Highly selective detection of copper(II) by a “ligand-free” conjugated copolymer in nucleophilic solvents

doi:10.1007/s11705-019-1791-6

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (1) : 105-111 https://doi.org/10.1007/s11705-019-1791-6

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Highly selective detection of copper(II) by a “ligand-free” conjugated copolymer in nucleophilic solvents

Weixing Deng¹, Pengfei Sun¹, Quli Fan¹(

), Lei Zhang¹, Tsuyoshi Minami²(

)

¹. Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023, China
². Institute of Industrial Science, The University of Tokyo, Meguro-ku, Tokyo 153-8505, Japan

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Abstract

The synthesis of N-cyclohexyl carbamate-attached fluorene-alt-phenylene copolymer (PFPNCC) and the use of PFPNCC as a “ligand-free” fluorescent chemosensor for Cu(II) are described. Addition of Cu(II) can efficiently quench the fluorescence of PFPNCC in nucleophilic solvents such as DMF and DMSO, but not in low nucleophilic solvents such as 1,4-dioxane and THF. Ultraviolet-visible spectra of the mixture of the conjugated polymer and Cu(II) indicate the presence of a reduced Cu(I) ion in the solution. Furthermore, fluorescence recovery of PFPNCC observed at low temperature suggests that the quenching and reducing mechanism is most probably due to a photo-induced electron transfer from excited PFPNCC to Cu(II). Our findings provide a novel strategy for highly selective conjugated polymer-based chemosensors for various target analytes, albeit “ligand-free”.

Keywords ligand-free fluorescent chemosensor copper photo-induced electron transfer

Corresponding Author(s): Quli Fan,Tsuyoshi Minami

Online First Date: 09 April 2019 Issue Date: 20 January 2020

Cite this article:

Weixing Deng,Pengfei Sun,Quli Fan, et al. Highly selective detection of copper(II) by a “ligand-free” conjugated copolymer in nucleophilic solvents[J]. Front. Chem. Sci. Eng., 2020, 14(1): 105-111.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1791-6
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I1/105

Fig.1 Scheme 1 Synthesis of PFPNCC

Fig.2 Fluorescence quenching efficiency of PFPNCC (1.0 × 10^?⁶ mol/L) in DMF by adding metal ions. l_ex = 370 nm, l_em= 420 nm. [Metal ion] = 4 mmol/L

Fig.3 Fluorescence spectra of PFPNCC (1.0 × 10⁻⁶ mol/L) in DMF upon addition of Cu(II). [Cu(II)] = 0–5 mmol/L. l_ex = 370 nm. Inset shows titration isotherm corresponding to the Cu(II)-induced fluorescence quenching

Fig.4 UV–vis spectra of PFPNCC (1.0 × 10⁻⁶ mol/L) in DMF with various concentrations of Cu(II). Inset shows UV–vis spectra of PFPNCC (1.0 × 10⁻⁶mol/L) with higher concentration of Cu(II) in DMF

Fig.5 Fluorescence spectra of PFPNCC in the presence or absence of Cu(II) in various solvents. [Cu(II)] = 4 m mol/L, λ_ex = 370 nm

Fig.6 Fluorescence spectra of PFPNCC (1.0 × 10^–6 mol/L) in DMF in the presence or absence of Cu(II) (4 mmol/L) (I: no Cu(II), at 25^○C; II: Cu(II), at 25^○C; III: Cu(II), at about –75^○C). l_ex = 370 nm

Fig.7 Scheme 2 A plausible mechanism of the fluorescence quenching of PFPNCC by adding Cu(II) in nucleophilic solvents

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