A ratiometric fluorescent sensing of proanthocyanidins by MnO2 nanosheets simultaneously tuning the photoluminescence of Au/AgNCs and thiamine

Abstract

By simultaneously regulating the photoluminescence of alloy Au/Ag nanoclusters (NCs) and thiamine (VB1) through MnO₂ nanosheets (MnO₂ NS), a novel ratiometric fluorescent probe (RF-probe) was established for sensitively and selectively monitoring proanthocyanidins (PAs). The introduction of Ag (I) ions could enhance significantly the quantum yields (QYs, 11.1%) of AuNCs based on the synthetic method of UVI (UV irradiation) combined with MWH (microwave heating). MnO₂ NS could quench the fluorescence (FL) of Au/AgNCs mainly coming from Förster resonance energy transfer (FRET), while it could act as a nanozyme catalyst for directly catalyzing the oxidation of VB1 to produce highly fluorescent oxVB1. In the presence of PAs, MnO₂ was reduced to Mn²⁺, which caused that its quenching capacity and oxidase-like activity were vanished, thus the FL of oxVB1 and Au/AgNCs was reduced and recovered. The concentration of PAs could be monitored by the RF-probe with a linear range of 0.27-22.4 μmol L^-1 and corresponding limit of detection (LOD) and limit of quantification (LOQ) were calculated to be 75.9 and 250.5 nmol L^-1. Furthermore, the RF-probe was successfully used for the determination of PAs in mineral water, PAs additive and PAs capsule with satisfactory results compared to the standard HPLC method.

Keywords: Assay; Au/AgNCs; Proanthocyanidins; Quenching mechanism; RF-probe.