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We have developed a chip-based nanofluidic device to amplify the electrochemical signal of catechols by orders of magnitude. The amplification is based on rapid redox cycling between plane parallel electrodes inside a nanochannel. We show that it is possible to monitor the signal of only a few hundred molecules residing in the active area of the nanofluidic sensor. Furthermore, due to the nanochannel design, the sensor is immune to interference by molecules undergoing irreversible redox reactions. We demonstrate the selectivity of the device by detecting catechol in the presence of ascorbic acid, whose oxidized form is only stable for a short time. The interference of ascorbic acid is usually a challenge in the detection of catecholamines in biological samples.

Electrochemical mapping of neurotransmitter concentrations on a chip promises to be an interesting technique for investigating synaptic release in cellular networks. In here, we present a novel chip-based device for the detection of neurotransmitter fluctuations in real-time. The chip features an array of plane-parallel nanocavity sensors, which strongly amplify the electrochemical signal. This amplification is based on efficient redox cycling via confined diffusion between two electrodes inside the nanocavity sensors. We demonstrate the capability of resolving concentration fluctuations of redox-active species in a microfluidic mixing gradient on the chip. The results are explained by a simulated concentration profile that was calculated on the basis of the coupled Navier−Stokes and convection-diffusion equations using a finite element approach.