Universal Covalent Grafting Strategy of an Aptamer on a Carbon Fiber Microelectrode for Selective Determination of Dopamine In Vivo

The chemical information on brain science provided by electrochemical sensors is critical for understanding brain chemistry during physiological and pathological processes. A major challenge is the selectivity of electrochemical sensors in vivo. This work developed a universal covalent grafting strategy of an aptamer on a carbon fiber microelectrode (CFE) for selective determination of dopamine in vivo. The universal strategy was proposed by oxidizing poly(tannic acid) (pTA) to form an oxidized state (pTAox) and then coupling a nucleophilic sulfhydryl molecule of the dopamine-binding mercapto-aptamer with the o-quinone moiety of pTAox based on click chemistry for the interfacial functionalization of the CFE surface. It was found that the universal strategy proposed could efficiently graft the aptamer on a glassy carbon electrode, which was verified by using electroactive 6-(ferrocenyl) hexanethiol as a redox reporter. The amperometric method using a fabricated aptasensor for the determination of dopamine was developed. The linear range of the aptasensor for the determination of dopamine was 0.2–20 μM with a sensitivity of 0.09 nA/μM and a limit of detection of 88 nM (S/N = 3). The developed method has high selectivity originating from the specific recognition of the aptamer in concert with the cation-selective action of pTA and could be easily applicable to probe dopamine dynamics in the brain. Furthermore, complex vesicle fusion modes were first observed at the animal level. This work demonstrated that the covalently grafted immobilization strategy proposed is promising and could be extended to the in vivo analysis of other neurochemicals.