A TCF-based colorimetric and fluorescent probe for palladium detection in an aqueous solution

doi:10.1016/j.tetlet.2018.06.016

Tetrahedron Letters

Volume 59, Issue 29, 18 July 2018, Pages 2804-2808

https://doi.org/10.1016/j.tetlet.2018.06.016 Get rights and content

Highlights

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A simple colorimetric and fluorescent probe TCF-AC for Pd⁰ detection has been developed.
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TCF-AC displays high selectivity and sensitivity to Pd⁰ with a low detection limit.
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TCF-AC exhibits fluorescence ‘turn on’ response to Pd⁰ with a large Stokes shift.
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TCF-AC is applicable to image Pd⁰ in living HeLa cells.

Abstract

A new fluorescent probe (TCF-AC) that contains 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) skeleton has been developed. Probe TCF-AC exhibits highly selective and sensitive detection toward Pd⁰ in EtOH/H₂O (1:1, v/v, PBS 20 mM, pH = 7.4) solution with fluorescence “turn on” and colorimetric changes. The Pd⁰ detection by TCF-AC holds some advantages including good anti-interference ability, a relative large Stokes shift (>100 nm), and a low detection limit (7.05 × 10⁻⁷ M). Cell imaging studies demonstrate that TCF-AC is applicable to detect Pd⁰ in living HeLa cells.

Graphical abstract

A new fluorescence ‘turn-on’ probe TCF-AC for Pd⁰ recognition in an aqueous media has been developed.

Introduction

Palladium, as a rare transition metal, plays critical roles in many modern organic syntheses due to its excellent catalytic properties [1]. Wide applications of palladium species also result in palladium contamination owing to the toxicity of palladium. It is also known that palladium can disturb normal cell metabolism through binding thiol-containing biomolecules including proteins, DNA, and RNA, etc [2]. Accordingly, the development of effective methods for palladium detection with high selectivity and sensitivity has attracted considerable attention. During the past decades, several analytical methods such as atomic absorption spectrometry, plasma emission spectroscopy and X-ray fluorescence have been developed for palladium detection. Although these methods are rapid and sensitive, they usually suffer from some drawbacks such as expensive instrumentation, complicated sample pre-treatment, and requirement of professional operators.

Detection of target analyte utilizing fluorescent probes becomes attractive due to the advantages of fluorescence technique such as high sensitivity, simplicity, and noninvasive real-time detection in living systems [3]. Recently, a number of reaction-based fluorescent probes for palladium species detection have been reported [4]. Based on the well-known Tsuji-Trost reaction, an allylcarbonate [5] or an allylcarbomide [6] moiety has been skillfully employed as the effective reaction site to develop fluorescent palladium probes. However, few reports on fluorescent Pd⁰ probes with the features of easy preparation, high selectivity and sensitivity, long-wavelength emission, and a large Stokes shift can be found.

2-Dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF), as a strong electron acceptor, has been widely used for preparation of nonlinear optical materials [7] and long-wavelength emission fluorophores [8]. In this work, we report a simple TCF-based far-red emissive fluorescent probe (TCF-AC) for the detection of Pd⁰ through “protection-deprotection” strategy. This probe exhibits high selectivity and sensitivity toward Pd⁰ in EtOH/H₂O (1:1, v/v, PBS 20 mM, pH = 7.4) solution with a detection limit of 7.05 × 10⁻⁷ M. Moreover, the probe was also applicable to detect Pd⁰ in living HeLa cells.

Section snippets

Results and discussion

The synthetic route of probe TCF-AC was shown in Scheme 1. Compound TCF-OH was prepared by condensation of TCF [9] with 4-hydroxybenzaldehyde following the reported method [10]. Subsequently, TCF-OH was reacted with allyl chloroformate in dry dichloromethane to give TCF-AC with a yield of 75%. The structure of TCF-AC was confirmed by ¹H NMR, ¹³C NMR and HRMS analysis (see Supplementary Data), respectively. The responses of TCF-AC to Pd⁰ and other metal ions were fully examined. As shown in Fig.

Conclusions

In summary, we have developed a simple TCF-derived fluorescent probe TCF-AC for Pd⁰ detection with colorimetric and fluorescence dual outputs in EtOH/H₂O (1:1, v/v, PBS 20 mM, pH = 7.4) solution. The probe displays high selectivity toward Pd⁰ over other metal ions and possesses good anti-interference ability and a low detection limit of 7.05 × 10⁻⁷ M. The probe has a good function at near neutral and alkaline conditions. In addition, probe TCF-AC is cell permeable and is applicable to image Pd⁰

Acknowledgements

The project was supported by the National Natural Science Foundation of China (Nos. 21476029, U1608222), the Program for Distinguished Professor of Liaoning Province, and the Research and Innovation Platform of Yangtze Normal University (No. 2015XJPT01).

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View full text

A TCF-based colorimetric and fluorescent probe for palladium detection in an aqueous solution

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Results and discussion

Conclusions

Acknowledgements

Chem Soc Rev

RSC Adv

Tetrahedron Lett

Inorg Chem

Sens Actuators, B

Anal Chim Acta

Chem Commun

Desalin Water Treat

Chem Commun

Chem Asian J

Chem Asian J

Chem Eur J

Mater Chem B

Analyst

Sens Actuators, B

Dalton Trans

Tetrahedron

J Am Chem Soc

Chem Rev

Chem Rev

Chem Rev

Sci Total Environ

Int J Hyg Environ Health