一种基于香豆素骨架的荧光化学传感器于水溶液中实现对Al3+和焦磷酸根(PPi)的连续识别

doi:10.6023/cjoc202010007

有机化学 ›› 2021, Vol. 41 ›› Issue (3): 1161-1167.DOI: 10.6023/cjoc202010007 上一篇下一篇

研究论文

一种基于香豆素骨架的荧光化学传感器于水溶液中实现对Al³⁺和焦磷酸根(PPi)的连续识别

孟宪娇^a, 赵晋忠^a, 张永坡^a, 李志春^b, 袁长春^b^,^*(), 马文兵^b^,^*()

a 山西农业大学基础部山西晋中 030801
b 中北大学化学工程与技术学院太原 030051

收稿日期:2020-10-06 修回日期:2020-10-28 发布日期:2020-11-12
通讯作者: 袁长春, 马文兵
基金资助:
山西省基础应用研究(201801D221087); 山西农业大学科技创新(2020BQ18); 山西省优秀博士来晋工作奖励(SXYBKY2019046); 山西省高等学校创新(2020L0140)

A Fluorescent Chemosensor Based on Coumarin for Squential Recognition of Al³⁺ and Pyrophosphate (PPi) in Aqueous Solution

Xianjiao Meng^a, Jinzhong Zhao^a, Yongpo Zhang^a, Zhichun Li^b, Changchun Yuan^b^,^*(), Wenbing Ma^b^,^*()

a Basic Sciences Depart, Shanxi Agricultural University, Jinzhong, Shanxi 030801
b School of Chemical Engineering and Technology, North University of China, Taiyuan 030051

Received:2020-10-06 Revised:2020-10-28 Published:2020-11-12
Contact: Changchun Yuan, Wenbing Ma
About author:
* Corresponding authors. E-mail: mawenbing@nuc.edu.cn;
ycc870108@126.com
Supported by:
Applied Basic Research Programs of Shanxi Province(201801D221087); Science and Technology Innovation Project of Shanxi Agricultural University(2020BQ18); Shanxi Excellent Doctor Grant Award(SXYBKY2019046); Science and Technology Innovation Project of Colleges and Universities(2020L0140)

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摘要/Abstract

合成了一种新型的荧光化学传感器(E)-N'-(3-((双(吡啶-2-亚甲基)氨基)甲基)-2-羟基-5-甲基亚苄基)-7-(二乙氨基)-2-氧代-2H-色烯-3-甲酰肼(1), 并通过¹H NMR、¹³C NMR和ESI-MS对其结构进行表征, 利用紫外/荧光分光光度法研究了传感器1的传感性能. 结果表明: 传感器1于水中对Al³⁺表现出明显的荧光增强响应, 而配合物1-Al³⁺对PPi表现出明显的荧光淬灭响应. 传感器1对Al³⁺和焦磷酸根(PPi)的检测限分别为0.26和0.1 μmol/L, 配位比均为1∶1. 配位机理通过荧光滴定、核磁滴定和高分辨质谱进行了证实, 另外传感器 1的有效测试pH范围是2~10, 且循环响应测试可达4次.

关键词: 香豆素, 荧光化学传感器, Al³⁺, PPi, 连续识别

A novel fluorescent chemosensor (E)-N'-(3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzyl- idene)-7-(diethylamino)-2-oxo-2H-chromene-3-carbohydrazide (1) has been synthesized and showed an obviously “off-on-off” fluorescence response toward Al ³⁺ and pyrophosphate (PPi) in aqueous solution. The detection limits of sensor 1 were 0.26 μmol/L to Al ³⁺ and 0.1 μmol/L to PPi, and the binding stoichiometry was 1∶1. In addition, the binding mechanism was further confirmed by fluorescence titration, nuclear magnetic titration and ESI-MS. The effective determination pH range for Al ³⁺ and PPi was from 2 to 10, and the cycle response test could reach 4 times.

Key words: coumarin, fluorescent chemosensor, Al³⁺, PPi, sequential recognition

引用此文

孟宪娇, 赵晋忠, 张永坡, 李志春, 袁长春, 马文兵. 一种基于香豆素骨架的荧光化学传感器于水溶液中实现对Al³⁺和焦磷酸根(PPi)的连续识别[J]. 有机化学, 2021, 41(3): 1161-1167.

