Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (8): 797-804.DOI: 10.6023/A20050146 Previous Articles     Next Articles

Special Issue: 分子探针、纳米生物学与生命分析化学



王培培a, 梁涛a, 左苗苗b, 李贞b, 刘志洪a   

  1. a 武汉大学 化学与分子科学学院 武汉 430072;
    b 湖北大学 化学化工学院 武汉 430062
  • 投稿日期:2020-05-06 发布日期:2020-06-04
  • 通讯作者: 李贞, 刘志洪;
  • 基金资助:

A Ratiometric Upconversion Nanoprobe for Detection of HNO Based on Luminescence Resonance Energy Transfer

Wang Peipeia, Liang Taoa, Zuo Miaomiaob, Li Zhenb, Liu Zhihonga   

  1. a College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072;
    b College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062
  • Received:2020-05-06 Published:2020-06-04
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21625503, 21807028).

Nitroxyl (HNO), produced by nitric oxide (NO) with one-electron reduction and protonation, has recently received substantial interest due to its important roles in various biological functions and pharmacological activities. Research indicates that HNO also has many potential pharmacological applications for different diseases. Therefore, the development of a reliable method for HNO assay in biosystems is highly desired. Ratiometric fluorescent probes show significant advantages over traditional “turn-on” ones, because simultaneous measurement of two emission signals can provide a built-in correction and thus minimize the inaccurate fluorescence signal readouts. As far as we know, there is no ratiometric fluorescent probe for HNO detection based on upconversion nanoparticles (UCNPs). Herein, a ratiometric nanoprobe for HNO assay was constructed based on the luminescence resonance energy transfer (LRET) principle by using UCNPs with a core-shell structure (NaYbF4:30%Gd@NaYF4:2%Yb:1%Tm) as the energy donor and an organic dye Fl-TP as the potential energy acceptor. The oleate-coated UCNPs (OA-UCNPs) and Fl-TP were assembled through hydrophobic interaction to construct the upconversion nanoprobe (termed as Fl-TP-UCNPs). Because of the ring-closed form, Fl-TP displayed weak absorption and was non-fluorescent, which blocked the LRET process. After reaction with HNO, the triphenylphosphine moiety left and released Fl-HNO with the fluorescent ring-open form. Fl-HNO showed strong absorption in the range of 400~500 nm, which completely overlapped with the blue luminescence of UCNPs and triggered the LRET process between UCNPs and Fl-HNO. Thus, the luminescence from UCNPs around 480 nm decreased and the emission from Fl-HNO around 525 nm increased with a [HNO]-dependent manner. The ratiometric luminescence intensity F525 nm/F480 nm showed a good linear relationship (R2=0.9914) to the logarithm of AS (Angeli’s salt, a generally used HNO donor) concentration in the range of 3~100 μmol·L-1 and the limit of detection was 23.4 nmol·L-1. The excellent sensitivity, stability, selectivity and low cytotoxicity endow Fl-TP-UCNPs with the superior capability for HNO assay in vitro and in vivo. We found that Fl-TP-UCNPs probe is appropriate for monitoring HNO in living cells as well as imaging HNO in liver tissues. This probe may be a powerful tool for HNO assay in various physiological processes.

Key words: upconversion nanoparticles, luminescence resonance energy transfer, ratiometric signal, nitroxyl, fluorescence bioimaging