One-step synthesis of boron-doped graphene quantum dots for fluorescent sensors and biosensor

Heteroatom doping can endow graphene quantum dots (GQDs) with various new or improved structural, optical and physicochemical properties. In contrast to the widely reported oxygen, nitrogen or sulfur doping in GQDs, simple and scalable synthesis of boron-doped GQDs (B-GQDs) with high yield and quantum yields remains challenge. In this work, B-GQDs are one-step synthesized and serve as the fluorescence probes for the fabrication of sensors towards Fe³⁺ ion or phosphate (Pi) as well as biosensor towards cytochrome C (Cyt C). The B-GQDs are facile synthesized using one-step bottom-up molecular fusion between 1,3,6-trinitropyrene and borax in sodium hydroxide under hydrothermal process. The synthesis can be performed using large volume autoclave (500 ml) with a high yield of 71%, indicating possibility for gram-scale production of B-GQDs. The as-prepared B-GQDs exhibit single or bilayer graphene structure, high crystallinity, uniform size, bright (absolute photoluminescence quantum yield of 16.8%) and excitation-independent green fluorescence (maximum excitation wavelength and emission wavelength of 480 nm and 520 nm, respectively). Successful doping of B atoms in the lattice of GQDs enables high selectivity towards Fe³⁺. Based on quenching of fluorescence of B-GQDs by Fe³⁺ (turn-off model), detection of Fe³⁺ (with limit of detection-LOD of 31.2 nM) and Fe³⁺-rich Cyt C (with LOD of 5.9 μg/ml) are demonstrated. As Pi can recover Fe³⁺-quenched fluorescence of B-GQDs (turn-off-on model), indirect fluorescent detection of Pi is also achieved with LOD of 340 nM. In addition, detection of Fe³⁺, Cyt C and Pi in real samples is achieved.