基于氢化吡啶辅助氨基氧化策略的次氯酸根荧光探针的设计、合成及其性能研究

doi:10.6023/cjoc202205019

摘要/Abstract

以喹啉作为荧光团, 乙烯延展并在芳氨基邻位构建氢化吡啶基作为识别位点, 巧妙设计并合成了一种新颖的检测次氯酸根离子的荧光探针A4. 光谱实验研究表明, 该荧光探针对于次氯酸盐具有很高的选择性、极强的灵敏度(响应时间1.6 s)以及低检测限(77.8 nmol/L). 探针A4和次氯酸盐反应后, 紫外吸收光谱在421 nm处的吸收峰蓝移, 溶液颜色由黄色变成无色; 荧光发射光谱在642 nm处最大发射峰淬灭, 荧光颜色由橙红色变成无荧光. 通过光谱比较以及质谱分析, 确认了该探针识别机理为次氯酸根诱导氨基氧化亚硝基并伴随氢化吡啶转化为吡啶. 进一步, 将负载荧光探针A4的试纸条成功应用于次氯酸盐的检测. 此外, 考察了该探针随水含量的增加发生明显的荧光淬灭现象(ACQ).

关键词: 荧光探针, 次氯酸根离子, 氧化, 检测

In this paper, a novel fluorescent probe A4 for the detection of hypochlorite ions was designed and synthesized using quinoline as a fluorophore and ortho-vinylhydropyridine auxiliary amino group as a recognition site. Experimental studies show that the fluorescent probe has high selectivity for hypochlorite and extreme sensitivity (response time 1.6 s, limit of detection 77.8 nmol/L). After reacting with hypochlorite, the absorption peak of the UV-vis absorption spectrum at 421 nm was blue-shifted, and the color of the solution changed from yellow to colorless. In the fluorescence emission spectrum, the maximum emission peak at 642 nm was quenched, and the fluorescent color changed from orange red to non-fluorescent. The sensing mechanism was confirmed by liquid chromatograph mass spectrometer (LC-MS) analysis and comparison of UV-vis spectra, which involving the ortho-vinylhydropyridine-assisted amido-to-nitroso oxidation reaction. In addition, the A4-loaded test strip was prepared and applied on the detection of hypochlorite. Moreover, the probe showed moderate aggregation-caused quenching (ACQ) with increasing of water content.

Key words: fluorescent probe, hypochlorite ion, oxidation, detection

引用此文

陈志华, 胡艳, 马丽丽, 张子怡, 刘传祥. 基于氢化吡啶辅助氨基氧化策略的次氯酸根荧光探针的设计、合成及其性能研究[J]. 有机化学, 2023, 43(2): 718-724.

Zhihua Chen, Yan Hu, Lili Ma, Ziyi Zhang, Chuanxiang Liu. Rational Design of ortho-Vinylhydropyridine-Assisted Amino-fluorophore as Hypochlorite Fluorescent Probe[J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 718-724.

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图/表 9

图1. 探针A4的合成路线

Figure 1. Synthetic route of probe A4

图2. (a)探针A4 (20 μmol/L)与各种离子和氧化物在CH3CN/ PBS (V∶V=3∶7)的溶液中的紫外选择性测试图谱, 以及(b)探针A4 (20 μmol/L)在CH3CN/PBS (V∶V=3∶7)的溶液中与不同浓度NaClO (0到1.5 equiv.)条件下测得的紫外吸收光谱

Figure 2. (a) UV-selectivity test profiles of probe A4 (20 μmol/ L) with various ions and oxides in CH3CN/PBS (V∶V=3∶7) solutions, and (b) probe A4 (20 μmol/L) UV absorption spectra measured in CH3CN/PBS (V∶V=3∶7) solution with different concentrations of NaClO (0 to 1.5 equiv.) (a) The upper illustration shows the color change of pure probe A4 reacting with various ions and oxides (ClO-, H2O2, $\text{HSO}_{3}^{-}$, SH-, S2-, CN-, SCN-, F-, Cl-, Br-, I-, $\text{HSO}_{4}^{-}$, $\text{ClO}_{4}^{-}$, ${{\text{H}}_{2}}\text{PO}_{4}^{-}$, $\text{BF}_{\text{4}}^{-}$,, AcO-, $\text{NO}_{\text{2}}^{-}$, ONOO-, 1O2, ?OH, Na＋, K＋, Mg2＋, Ca2＋, Zn2＋, Al3＋, Fe3＋, Ba2＋) in a solution of CH3CN/PBS (V∶V=3∶7); (b) the upper right illustration shows the scatter diagram of UV absorption of probe A4 at 421 nm as a function of NaClO concentration

