Elsevier

Tetrahedron

Volume 72, Issue 41, 13 October 2016, Pages 6390-6396
Tetrahedron

A new fluorescence probe based on fluorescein-diarylethene fluorescence resonance energy transfer system for rapid detection of Cd2+

https://doi.org/10.1016/j.tet.2016.08.037Get rights and content

Abstract

A novel diarylethene derivative 1O with fluorescein-quinoline unit was designed and synthesized successfully. Under the stimulation of light and chemical, the diarylethene molecule exhibited multi-responsive photoswitchable properties. Moreover, the compound was a potential ‘naked eye’ chemosensor with significant color and fluorescence changes in the recognition of Cd2+ in tetrahydrofuran (THF). When the fluorescein spirolactam ring-opened form was triggered with Cd2+, an obvious red shift from 459 nm to 560 nm (101 nm) was observed in complex 1O′, and the emission intensity was enhanced by 8 fold with a concomitant fluorescence color change from dark to bright yellow. Significantly fluorescent quenching was observed in ring-closed isomer 1C′ due to the FRET (fluorescence resonance energy transfer) processes between fluorescein moiety and the ring-closed diarylethene moiety. The interference from other effective metal ions, particularly Zn2+, had not been observed. Finally, a molecular logic circuit was constructed with both light and chemical stimuli as inputs and fluorescence intensity at 560 nm as output.

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A novel diarylethene with fluorescein-quinoline unit was synthesized and its multi-controllable fluorescent switching behaviors with light, Cd2+ were investigated systematically. The diarylethene could serve as a highly selective ‘turn-on’ fluorescence chemosensor for recognition of Cd2+.

Introduction

Fluorescence probes have been widely utilized to detect pH,1, 2, 3 temperature,4 light,5, 6, 7 redox potential8 and metal ions9, 10, 11 conveniently in chemical, environmental, and biological field due to their high sensitivity, high selectivity, instantaneous response and convenient functionalization.12, 13, 14 Recently, fluorescence probes for the detection of heavy transition-metal (HTM) ions in environmental and biological processes have been attracted more and more attentions because of many transition metallic pollutants from industry, agriculture and many other fields,15, 16, 17, 18, 19, 20 in which cadmium is one of the most serious ones due to the toxicity of Cd2+ to bones, kidneys, the nerve system and tissues.21, 22 Additionally, Cd2+ could replace metallic center of many other enzymes to kill their catalytic activities.23 As a high hazard of toxic substances and carcinogens with a long metabolic half-life (10–30 years) in the human body,24 it is very important to develop methods to efficiently detect and monitor cadmium in vitro and in vivo.

Up to present, several feasible approaches, including atomic absorption and inductively coupled plasma, have been previously reported to detect Cd2+. However, these methods are still considerably expensive and unsuitable for real-time monitoring. Florescent probes have been reported as a privileged approach for the detection of metal ions in biology and the environment with high selectivity, high sensitivity and simplicity.25 And different external stimuli, including chemicals, electrons and photons, could induce significant changes to the spectral shape and/or peak intensity of these florescent probes.26 For example, many fluorescein derivatives have been widely used as fluorescent probes to detect and analyze transition metal ions (Yb3+, Hg2+, Pd2+, Cu2+, Fe3+ and Cr3+)27, 28, 29, 30, 31 owing to their high extinction coefficients, high quantum yield, excellent photostability, and broad fluorescence in the visible region. Because fluorescein has an equilibrium between a fluorescent (open) carboxylate form and a non-fluorescent (closed) lactone form, thus it can be used as colorimetric ‘naked eye’ and fluorescence ‘OFF-ON’ probes.32 Additionally, quinoline and its derivatives, particularly 8-aminoquinoline and 8-hydroxyquinoline, are widely used as chelating moieties to construct chelation-enhanced fluorescent sensors for transition metals.33, 34 Therefore, quinolone-based ligands with extended conjugated fluorophores could exhibit excellent fluorescence properties to sense many metal ions (Cd2+, Zn2+, Mg2+, Al3+, Sn4+, etc.) based on photo-induced electron transfer (PET), internal charge transfer (ICT) or/and fluorescence resonance energy transfer (FRET).35, 36, 37, 38, 39, 40 On the other hand, Cd2+ and Zn2+, which are in the same group of the periodic table, have similar chemical properties, thus the greatest challenge for detecting Cd2+ comes from the interference of other transition metal ions, in particular Zn2+. However, only a few Cd2+-selective fluorescence probes have been synthesized to discriminate Cd2+ from other metal ions, especially the Zn2+.41, 42, 43, 44 As a result, a highly selective fluorescence probes for Cd2+ with the interference of other transition metal ions, in particular Zn2+ are just around the corner.

