Microelectrode-based electrochemical (EC) and photoelectrochemical (PEC) sensors are promising candidates for in vivo analysis of biologically important chemicals. However, limited selectivity in complicated biological systems and poor adaptability to electrochemically non-active species restrained their applications. Herein, we propose the concept of modulating the PEC output by a fluorescence resonance energy transfer (FRET) process. The emission of energy donor was dependent on the concentration of target SO , which in turn served as the modulator of the photocurrent signal of the photoactive material. The employment of optical modulation circumvented the problem of selectivity, and the as-fabricated PEC microelectrode showed good stability and reproducibility in vivo. It can monitor fluctuations of SO levels in brains of rat models of cerebral ischemia-reperfusion and febrile seizure. More significantly, such a FRET modulated signaling strategy can be extended to diverse analytes.
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