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.

Sensitive and selective electrochemical aptasensing method for the voltammetric determination of dopamine based on AuNPs/PEDOT-ERGO nanocomposites.

In this study, the effects of phosphate buffered saline (PBS) and graphene oxide (GO) as supporting electrolytes and dopants on the electropolymerization process of 3,4-ethylenedioxythiophene (EDOT) on glassy carbon electrode (GCE) were investigated. It was found that the PEDOT-ERGO nanocomposites obtained by a simple one-step electrochemical redox polymerization method using GO as the only supporting electrolyte and dopant possess excellent electrochemical properties. Then, the PEDOT-ERGO nanocomposites were used as electrode substrate to further modify with AuNPs, and an electrochemical aptasensor based on AuNPs/PEDOT-ERGO nanocomposites was successfully constructed for the sensitive and selective determination of dopamine (DA). Comparison of the cyclic voltammetric response of different neurotransmitters before and after aptamer assembly showed that the aptamer significantly improved the selectivity of the sensor for DA. The low detection limit of 1.0 µM (S/N = 3) indicated the good electrochemical performance of the PEDOT-ERGO nanocomposite film. Moreover, the aptasensor showed good recoveries in 50-fold diluted fetal bovine serum with RSD values all less than 5 % (n = 5), indicating that the PEDOT-ERGO nanocomposites and the electrochemical aptasensor have promising applications in other neurochemicals assay and biomedical analysis.