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.

Keywords: Bimodal off-on sensing; Heteroatom-doping; Multicolor lignin carbon dots.