Morphology-Dependent Performance of MnO2 Nanostructure-Carbon Dot-Based Biosensors for the Detection of Glutathione.

Abstract

Herein, we develop a facile, sensitive, and selective fluorescent nanosensor for the detection of glutathione (GSH). In this protocol, carbon dots (Cdots) with a fairly high quantum yield were synthesized by a microwave-assisted pyrolysis technique. Moreover, different shapes of the MnO2 nanostructure were also prepared by the hydrothermal technique. A comparative photophysical study of different morphology-dependent Cdots@MnO2 nanostructure-based biosensors was explored, which showed different results for the quenching values of ("turn-off") fluorescence intensity, quantum yields, electron transfer rate, and average lifetime. The structure, property, and performance of nanomaterials are interdependent. Therefore, the different shapes of MnO2, that is, nanoflowers (NFs), nanorods (NRs), and a mixture of NFs/NRs was prepared by the hydrothermal method owing to different specific surface areas (23-69 m2 g-1) which put the impact on their sensing activity. It was observed that the variation in the different photophysical parameters of fluorescent Cdots such as quantum yield (Φ), average lifetime values [τav (ns)], radiative (kr) rate constant, nonradiative (knr) rate constant, rate of electron transfer (kET), the efficiency of electron transfer (ΦEET), FRET efficiency (E), and Förster distance (R0) were dependent on the different shapes of the MnO2 nanostructure. These results indicate that the transfer of energy occurs between the Cdots and different shapes of MnO2 nanostructures based on fluorescence resonance energy transfer at different charge-transfer rates. The recovery rate ("turn-on") of fluorescence of Cdots with the addition of GSH was obtained best for the NF structure by conversion of MnO2 to Mn2+, and the limit of detection was obtained as ∼19 μM for GSH. The developed sensing probes were rapid, easy, cheap, and eco-friendly for the determination of GSH.