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In this paper, by employing a rigid xanthene scaffold as a bridge, we for the first time report a cofacial bispyrene derivative DPH as an efficient ratiometric fluorescent excimer probe for hypochlorite (OCl−). The probe is comprised of a rigid xanthene scaffold and two parallel pyrenes, which are linked by an OCl−-sensitive dicarboxylic acid hydrazide group. The introduction of OCl−, however, will induce oxidation of the dicarboxylic acid hydrazide moiety into a diimide group, and the subsequent hydrolysis of the diimide, to give 1-pyrenecarboxylic acid which exhibits a monomer emission at about 380 nm, with its intensity increasing with the addition of increased concentration of OCl−. Meanwhile, the excimer emission intensity gradually decreases. Such a ratiometric fluorescent response of the probe affords a high sensitivity to OCl−, with a linear response concentration range of 1 to 300 μM, and a detection limit of 0.35 μM for OCl−. It also shows a high selectivity for OCl− with no interference observed from other common anions and small molecules. Moreover, it can also act as a colorimetric probe for OCl− due to the cyan-to-blue fluorescence color change. It has been preliminarily used for practical detection of OCl− in river water samples with satisfying results.

Development of fluorescent probes for Hg(2+) has become a hot topic in modern chemical research due to its high toxicity. In this paper, we for the first time report the synthesis and application of a thioether spirocyclic rhodamine B derivative (TR) as an efficient fluorescent probe for Hg(2+). TR was synthesized using a simple procedure under mild condition. By employing a thioether spirocycle instead of classic spirolactam as recognition unit, our proposed probe TR is acidity-insensitive, and exhibits a pH-independent and ultrasensitive response to Hg(2+). The probe works well within a wide pH range from 3.5 to 11.5, and exhibits a 350-fold fluorescence enhancement upon 0.5 equiv of Hg(2+) triggered, with a detection limit of 2.5 nM estimated for Hg(2+). In virtue of the strong thiophilic characteristic of Hg(2+), the response of the probe to Hg(2+) is instantaneous and highly selective, which make it favorable for cellular Hg(2+) imaging applications. It has been preliminarily used for highly sensitive monitoring of Hg(2+) level in living cells with satisfying resolution, demonstrating its value of the practical applications in biological systems.

Fluorescence resonance energy transfer (FRET) strategy has been widely applied in designing ratiometric probes for bioimaging applications. Unfortunately, for FRET systems, sufficiently large spectral overlap is necessary between the donor emission and the acceptor absorption, which would limit the resolution of double-channel images. The through-bond energy transfer (TBET) system does not need spectral overlap between donor and acceptor and could afford large wavelength difference between the two emissions with improved imaging resolution and higher energy transfer efficiency than that of the classical FRET system. It seems to be more favorable for designing ratiometric probes for bioimaging applications. In this paper, we have designed and synthesized a coumarin-rhodamine (CR) TBET system and demonstrated that TBET is a convenient strategy to design an efficient ratiometric fluorescent bioimaging probe for metal ions. Such TBET strategy is also universal, since no spectral overlap between the donor and the acceptor is necessary, and many more dye pairs than that of FRET could be chosen for probe design. As a proof-of-concept, Hg(2+) was chosen as a model metal ion. By combining TBET strategy with dual-switch design, the proposed sensing platform shows two well-separated emission peaks with a wavelength difference of 110 nm, high energy transfer efficiency, and a large signal-to-background ratio, which affords a high sensitivity for the probe with a detection limit of 7 nM for Hg(2+). Moreover, by employing an Hg(2+)-promoted desulfurization reaction as recognition unit, the probe also shows a high selectivity to Hg(2+). All these unique features make it particularly favorable for ratiometric Hg(2+) sensing and bioimaging applications. It has been preliminarily used for a ratiometric image of Hg(2+) in living cells and practical detection of Hg(2+) in river water samples with satisfying results.