可视化检测次氯酸的苯并咪唑类荧光增强型探针

doi:10.7503/cjcu20190366

摘要/Abstract

摘要：

合成了一种新型的苯并咪唑类荧光增强型探针2-{[4-(1H-苯并咪唑-2-基)苯亚甲基]氨基}-3-氨基马来腈(ZY12), 用光谱方法研究了其对次氯酸的识别作用. 实验结果表明, ZY12对ClO ^-表现出较高的选择性和灵敏度, 且响应快速, 抗干扰能力强; 将ClO ^-加入到ZY12溶液中后, 反应体系的荧光强度随ClO ^-浓度的增加而逐渐增强, 并伴随着荧光颜色由微蓝色到亮蓝色的变化, 可实现对ClO ^-的可视化检测; 在1.8×10 ^-6~3.4×10 ^-5 mol/L浓度范围内, ZY12能够定量检测ClO ^-, 检测限为2.8×10 ^-7 mol/L; ZY12可应用于不同水样中ClO ^-的检测, 并能对HeLa活细胞中的ClO ^-进行荧光成像.

关键词: 次氯酸, 荧光探针, 可视化检测, 荧光成像

Abstract:

A novel benzimidazole-derived fluorescence enhancement probe 2-{[4-(1H-benzo[d]imidazol-2-yl)benzylidene]amino}-3-aminoma-leonitrile(ZY12) was synthesized, and its recognition of HClO was researched with spectral methods. The results showed that ZY12 demonstrated relatively high selectivity and sensitivity to ClO ^-. It had quick response and strong anti-interference ability. Upon addition of ClO ^- to ZY12 solution, the fluorescence intensity of reaction system increased with the increasing concentration of ClO ^-, accompanied with fluorescence color change from faint blue to bright blue, realizing the visual detection of ClO ^-. ZY12 could quantitatively detect ClO ^- at concentrations ranging from 1.8×10 ^-6—3.4×10 ^-5 mol/L with a detection limit of 2.8×10 ^-7 mol/L. ZY12 was used to determine ClO ^- in various water samples, and it could also be applied to intracelluar ClO ^- imaging in living HeLa cells.

Key words: Hypochlorous acid, Fluorescent probe, Visual detection, Fluorescence imaging

中图分类号:

O657
O626.23

TrendMD:

张勇,申城,幸志荣,陈归柒,卢资,侯志兵,陈雪梅. 可视化检测次氯酸的苯并咪唑类荧光增强型探针. 高等学校化学学报, 2019, 40(12): 2480.

Yong ZHANG,Cheng SHEN,Zhirong XING,Guiqi CHEN,Zi LU,Zhibing HOU,Xuemei CHEN. Benzimidazole-Derived Fluorescence Enhancement Probe for Visual Detection of HClO ^†. Chem. J. Chinese Universities, 2019, 40(12): 2480.

图/表 10

Scheme 1 Synthesis of the probe ZY12

Fig.1 Fluorescent response of ZY12(10 μmol/L, a) to different analytes(30 μmol/L, b—p) Analyte: b. F-; c. Cl-; d. Br-; e. I-; f. Ac-; g. C$O_{3}^{2-}$; h.$N_{3}^{-}$; i. N$O_{2}^{-}$; j. N$O_{3}^{-}$; k. S2-; l. S$O_{3}^{2-}$; m. SCN-; n. t-BuOOH; o. H2O2; p. ClO-.

Fig.2 Effect of ClO- on ZY12(10 μmol/L) in the presence of different interferents(100 μmol/L) Interferent: a. F-; b. Cl-; c. Br-; d. I-; e. Ac-; f. C$O_{3}^{2-}$; g.$NO_{3}^{-}$; h. N$O_{2}^{-}$; i. N$O_{3}^{-}$; j. SCN-; k. S2-; l. S$O_{3}^{2-}$; m. t-BuOOH; n. H2O2.

Fig.3 Fluorescence intensity changes of ZY12(10 μmol/L) upon gradual addition of ClO-(0—30 μmol/L) The inset shows the linear relationship between the fluorescence intensity of ZY12 and concentrations of ClO-.

Table 1 Comparison of different fluorescent probes for detection of ClO-

Fluorescent probe	λ_ex/λ_em(nm)	Solvent	Detection limit/(μmol·L^-1)	Ref.
HQ	370/495	PBS/DMSO(volume ratio 1:9)	0.31	[18]
1b	398/455	PBS/CH₃CN(volume ratio 8:2)	0.36	[19]
L1	405/505	PBS	0.67	[20]
BDP-OX	488/538, 589	PBS/DMSO(volume ratio 1:9)	0.85	[21]
HA	340/460, 570	PBS/DMF(volume ratio 99:1)	0.70	[22]
ZY12	322/472	EtOH/H₂O(volume ratio 1:9)	0.28	This work

Fig.4 Time-dependent fluorescence intensity changes of ZY12(10 μmol/L) in the presence of ClO-(30 μmol/L) The inset shows the fluorescence color of ZY12 before(left) and after(right) addition of ClO- under UV light(365 nm).

Fig.5 Fluorescence intensity vs. pH values of ZY12(10 μmol/L) in the absence and presence of ClO-(30 μmol/L)

Fig.6 Proposed mechanism of the response of probe ZY12 towards ClO-

Table 2 Detection of ClO- in various water samples

Water sample	ClO^- added/(μmol·L^-1)	ClO^- found/(μmol·L^-1)	Recovery(%)	RSD(%)
Tap water	10.0	9.60	96.0	3.8
	20.0	19.30	96.5
	30.0	30.81	102.7
Mineral water	10.0	9.71	97.1	3.0
	20.0	19.52	97.5
	30.0	30.73	102.3
Changjiang river water	10.0	10.32	103.2	4.7
	20.0	19.10	95.5
	30.0	31.29	104.3

Fig.7 Bright-field(A, C) and fluorescence(B, D) images of HeLa cells treated with probe ZY12(10 μmol/L)(A, B) and treated with probe ZY12(10 μmol/L) and NaClO (50 μmol/L) for 30 min(C, D)

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