Zhangyan Ma

MnO2 nanomaterials have aroused widespread attention because of their nanozyme activity, redox properties, good biocompatibility, and therapy-related activities. However, not many reports on self-luminescent MnO2 materials have been concerned to date, which greatly hampered their further development in various fields. In this paper, luminescent MnO2 quantum dots (MnO2 QDs) have been first prepared via a facile one-step ultrasonic method. With the assistance of bovine serum albumin (BSA) or cysteine (Cys), the synthesized MnO2 QDs (BSA-MnO2 QDs or Cys-MnO2 QDs) display strongly enhanced fluorescence (FL). The prepared BSA-MnO2 QDs with a particle size of about 1 to 2 nm show the maximum excitation and emission peaks at 320 and 410 nm with excellent salt stability, anti-photobleaching ability, and time stability. It is confirmed that BSA plays a dual function as the exfoliating agent to promote the exfoliation of bulk MnO2 nanosheets and as the capping agent to provide a friendly microenvironment for MnO2 QDs. Ag ions can destroy the microenvironment of BSA-MnO2 QDs owing to the in situ formation of Ag nanoparticles (Ag NPs) mediated by BSA on the surface of the QDs. Then, these Ag NPs can quench the FL intensity of the QDs by fluorescence resonance energy transfer. However, the FL strength of the BSA-MnO2 QDs is recovered after adding H2O2 and NaHS since they may react with Ag NPs to produce Ag+ and Ag2S, which further confirmed the role of BSA. This work not only opens up a facile and universal avenue to synthesize luminescent MnO2 QDs with enhanced FL but also provides a possible sensing platform through tuning the microenvironment of the MnO2 QDs. The MnO2 QDs with outstanding performance may show great potential as fluorescent probes in the fields of biological imaging, optical sensing, drug delivery, and therapy.

A simple one-step ultrasonic method was developed for the synthesis of luminescent MnO2 quantum dots (MnO2 QDs) in the presence of cysteine, in which cysteine acted as the exfoliating agent and stabilization ligand. The cysteine-stabilized MnO2 QDs (Cys-MnO2 QDs) possess a fluorescence quantum yield of 4.7%, and the fluorescence intensity of Cys-MnO2 QDs is sensitive to dopamine (DA). The mechanism by which the Cys-MnO2 QDs catalyzed the self-polymerization of DA to form polydopamine nanoparticles (PDA NPs) and caused the fluorescence resonance energy transfer (FRET) between MnO2 QDs and PDA NPs was revealed. The sensing platform displayed a wide detection range (0.1–200 μM) with a low detection limit of 28 nM for the detection of DA. Moreover, the Michael addition/Schiff base reaction between the PDA NPs and cysteine on MnO2 QDs was demonstrated to facilitate the excellent selectivity toward DA detection in the presence of various interferences. This work not only develops a robust method for the preparation of highly luminescent MnO2 QDs but also provides a universal strategy on the basis of surface chemical reaction-induced FRET for the detection of DA with high sensitivity and selectivity, which is promising in the application of clinical diagnosis, drug delivery, and fluorescence-guided cancer therapy.