A Highly Selective and High-Contrast Colorimetric “Off-On” Chemosensor for Cu2＋ Based on Boron-Dipyrromethene (BODIPY) Derivatives

doi:10.6023/cjoc202204026

Abstract

Based on the platform of boron-dipyrromethene (BODIPY) derivatives, a fluorescence turn-on probe BDP-2Z was rationally designed and synthesized with good water-solubility. With high sensitivity and selectivity for Cu^2＋ over other competitive ions, the reaction-based probe showed low detection limit and fast response in a wide pH range (pH=3.0~12.0). The contrast of color and fluorescence caused by Cu^2＋ was remarkable so much so that it was easily to distinguish Cu^2＋ from other ions with naked-eye detection. Along with adding of Cu^2＋, a blue shift of maximum absorption was observed from 548 nm to 496 nm, the corresponding solution color changed obviously from purple to light orange, and the fluorescence is enhanced by nearly 5-fold. Furthermore, the recognition mechanism was confirmed by UV-Vis, fluorescence spectra, and mass spectral analysis. The identified product of recognition process was even obtained by original silica gel column chromatography separation method. Also, the rapidly naked-eye application in real water samples provides an alternative to extension environmental detection.

Key words: water-soluble, naked-eye, BODIPY derivatives, fluorescence turn-on

Cite this article

Xiaolong Zhao, Yuqing Li, Liangwu Guo, Qiyuan Ran, Huihui Wu, Zhen Zhang, Yingpeng Su, Pengxin Zhou, Na Yan. A Highly Selective and High-Contrast Colorimetric “Off-On” Chemosensor for Cu^2＋ Based on Boron-Dipyrromethene (BODIPY) Derivatives[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3757-3765.

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Fig. & Tab. 10

Scheme 1. Synthetic route of BDP-2Z

Figure 1. (a) UV-vis spectra of BDP-2Z (5 μmol/L) with addition of 10.0 equiv. of Cu2＋ and the competing agents (Ag＋, Al3＋, Ba2＋, Ca2＋, Cd2＋, Co2＋, Cr3＋, Cu＋, Fe2＋, Fe3＋, Hg2＋, K＋, Li＋, Mg2＋, Mn2＋, Na＋, Ni2＋, Zn2＋) in DMF/H2O (pH=7.4, V∶V=9∶1) solutions (λex=478 nm); (b) fluorescence emission spectra of probe BDP-2Z (5 μmol/L) with 50 μmol/L of Cu2＋ or 50 μmol/L of other ions; (c) emission intensity ratio (F511/F0) of BDP-2Z (5 μmol/L) in DMF/H2O (pH=7.4, V∶V=9∶1) solutions in the presence of various species (50 μmol/L)

Figure 2. Colorimetric changes (up) and fluorescence photographs (down) of BDP-2Z (5 μmol/L) with 10 equiv. of different metal ions in DMF/H2O (V∶V=9∶1) (including 1: Ag＋, 2: Al3＋, 3: Ba2＋, 4: Ca2＋, 5: Cd2＋, 6: Co2＋, 7: Cr3＋, 8: Cu＋, 9: Fe2＋, 10: Fe3＋, 11: Hg2＋, 12: K＋, 13: Li＋, 14: Mg2＋, 15: Mn2＋, 16: Na＋, 17: Ni2＋, 18: Zn2＋, 19: Cu2＋)

Figure 3. The blue bars represent the fluorescent intensity of sensor BDP-2Z and various metal ions (20 equiv.) in DMF/H2O (V∶V=9∶1) solution; the red bars represent the fluorescent intensity of sensor BDP-2Z and Cu2＋ (10 equiv.) in DMF/H2O (V∶V=9∶1) solution

Figure 4. (a) UV-vis spectra of BDP-2Z in the presence of increasing concentration of Cu2＋over the range from 0 to 50 μmol/L (λex=478 nm. Inset: images of BDP-2Z (pink, left) and in the absence Cu2＋ under day light (orange, right)); (b) the relationship of A496/A548 versus the concentration of Cu2＋ over the range from 0 to 50 μmol/L (λex=478 nm); (c) Color changes of BDP-2Z (5 μmol/L) in DMF/H2O (V∶V=9∶1) upon addition of different concentration Cu2＋: 0 (A), 5 (B), 10 (C) and 15 (D) μmol/L

Figure 5. (a) Fluorescence response of BDP-2Z in the presence of increasing concentration of Cu2＋over the range from 0 to 50 μmol/L (λex=478 nm); (b) the relationship of F511/F0 versus the concentration of Cu2＋ over the range from 0 to 50 μmol/L (λex=478 nm)

Figure 6. (a) Fluorescence response of probe BDP-2Z (5 μmol/L) in presence of different concentrations of Cu2＋ ion; (b) the fluorescence intensity changed at 511 nm of probe BDP-2Z (5 μmol/L) in the absence and presence of 10.0 equiv. Cu2＋ in DMF/H2O (V/V=9/1). The pH was modulated by adding 0.1 mol/L HCl or 0.1 mol/L NaOH

Scheme 2. Recognition mechanism of probe BDP-2Z toward Cu2＋

Figure 7. Mass spectrum of probe BDP-2Z (a), BDP-2 (b) and the mixture of BDP-2Z with addition of Cu2＋ (c)

Sample		Found/ (μmol•L^－1)	Recovery/%	RSD/%
	0.5	0.52±0.063	105.27
River water	2.5	2.53±0.021	100.06	2.60
	5.0	5.14±0.010	102.96
	0.5	0.49±0.022	98.44
Tap water	2.5	2.46±0.077	98.71	2.78
	5.0	5.16±0.063	103.33

Table 1. Determination of Cu2＋ concentrations in water samplesa

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一种基于氟硼二吡咯(BODIPY)衍生物的高选择性“Off-On”型Cu^2＋比色-荧光探针