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The carbon-fiber microelectrode has been used for decades as a neurotransmitter sensor. Recently, new strategies have been developed for making carbon electrodes, including using carbon nanomaterials or pyrolyzing photoresist etched by nanolithography or 3D printing. This review summarizes how chemical and 3D surface structures of new carbon electrodes are optimized for neurotransmitter detection. There are effects of the chemical structure that are advantageous and nanomaterials are used ranging from carbon nanotube (CNT) to graphene to nanodiamond. Functionalization of these materials promotes surface oxide groups that adsorb dopamine and dopants introduce defect sites good for electron transfer. Polymer coatings such as poly(3,4-ethylenedioxythiophene) (PEDOT) or Nafion also enhance the selectivity, particularly for dopamine over ascorbic acid. Changing the 3D surface structure of an electrode increases current by adding more surface area. If the surface structure has roughness or pores on the micron scale, the electrode also acts as a thin layer cell, momentarily trapping the analyte for redox cycling. Vertically-aligned CNTs as well as lithographically-made or 3D printed pillar arrays act as thin layer cells, producing more reversible cyclic voltammograms. A better understanding of how chemical and surface structure affects electrochemistry enables rational design of electrodes. New carbon electrodes are being tested in vivo and strategies to reduce biofouling are being developed. Future studies should test the robustness for long term implantation, explore electrochemical properties of neurotransmitters beyond dopamine, and combine optimized chemical and physical structures for real-time monitoring of neurotransmitters.

Review: new insights into optimizing chemical and 3D surface structures of carbon electrodes for neurotransmitter detection