A novel ratiometric fluorescent Fe3+ sensor based on a phenanthroimidazole chromophore

doi:10.1016/j.aca.2008.12.049

Analytica Chimica Acta

Volume 634, Issue 2, 23 February 2009, Pages 262-266

https://doi.org/10.1016/j.aca.2008.12.049 Get rights and content

Abstract

Phenanthroimidazole derivative 1 has been developed as a rare example of ratiometric fluorescent sensors for Fe³⁺. Interestingly, upon treatment with Fe³⁺, the sensor displayed a ratiometric fluorescent response with an enhancement of the ratios of emission intensities at 440 and 500 nm from 0.36 to 3.24. The detection range of the sensor for Fe³⁺ is in the 1.0 × 10⁻⁵–1.5 × 10⁻⁴ M concentration range and the detection limit is 5.26 × 10⁻⁶ M. In addition, the sensor showed good selectivity to Fe³⁺ with the selectivity coefficients $(K_{F e^{3+}} = S_{F e^{3+}} / S_{0})$ of Fe³⁺ over other metal ions tested in the range of 5–68.

Introduction

Fluorescent sensors for metal ions have received intense attention due to their potential applications in environment, chemistry, biology, and medicine [1], [2], [3]. Iron is an essential trace element that plays a significant role in many chemical and biological processes [4], [5]. Therefore, it is of great interest to detect trace amounts of Fe³⁺ ions. Although some Fe³⁺ fluorescent sensors have been reported, most of them exhibited a response to Fe³⁺ with changes only in fluorescent intensity [6], [7], [8], [9], [10], [11], [12], [13], [14], [15], [16], [17]. A major limitation of intensity-based sensors is that variations in sample and probe environment are problematic for utilization in quantitative measurements [18], [19]. By contrast, ratiometric fluorescent sensors allow the measurement of emission intensities at two different wavelengths, which should provide a built-in correction for environmental effects and can also enhance the dynamic range of fluorescence measurement [20], [21], [22]. However, ratiometric fluorescent sensors for Fe³⁺ are extremely scarce. Thus, there is a great need to develop fluorescent sensors that can display a ratiometric fluorescent response to Fe³⁺. Herein, we present compound 1 consisted of a phenanthroimidazole chromophore and a bipyridyl group as a novel ratiometric fluorescent Fe³⁺ sensor. Importantly, upon addition of Fe³⁺ from free to 30 equiv, the sensor displayed a ratiometric fluorescent response with an enhancement of the ratios of emission intensities at 440 and 500 nm from 0.36 to 3.24. Furthermore, the ratiometric fluorescent sensor also exhibited a high selectivity for Fe³⁺ over other metal ions.

Section snippets

Reagents

Unless otherwise stated, all reagents were purchased from commercial suppliers and used without further purification. Solvents were purified and dried by standard methods prior to use. Twice-distilled water was used throughout all experiments. The solutions of metal ions were prepared from ZnCl₂, CoCl₂·6H₂O, CuCl₂·2H₂O, NiCl₂·6H₂O, MgCl₂, KCl, NaCl, CaCl₂, HgCl₂, CdCl₂·1/2H₂O, Cr₂(SO₄)₃·15H₂O, MnSO₄·H₂O, FeCl₃, and Fe(NO₃)₃ respectively. TLC analyses were performed on silica gel plates and

Synthesis of sensor 1

Sensor 1 is consisted of a phenanthroimidazole dye [23] and a bipyridine group [24], [25]. The intermediate 2, 4-formylphenyl-2, 2′-bipyridine, was synthesized according to a procedure reported by us [26]. Compound 1 was then readily prepared by reaction of 9,10-phenanthrenequinone with 4-formylphenyl-2, 2′-bipyridine and NH₄OAc in AcOH based on a similar protocol [27] in a 42% yield (Scheme 1).

Ratiometric response to Fe³⁺

Fig. 1 displays the absorption spectra of sensor 1, control compounds 3 and 4 (the structures of

Conclusion

Phenanthroimidazole derivative 1 has been developed as a novel ratiometric fluorescent sensor for Fe³⁺. It is worthy to note that the examples of ratiometric fluorescent sensors for Fe³⁺ are very sparse. Importantly, upon treatment with Fe³⁺, the sensor displayed a ratiometric fluorescent response with an enhancement of the ratios of emission intensities at 440 and 500 nm from 0.36 to 3.24. Furthermore, the sensor also exhibited high selectivity for Fe³⁺ over other metal ions.

Acknowledgments

Funding was partially provided by the Key Project of Chinese Ministry of Education (no. 108167), the National Science Foundation of China (no. 20872032), the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (2007–24), and the Hunan University research funds.

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Analytica Chimica Acta

Abstract

Introduction

Section snippets

Reagents

Synthesis of sensor 1

Ratiometric response to Fe³⁺

Conclusion

Acknowledgments

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Cited by (147)

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Colorimetric and fluorescent Schiff base sensors for trace detection of pollutants and biologically significant cations: A review (2010–2021)

Green and sustainable tannin-immobilized cellulose dipstick for metallochromic sensing of ferric cations

Nitrogen-doped carbon dots based on arginine and maleic acid for fabrication of PVA composite films and iron fluorescence probes

A fluorescent sensor for Zn<sup>2+</sup> and Cd<sup>2+</sup> based on a diarylethene derivative with an indole-2-methylhydrazone moiety

A novel ratiometric fluorescent Fe3+ sensor based on a phenanthroimidazole chromophore

Abstract

Introduction

Section snippets

Reagents

Synthesis of sensor 1

Ratiometric response to Fe3+

Conclusion

Acknowledgments

Coord. Chem. Rev.

Curr. Opin. Chem. Biol.

Arch. Biochem. Biophys.

Tetrahedron

Tetrahedr. Lett.

J. Biol. Chem.

Tetrahedr. Lett.

Tetrahedr. Lett.

Spectrochim. Acta Part A

Chem. Rev.

Analyst

J. Med. Chem.

BioMetals

Curr. Med. Chem.

Org. Lett.

J. Am. Chem. Soc.

Org. Lett.

Eur. J. Org. Chem.

J. Am. Chem. Soc.

A novel ratiometric fluorescent Fe³⁺ sensor based on a phenanthroimidazole chromophore

Ratiometric response to Fe³⁺