Xianjiao Meng, Jinzhong Zhao, Yongpo Zhang, Zhichun Li, Changchun Yuan, Wenbing Ma. A Fluorescent Chemosensor Based on Coumarin for Squential Recognition of Al³⁺ and Pyrophosphate (PPi) in Aqueous Solution[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1161-1167.

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图/表 11

图式1. 传感器1的合成

Scheme 1. Synthesis of sensor 1

图1. 传感器1 (1 μmol/L)的水溶液中[含有微量的N,N-二甲基甲酰胺(DMF)]加入20 equiv.金属阳离子时的荧光响应

Figure 1. Fluorescence spectra of sensor 1 in aqueous solution [trace amounts of N,N-dimethylformamide (DMF)] with the addition of 20 equiv. of metal ions Inset: the solution fluorescence change of sensor 1 (1 μmol/L) in the absence and presence of 20 equiv. Al 3+ (λex: 450 nm)

图2. 水溶液中传感器1 (1 μmol/L)和其它金属阳离子(20 equiv.)在有无Al 3+的存在下对应的荧光强度

Figure 2. Fluorescence intensity of sensor 1 (1 μmol/L) with selected cations (20 equiv.) in the absence or presence of Al 3+ in aqueous solution

图3. 传感器1在水溶液中(含有微量的DMF)随着Al3+浓度的变化的荧光滴定谱图

Figure 3. Fluorescence titration spectra of sensor 1 upon addition of Al3+ in aqueous solution (trace amounts of DMF) [Al3+]: 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 3.0, 4.0 and 5.0 equiv. The Job plot showed that sensor 1 formed a 1∶1 complex with Al3+

图4. 配合物1-Al3+的水溶液中(含有微量的DMF)加入10 equiv.阴离子时的荧光响应

Figure 4. Fluorescence spectra of complex 1-Al3+ in aqueous solution (trace amounts of DMF) with the addition of 10 equiv. of different anions

图5. 水溶液中配合物1-Al3+ (1 μmol/L)和其它阴离子(10 equiv.)在有无PPi的存在下对应的荧光强度

Figure 5. Fluorescence intensity of complex 1-Al3+ (1 μmol/L) with selected anions (10 equiv.) in the absence or presence of pyrophosphate (PPi) in aqueous solution

图6. 配合物1-Al3+在水溶液中(含有微量的DMF)随着PPi浓度变化的荧光滴定谱图

Figure 6. Fluorescence titration spectra of complex 1-Al3+ upon addition of PPi in aqueous solution (trace amounts of DMF) [PPi]: 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 4, 5, 6, 7, 8, 9 and 10 equiv. The Job plot indicated that 1-Al3+ formed a 1∶1 complex with Ppi

图7. 传感器1随着0.2 equiv. Al3+加入的核磁滴定谱图

Figure 7. 1H NMR titration spectra of sensor 1 upon addition of 0.2 equiv. Al3+

图式2. 传感器1对Al3+以及配合物1-Al3+对PPi可能的作用机理

Scheme 2. Possible mechanism of sensor 1 for Al3+ and 1-Al3+ for PPi

图8. 传感器1在室温水溶液中(含有微量的DMF)于不同pH条件下对Al3+和PPi的荧光响应情况

Figure 8. Change of fluorescence intensity recorded for sensor 1 toward Al3+ and PPi under various pH values in aqueous solution (trace amounts of DMF) medium at room temperature

图9. 在传感器1 (1 μmol/L)的水溶液中(含有微量的DMF)交替加入Al 3+和PPi之后的循环响应测试

Figure 9. Sequential recognition of sensor 1 (1 μmol/L) upon alternate addition of Al 3+ and PPi in aqueous solution (trace amounts of DMF) The inset shows the alternate change of the fluorescence color of the test solution after Al3+ and PPi are alternately added.