图3. (a)探针A4 (20 μmol/L)与各种离子和氧化物在CH3CN/PBS (V∶V=3∶7)的溶液中的荧光发射光谱图. (b)探针A4 (20 μmol/L)在CH3CN/PBS (V∶V=3∶7)的溶液中, 与不同浓度NaClO (0到1.4 equiv.)条件下测得的荧光发射光谱

Figure 3. (a) Fluorescence emission spectra of probe A4 (20 μmol/L) with various ions and oxides in CH3CN/PBS (V∶V=3∶7), and (b) fluorescence emission spectra of probe A4 (20 μmol/L) were measured at different concentrations of NaClO (0 to 1.4 equiv.) in CH3CN/PBS (V∶V=3∶7) (a) The upper illustration shows the fluorescence color change of probe A4 reacting with various ions and oxides (ClO-, H2O2, $\text{HSO}_{3}^{-}$, SH-, S2-, CN-, SCN-, F-, Cl-, Br-, I-, $\text{HSO}_{4}^{-}$, $\text{ClO}_{4}^{-}$, ${{\text{H}}_{2}}\text{PO}_{4}^{-}$, $\text{BF}_{\text{4}}^{-}$, AcO-, $\text{NO}_{\text{2}}^{-}$, ONOO-, 1O2, ?OH, Na＋, K＋, Mg2＋, Ca2＋, Zn2＋, Al3＋, Fe3＋, Ba2＋) in CH3CN/PBS (V∶V=3∶7). (b) The upper right inset indicates the relationship chart between fluorescence emission of probe A4 at 642 nm and NaClO concentration (λex=410 nm)

图4. (a)在CH3CN/PBS (V∶V=3∶7)的溶液中探针A4 (20 μmol/L)在642 nm处的最大荧光发射与时间的关系图, 以及(b)在不同pH条件下探针A4 (20 μmol/L)和NaClO (1.5 equiv.)反应后在642 nm处的荧光强度与pH的关系图(λex=410 nm)

Figure 4. Relationship chart between maximum fluorescence emission of probe A4 (20 μmol/L) at 642 nm in CH3CN/PBS (V∶V=3∶7), and (b) relationship between fluorescence intensity of probe A4 (20 μmol/L) and NaClO (1.5 equiv.) at 642 nm and under different pH conditions (λex=410 nm)

图5. 在不同水含量(体积分数为0~90%)的溶液中探针A4 (20 μmol/L)的荧光光谱图(λex=410 nm)

Figure 5. Fluorescence spectra of probe A4 (20 μmol/L) in solutions with different water contents (volume fraction 0~90%) (λex=410 nm)

图6. 探针A4与次氯酸根离子作用的机理图

Figure 6. Mechanism of the probe A4 with hypochlorite ion

图7. 探针A4和次氯酸根离子反应后的吸收光谱与中间体A3的吸收光谱对比图

Figure 7. Comparison of absorption spectra of probe A4 after reaction with hypochlorite ion and intermediate A3

图8. 探针A4与次氯酸根离子作用后的质谱图

Figure 8. MS of probe A4 with hypochlorite ion

图9. (a)日光灯照射下含有探针A4的试纸与不同浓度的 ClO-溶液反应后的颜色变化图, 以及(b)紫外灯照射下含有探针A4的试纸与不同浓度的ClO-溶液反应后的荧光颜色变化图.

Figure 9. (a) Color change of the test paper containing probe A4 after reaction with different concentrations of ClO- solution under the illumination of fluorescent lamps, and (b) fluorescence color change of the test paper containing probe A4 after reaction with ClO- solutions of different concentrations under UV light irradiation

