Heteroatom-engineered multicolor lignin carbon dots enabling bimodal fluorescent off-on detection of metal-ions and glutathione

Abstract

Carbon dots (CDs) have emerged as a promising subclass of optical nanomaterials with versatile functions in multimodal biosensing. Howbeit the rapid, reliable and reproducible fabrication of multicolor CDs from renewable lignin with unique groups (e.g., –OCH3, –OH and –COOH) and alterable moieties (e.g., β-O-4, phenylpropanoid structure) remains challenging due to difficult-to-control molecular behavior. Herein we proposed a scalable acid-reagent strategy to engineer a family of heteroatom-doped multicolor lignin carbon dots (LCDs) that are functioned as the bimodal fluorescent off-on sensing of metal-ions and glutathione (GSH). Benefiting from the modifiable photophysical structure via heteroatom-doping (N, S, W, P and B), the multicolor LCDs (blue, green and yellow) with a controllable size distribution of 2.06–2.22 nm deliver the sensing competences to fluorometric probing the distinctive metal-ion systems (Fe3+, Al3+ and Cu2+) under a broad response interval (0–500 μM) with excellent sensitivity and limit of detection (LOD, 0.45–3.90 μM). Meanwhile, we found that the addition of GSH can efficiently restore the fluorescence of LCDs by forming a stable Fe3+-GSH complex with a LOD of 0.97 μM. This work not only sheds light on evolving lignin macromolecular interactions with tunable luminescent properties, but also provides a facile approach to synthesize multicolor CDs with advanced functionalities.