Nitrogen doped graphene quantum dots based on host guest interaction for selective dual readout of dopamine

Herein, yellow emissive nitrogen doped graphene quantum dots (N@GQDs) were prepared by a novel advanced thermal driven oxidation. The N@GQDs was functionalized with β-cyclodextrin (β-CD) to improve its catalytic performance towards dopamine (DA) detection. The β-CD/N@GQDs exhibited strong fluorescence at λ_em. = 550 nm after excitation at 460 nm with a quantum yield of 38.6%. The β-CD/N@GQDs showed good peroxidase like activity via catalyzing the oxidation of tetramethylbenzidine (TMB) in presence of H₂O₂ to form blue colored product at λ_max = 652 nm. In the colorimetric assay of DA, the detection based on the oxidation of TMB by H₂O₂ in presence of β-CD/N@GQDs as a catalyst. Then, the color of the blue oxidized TMB (oxTMB) product was reduced by addition of DA. While the fluorometric detection of DA based on the "inner filter effect" of the overlapped emission spectrum of β-CD/N@GQDs with the absorption spectrum of oxTMB, where, addition of DA reduces oxTMB to TMB and restores the fluorescence intensity of β-CD/N@GQDs. Under the optimized conditions, the colorimetric method achieved linearity range of 0.12-7.5 µM and LOD (S/N = 3) of 0.04 µM, while the fluorometric method achieved linearity range of 0.028-1.5 µM and LOD (S/N = 3) of 0.009 µM. The peroxidase like activity of β-CD/N@GQDs was used to detect DA in human plasma and serum samples with good % recoveries. The colorimetric and fluorometric methods exhibited good sensitivity and selectivity toward DA detection.