Ultrasensitive Detection of Dopamine with Carbon Nanopipets

Carbon fiber micro- and nanoelectrodes have been extensively used to measure dopamine and other neurotransmitters in biological systems. Although the radii of some reported probes were ≪1 μm, the lengths of the exposed carbon were typically on the micrometer scale, thus limiting the spatial resolution of electroanalytical measurements. Recent attempts to determine neurotransmitters in single cells and vesicles have provided additional impetus for decreasing the probe dimensions. Here, we report two types of dopamine sensors based on carbon nanopipets (CNP) prepared by chemical vapor deposition of carbon into prepulled quartz capillaries. These include 10-200 nm radius CNPs with a cavity near the orifice and CNPs with an open path in the middle, in which the volume of sampled solution can be controlled by the applied pressure. Because of the relatively large surface area of carbon exposed to solution inside the pipet, both types of sensors yielded well-shaped voltammograms of dopamine down to ca. 1 nM concentrations, and the unprecedented voltammetric response to 100 pM dopamine was obtained with open CNPs. TEM tomography and numerical simulations were used to model CNP responses. The effect of dopamine adsorption on the CNP detection limit is discussed along with the possibilities of measuring other physiologically important analytes (e.g., serotonin) and eliminating anionic and electrochemically irreversible interferences (e.g., ascorbic acid).