Preparation of B, N, S co-Doped Graphene Quantum Dots for Fluorescence Detection of Fe 3+ and H2P       O   4   -     †

doi:10.7503/cjcu20190464

Abstract

Abstract:

By doping heteroatoms(B, N, S, P and Si) into graphene quantum dots(GQDs), the surface and local chemical features of GQDs could be effectively improved and the optical characteristics be adjusted. Herein, a (B, N, S) co-doped BNS-GQDs was designed and synthesized for “OFF-ON-OFF” fluorescence detection to Fe ³⁺ and H₂P $O 4 -$ in pure water. BNS-GQDs prepared by hydrothermal method had a uniform particle size with average diameter of 4 nm. TEM, XRD, Raman, FTIR and XPS analysis results showed that BNS-GQDs had a similar structure to graphene, and the heteroatoms(B, N, S) had been successfully doped into GQDs. The fluorescence spectra showed that the selective detection of Fe ³⁺ was achieved based on fluorescence quenching of BNS-GQDs, and its fluorescence could be restored after the addition of H₂P $O 4 -$ that could be used to detect H₂P $O 4 -$ with high sensitivity. Meanwhile, the detection limits for Fe ³⁺ and H₂P $O 4 -$ were 4.35 μmol/L and 1.02 μmol/L, respectively. The interaction mechanism between BNS-GQDs and ions was discussed by fluorescence attenuation test and TEM. It was suggested that the fluorescence quenching of BNS-GQDs caused by Fe ³⁺ might be based on static quenching and/or excited state electron transfer. The introduction of H₂P $O 4 -$ destroys the interaction between BNS-GQDs and Fe ³⁺. The recognition of BNS-GQDs for Fe ³⁺ and H₂P $O 4 -$ had good reversibility. Also, BNS-GQDs was successfully applied to monitor concentration of Fe ³⁺ and H₂P $O 4 -$ in Hela cells and real water samples by fluorescence response, suggesting its potential and significance in bioanalysis and environment detection in the future.

Key words: B,N,S co-Doped graphene quantum dots, Fluorescence probe, Fe ³⁺, H₂P $O 4 -$ , Cell imaging

CLC Number:

TrendMD:

YU Zhaochuan, MA Wenhui, WU Tao, WEN Jing, ZHANG Yong, WANG Liyan, CHU Hongtao. Preparation of B, N, S co-Doped Graphene Quantum Dots for Fluorescence Detection of Fe ³⁺ and H₂P $O 4 - †$ [J]. Chem. J. Chinese Universities, 2019, 40(11): 2286.

Figures/Tables 11

Scheme 1 Synthesis of BNS-GQDs(A) and the proposed mechanism for Fe3+ and H2PO4- detection by BNS-GQDs(B)

Fig.1 HRTEM images(A), the corresponding size distribution(B), XRD pattern(C) and Raman spectrum(D) of as-prepared BNS-GQDs

Fig.2 FTIR(A) and full-scan XPS(B) spectra of BNS-GQDs

Fig.3 Ultraviolet absorption(a) and fluorescence(b)(λex=350 nm) spectra of BNS-GQDs Inset: the photographs of BNS-GQDs under visible(left) and UV(right, 365 nm) lights

Fig.4 Fluorescence spectra of BNS-GQDs in the presence of different concentrations of Fe3+(0—666.7 μmol/L) in pure water Inset: variation of F/F0 as a function of the concentration of Fe3+.

Fig.5 Selectivity of BNS-GQDs towards Fe3+ over the other competing metal ions Represent the fluorescence response of BNS-GQDs to different metal ions(333 μmol/L) in the absence of Fe3+, and represent the fluorescence response of BNS-GQDs to different metal ions(1000 μmol/L) in the presence of Fe3+(333 μmol/L). λex=350 nm, λem=427 nm.

Fig.6 Fluorescence spectra of BNS-GQDs+Fe3+ in the presence of different concentrations of H2PO4-(0—1833.3 μmol/L) in pure water Inset: variation of F/F0 as a function of the concentration of H2P O 4 - .

Fig.7 Selectivity of BNS-GQDs+Fe3+ towards H2PO4- over the other competing anions Represent the fluorescence response of BNS-GQDs+Fe3+ to different anions(1166.7 μmol/L) in the absence of H2P , and represent the fluorescence response of BNS-GQDs+Fe3+ to different anions(3000 μmol/L) in the presence of H2P (1166.7 μmol/L).

Fig.8 Change in the fluorescence intensity of BNS-GQDs system on alternate addition of Fe3+(333 μmol/L) and H2PO4-(1166.7 μmol/L) λex=350 nm, λem=427 nm.

Fig.9 Fluorescence decay curves of BNS-GQDs before(a) and after(b) the addition of 333 μmol/L Fe3+(A) and TEM image of BNS-GQDs after the addition of 333 μmol/L Fe3+(B)

Fig.10 Images of Fe3+and H2PO4- in living Hela cells with BNS-GQDs The bright-field images(A—C), fluorescence images(D—F) and merged images(G—I) of the cells are treated with BNS-GQDs(A, D, G), BNS-GQDs+Fe3+(B, E, H), BNS-GQDs+Fe3++H2P O 4 - (C, F, I).

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Preparation of B, N, S co-Doped Graphene Quantum Dots for Fluorescence Detection of Fe ³⁺ and H₂P $O 4 - †$

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