single-stranded DNA functionalized single-walled carbon nanotubes greatly improved the electrochemical activity of the polymer in a physiologically-relevant buffer, and the large surface area of the carbon nanotubes increased the density of the boronic acid receptors. The high sensitivity and selectivity of the sensor show excellent promise toward molecular diagnosis of Parkinson's disease. In this review, we will focus on the discussion of this novel detection approach, the new interferences in this detection approach, and how to eliminate these interferences toward in vivo and in vitro detection of the neurotransmitter dopamine.

The electrochemistry of a poly(anilineboronic acid)/carbon nanotube composite was studied in the presence of dopamine and ascorbic acid. To understand the binding affinity of dopamine and ascorbic acid to the boronic acid functional groups in the composite, the association constants between the diol groups in dopamine and ascorbic acid and the boronic acid were experimentally determined using a fluorescence-based binding assay. The results demonstrate that ascorbic acid could severely interfere with the detection of dopamine in nonoxidative boronic acid-binding approaches: Ascorbic acid was able to electrocatalytically reduce the fully oxidized polyaniline backbone during the electrochemical oxidation process; similarly to dopamine, ascorbic acid was also able to bind to the boronic acid groups through its planar diol group even though the binding affinity is much lower. The examination of the dopamine transduction mechanism and ascorbic acid interference mechanism in this nonoxidative approach will benefit the design of future boronic acid-based sensors.