参考文献 23

[1]	Song, W.; Dong, B.; Lu, Y.; Kong, X.; Mehmood, A. H.; Lin, W. New J. Chem. 2019, 43, 12103. doi: 10.1039/C9NJ02666E
[2]	Cheng, T.; Zhao, J.; Wang, Z.; An, J.; Xu, Y.; Qian, X.; Liu, G. Dyes Pigm. 2016, 126, 218. doi: 10.1016/j.dyepig.2015.10.020
[3]	Pattison, D. I.; Hawkins, C. L.; Davies, M. J. Chem. Res. Toxicol. 2009, 22, 807. doi: 10.1021/tx800372d pmid: 19326902
[4]	Maitra, D.; Byun, J.; Andreana, P. R.; Abdulhamid, I.; Saed, G. M.; Diamond, M. P.; Pennathur, S.; Abu-Soud, H. M. Free Radical Biol. Med. 2011, 51, 364. doi: 10.1016/j.freeradbiomed.2011.03.040
[5]	Wright, A. F.; Jacobson, S. G.; Cideciyan, A. V.; Roman, A. J.; Shu, X.; Vlachantoni, D.; McInnes, R. R.; Riemersma, R. A. Nat. Genet. 2004, 36, 1153. doi: 10.1038/ng1448 pmid: 15514669
[6]	Hazell, L. J.; Arnold, L.; Flowers, D.; Waeg, G.; Malle, E.; Stocker, R. J. Clin. Invest. 1996, 97, 1535.
[7]	Wu, S. M.; Pizzo, S. V. Arch. Biochem. Biophys. 2001, 391, 119. pmid: 11414692
[8]	Casciaro, M.; Di Salvo, E.; Pace, E.; Ventura-Spagnolo, E.; Navarra, M.; Gangemi, S. Immun. Ageing 2017, 14, 21. doi: 10.1186/s12979-017-0104-5 pmid: 29163665
[9]	Güngör, N.; Knaapen, A. M.; Munnia, A.; Peluso, M.; Haenen, G. R.; Chiu, R. K. Mutagenesis 2009, 25, 149. doi: 10.1093/mutage/gep053
[10]	Jin, L.; Tan, X.; Dai, L.; Sheng, L.; Wang, Q. RSC Adv. 2019, 9, 15926. doi: 10.1039/C9RA01457H
[11]	Cheng, D.; Pan, Y.; Wang, L.; Zeng, Z.; Yuan, L.; Zhang, X.; Chang, Y.-T. J. Am. Chem. Soc. 2017, 139, 285. doi: 10.1021/jacs.6b10508 pmid: 27996249
[12]	Song, Z.; Kwok, R. T. K.; Ding, D.; Nie, H.; Lam, J. W. Y.; Liu, B.; Tang, B. Z. Chem. Commun. 2016, 52, 10076. doi: 10.1039/C6CC05049B
[13]	He, X.; Chen, H.; Xu, C.; Fan, J.; Xu, W.; Li, Y.; Deng, H.; Shen, J. J. Hazard. Mater. 2020, 388, 122029. doi: 10.1016/j.jhazmat.2020.122029
[14]	Bhatnagar, S.; Khera, E.; Liao, J.; Eniola, V.; Hu, Y.; Smith, D. E.; Thurber, G. M. Sci. Rep. 2019, 9, 4661. doi: 10.1038/s41598-019-38548-0 pmid: 30858419
[15]	Liu, S.; Zhu, Y.; Wu, P.; Xiong, H. Anal. Chem. 2021, 93, 4975. doi: 10.1021/acs.analchem.1c00281
[16]	He, L.; Xiong, H.; Wang, B.; Zhang, Y.; Wang, J.; Zhang, H.; Li, H.; Yang, Z.; Song, X. Anal. Chem. 2020, 92, 11029. doi: 10.1021/acs.analchem.0c00030
[17]	Liu, L.; Wei, P.; Yuan, W.; Liu, Z.; Xue, F.; Zhang, X.; Yi, T. Anal. Chem. 2020, 92,10971.
[18]	Wei, P.; Liu, L.; Wen, Y.; Zhao, G.; Xue, F.; Yuan, W.; Li, R.; Zhong, Y.; Zhang, M.; Yi, T. Angew. Chem., Int. Ed. 2019, 58, 4547. doi: 10.1002/anie.201813648
[19]	Gao, Y.; Pan, Y.; He, Y.; Chen, H.; Nemykin, V. N. Sens. Actuators, B 2018, 269, 151. doi: 10.1016/j.snb.2018.04.135
[20]	Wang, B.; Zhang, F.; Wang, S.; Yang, R.; Chen, C.; Zhao, W. Chem. Commun. 2020, 56, 2598. doi: 10.1039/C9CC07256J
[21]	Wu, P.; Zhu, Y.; Chen, L.; Tian, Y.; Xiong, H. Anal. Chem. 2021, 93, 13014. doi: 10.1021/acs.analchem.1c02831
[22]	Ma, C.; Hou, S.; Zhou, X.; Wang, Z.; Yoon, J. Anal. Chem. 2021, 93, 9640. doi: 10.1021/acs.analchem.1c02025
[23]	Zhang, C.; Ji, K.; Wang, X.; Wu, H.; Liu, C. Chem. Commun. 2015, 51, 8173. doi: 10.1039/C5CC01280E