参考文献 42

[1]	Zhong, K. L.; Zhou, L. L.; Deng, L. L.; Tang, L. J.; Gao, X.; Liu, X. Y.; Yan, X. M. Chin. J. Org. Chem. 2020, 40, 1251. (in Chinese)
	(钟克利, 周璐璐, 邓隆隆, 汤立军, 高雪, 刘秀英, 燕小梅, 有机化学, 2020, 40, 1251.)
[2]	Kim, S.; Noh, J. Y.; Kim, K. Y.; Kim, J. H.; Kang, H. K.; Nam, S. W.; Kim, S. H.; Park, S.; Kim, C.; Kim, J. Inorg. Chem. 2012, 51, 3597. pmid: 22385332
[3]	Wang, B.; Xing, W.; Zhao, Y.; Deng, X. Environ. Toxicol. Pharmacol. 2010, 29, 308. pmid: 21787618
[4]	Bothra, S.; Upadhyay, Y.; Kumar, R.; Sahoo, S. K. Spectrochim. Acta, Part A 2017, 174, 1.
[5]	Wang, F.; Xu, Y. L.; Aderinto, S. O.; Peng, H. P.; Zhang, H.; Wu, H. L. J. Photochem. Photobiol., A 2017, 332, 273.
[6]	Shree, G. J.; Sivaraman, G.; Siva, A.; Chellappa, D. Dyes Pigm. 2019, 163, 204.
[7]	Peng, H. N.; Han, Y. J.; Lin, N.; Liu, H. H. Opt. Mater. 2019, 95, 109210.
[8]	Zhu, Y. L.; Gong, X. S.; Li, Z. P.; Zhao, X.; Liu, Z. Q.; Cao, D. X.; Guan, R. F. Spectrochim. Acta, Part A 2019, 219, 202.
[9]	Fan, L.; Qin, J. C.; Li, C. R.; Yang, Z. Y. Spectrochim. Acta, Part A 2019, 218, 342.
[10]	Nikfar, Z.; Shariatinia, Z. J. Mol. Graphics Modell. 2017, 76, 86.
[11]	Taha, A.; Akram, M.; Jawad, Z.; Alshemary, A. Z.; Hussain, R. Mater. Sci. Eng., C 2017, 80, 93.
[12]	Zhao, L.; Cao, X. D.; Zheng, W.; Scott, J. W.; Sharma, B. K.; Chen, X. ACS Sustainable Chem. Eng. 2016, 4, 1630.
[13]	Tang, Y. F.; Wang, X. Y.; Yang, Y. C.; Gao, B.; Wan, Y. S.; Li, Y. C.; Chen, D. D. J. Agric. Food Chem. 2017, 65, 5879. pmid: 28671837
[14]	Slaughter, G.; Sunday, J.; Stevens, B. Mater. Chem. Phys. 2015, 163, 245.
[15]	Hu, Y.; Yang, J.; Jia, R.; Ding, Y.; Li, S.; Huang, H. Bioprocess Biosyst. Eng. 2014, 37, 1617. pmid: 24488260
[16]	Strianese, M.; Milione, S.; Maranzana, A.; Grassi, A.; Pellecchia, C. Chem. Commun. 2012, 48, 11419.
[17]	Ronaghi, M.; Karamohamed, S.; Pettersson, B.; Uhlén, M.; Nyrén, P. Anal. Biochem. 1996, 242, 84. pmid: 8923969
[18]	Zhang, J.; She, M.; Li, J.; Wang, C.; Wang, S.; Liu, P.; Zhang, S. Y.; Li, J. L. Sens. Actuators, B 2018, 270, 362.
[19]	Aragoni, M. C.; Arca, M.; Bencini, A.; Caltagirone, C.; Garau, A.; Isaia, F.; Light, M. E.; Lippolis, V.; Lodeiro, C.; Mameli, M.; Montis, R.; Mostallino, M. C.; Pintusa, A.; Puccioni, S. Dalton Trans. 2013, 42, 14516. doi: 10.1039/c3dt51292d pmid: 23977671
[20]	Meng, X. J.; Zhao, J. Z.; Ma, W. B. Chin. J. Org. Chem. 2020, 40, 276. (in Chinese)
	(孟宪娇, 赵晋忠, 马文兵, 有机化学, 2020, 40, 276.)
[21]	Fu, J. X.; Chang, Y. X.; Li, B.; Wang, X. H.; Xie, X. M.; Xu, K. X. Spectrochim. Acta, Part A 2020, 225, 117493.
[22]	Tang, L. J.; Xia, J. Y.; Zhong, K. L.; Tang, Y. W.; Gao, X.; Li, J. R. Dyes Pigm. 2020, 178, 108379.