Furthermore, among various photochromic compounds for optical information storage media and photonic switch devices,45, 46, 47 photochromic diarylethene (DAE) derivatives have received the most attentions because of their reversible transformations between the ring-open and ring-closed forms, excellent thermal stability, excellent fatigue resistance, high sensitivity and fast response.48, 49 When fluorescent DAEs or its derivatives with other fluorophores are irradiated with light, the intensity of maximum emission could be changed dramatically. Up to present, a lot of specific recognition groups, such as quinolone,50 rhodamine51 and pyridine,52 had been successfully embedded in photochromic systems to construct various multi-responsively photoswitchable DAEs fluorescence probes to metal ions recognition, pH detection and living cell imagination.53, 54, 55 However, DATs-based Cd2+ fluorescence probes have been rarely reported.56

In this article, we designed and synthesized a novel fluorescein-diarylethene derivative bridged by quinoline as a ‘turn-on’ fluorescent probe to detect Cd2+ in aqueous solution with a dual-channel mode (fluorescence emission and UV–vis). The diarylethene could detect Cd2+ selectively and sensitively based on the fluorescence resonance energy transfer (FRET) mechanism and possessed strict Cd2+/Zn2+ discrimination. The photochromic process of the new diarylethene was shown in Scheme 1.

Section snippets

General methods

1H and 13C NMR spectra were recorded on Bruker AV400 (400 MHz) spectrometer with CDCl3 or DMSO-d6 as the solvent and tetramethylsilane (TMS) as an internal standard. Mass spectra were measured on a Bruker AmaZon SL Ion Trap Mass spectrometer. IR spectra were recorded on a Bruker Vertex-70 spectrometer. UV–vis spectra were measured on an Agilent 8453 UV–vis spectrophotometer. Fluorescence spectra were recorded on a Hitachi F-4600 fluorescence spectrophotometer. Melting point was measured on a

Photochromism and fluorescence of 1O

Photochromic and fluorescent properties of 1O induced by photoirradiation were tested in THF (2.0×10−5 mol L−1) at room temperature. As shown in Fig. 1A, the colorless 1O had a sharp absorption band centered at 339 nm (ɛ=2.33×104 mol−1 L cm−1) in THF due to π→π transition of diarylethene moiety.59 Upon the irradiation with 297 nm light, a new absorption band centered at 514 nm (ɛ=4.11×103 mol−1 L cm−1) appeared along with a color change from colorless to pink, which was due to the formation of

Conclusions

In summary, a new fluorescein-diarylethene-based fluorescence probe was successfully synthesized to selectively and sensitively discriminate Cd2+ from other metal ions efficiently without time-dependence. Based on the fact that the fluorescence of the diarylethene compound could be effectively modulated with the stimulation of light and chemical species, a logic circuit was also designed successfully.

Acknowledgements

The authors are grateful for the financial support from the National Natural Science Foundation of China (51373072, 21362013, 21363009), the Project of Jiangxi Advantage Sci-Tech Innovative Team (20142BCB24012), the Project of Jiangxi Science and Technology Normal University Advantage Sci-Tech Innovative Team (2015CXTD002), the Science Funds of Natural Science Foundation of Jiangxi Province (20142BAB203005).

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