高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (11): 2286-2293.doi: 10.7503/cjcu20190464

• 分析化学 • 上一篇    下一篇

B,N,S共掺杂石墨烯量子点的制备及对Fe 3+和H2P O 4 - 的荧光检测

喻照川1,马文辉1,*(),吴涛1,问婧1,张永2,王丽艳1,初红涛1   

  1. 1. 齐齐哈尔大学化学与化学工程学院
    2. 材料科学与工程学院, 齐齐哈尔 161006
  • 收稿日期:2019-08-26 出版日期:2019-11-10 发布日期:2019-10-18
  • 通讯作者: 马文辉 E-mail:mwh972@163.com
  • 基金资助:
    黑龙江省自然科学基金(B2015017);黑龙江省教育厅基本科研业务专项资助(135209201)

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

YU Zhaochuan1,MA Wenhui11,*(),WU Tao1,WEN Jing1,ZHANG Yong2,WANG Liyan1,CHU Hongtao1   

  1. 1. College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China
    2. College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006, China
  • Received:2019-08-26 Online:2019-11-10 Published:2019-10-18
  • Contact: MA Wenhui1 E-mail:mwh972@163.com
  • Supported by:
    ? Supported by the Natural Science Foundation of Heilongjiang Province, China(B2015017);The Fundamental Research Funds in Heilongjiang Provincial Universities of China(135209201)

摘要:

利用水热法制备了一种可在纯水体系中连续“OFF-ON-OFF”荧光识别Fe 3+和H2P O 4 - 的B, N, S共掺杂的石墨烯量子点探针材料(BNS-GQDs), 并对其形貌和结构进行了表征, 结果表明, BNS-GQDs粒径分布均匀, 平均粒径为4 nm, 具有类似石墨烯的结构, 且成功掺杂了B, N, S原子. 光谱表征结果表明, 其在纯水体系中可以实现对Fe 3+的荧光猝灭识别; 同时, BNS-GQDs+Fe 3+体系能够专一性地荧光增强识别H2P O 4 - . 识别机理研究表明, BNS-GQDs可与Fe 3+通过静电作用形成配合物并向Fe 3+转移电子, 从而引起荧光猝灭; H2P O 4 - 可从上述配合物中置换出Fe 3+, 引起体系荧光恢复. BNS-GQDs识别Fe 3+和H2P O 4 - 具有较好的可逆性, 可应用于Hela细胞和实际水样中Fe 3+和H2P O 4 - 的检测.

关键词: B,N,S共掺杂石墨烯量子点, 荧光探针, Fe 3+, H2P O 4 - , 细胞成像

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

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