[23]	Zhong, K. L.; Guo, B. F.; Sun, X. H.; Zhou, X.; Zhang, Q.; Tang, L. J.; Zhang, X. R. Chin. J. Org. Chem. 2017, 37, 2002. (in Chinese)
	(钟克利, 郭宝峰, 孙笑寒, 周雪, 张强, 汤立军, 张行荣, 有机化学, 2017, 37, 2002.)
[24]	Fu, J. X.; Li, B.; Mei, H. H.; Chang, Y. X.; Xu, K. X. Spectrochim. Acta, Part A 2020, 227, 117678.
[25]	Li, F. J.; Bian, Y. J.; Chen, Z. X.; Tang, L. J.; Zhong, K. L.; Hou, S. H. Chem. Bull. 2019, 82, 743. (in Chinese)
	(李方霁, 边延江, 陈志新, 汤立军, 钟克利, 侯淑华, 化学通报, 2019, 82, 743.)
[26]	Geng, F. H.; Zou, C. P.; Liu, J. H.; Zhang, Q. C.; Guo, X. Y.; Fan, Y. C.; Yu, H. D.; Yang, S.; Liu, Z. P.; Li, L. Anal. Chim. Acta 2019, 1076, 131. doi: 10.1016/j.aca.2019.05.026 pmid: 31203957
[27]	Zhu, Y.; Gong, X.; Li, Z.; Zhao, X.; Liu, Z.; Cao, D.; Guan, R. Spectrochim. Acta, Part A 2019, 219, 202.
[28]	Suresh, S.; Bhuvanesh, N.; Prabhu, J.; Thamilselvan, A.; Kannan, K.; Nandhakumar, R. K. V. R. J. Photochem. Photobiol., A 2018, 359, 172.
[29]	Yang, S. J.; Feng, W. Y.; Feng, G. Q. Anal. Chim. Acta 2018, 1034, 119. pmid: 30193625
[30]	Wang, Y.; Hou, X. F.; Li, Z. S.; Zhou, Q. H.; Lei, M. M.; Hu, S. S.; Wu, X. P.; Li, C. M.; Xu, Z. H.; Wang, Y. Anal. Methods 2018, 10, 5790.
[31]	Meng, X. J.; Li, S. L.; Ma, W. B.; Wang, J. L.; Hu, Z. Y.; Cao, D. L. Dyes Pigm. 2018, 154, 194. doi: 10.1016/j.dyepig.2018.03.002
[32]	Meng, X. J.; Cao, D. L.; Hu, Z. Y.; Han, X. H.; Li, Z. C.; Liang, D.; Ma, W. B. Tetrahedron Lett. 2018, 59, 4299.
[33]	Chen, Y.; Bi, K. Y.; Hao, R. T.; Xie, P.; Huang, L. N.; Wang, Y. M.; Zhang, J. F.; Xu, R.; Wu, X. H. Chin. J. Org. Chem. 2020, 40, 511. (in Chinese)
	(陈宇, 毕克英, 郝瑞亭, 谢萍, 黄丽娜, 王玉敏, 张俊峰, 徐锐, 吴相华, 有机化学, 2020, 40, 511.)
[34]	Meng, X. J.; Cao, D. L.; Hu, Z. Y.; Han, X. H.; Li, Z. C.; Ma, W. B. RSC Adv. 2018, 8, 33947.
[35]	Li, S. L.; Cao, D. L.; Meng, X. J.; Hu, Z. Y.; Li, Z. C.; Yuan, C. C.; Zhou, T.; Han, X. H.; Ma, W. B. Spectrochim. Acta, Part A 2020, 230, 118022.
[36]	Li, S. L.; Cao, D. L.; Meng, X. J.; Hu, Z. Y.; Li, Z. C.; Yuan, C. C.; Zhou, T.; Han, X. H. Ma W. B. J. Photochem. Photobiol., A 2020, 392, 112427.
[37]	Xu, Y.; Wang, H.; Zhao, J.; Yang, X.; Pei, M.; Zhang, G.; Zhang, Y. New J. Chem. 2019, 43, 14320.
[38]	Xu, Y.; Wang, H.; Zhao, J.; Yang, X.; Pei, M.; Zhang, G.; Zhang, Y.; Lin, L. J. Photochem. Photobiol., A 2019, 383, 112026.
[39]	Xing, Z. T.; Wang, H. C.; Cheng, Y. X.; James, T. D.; Zhu, C. J. Chem.-Asian J. 2011, 6, 3054. pmid: 21954142
[40]	Dutta, A.; Biswas, S.; Escuer, A.; Dolai, M.; Ghosh, S.; Ali, M. ChemPlusChem 2015, 80, 1440. doi: 10.1002/cplu.201500090 pmid: 31973354
[41]	Zhu, G. H.; Huang, Y.; Lu, L. X.; Wang, C.; Sun, T. M.; Tang, Y. F.; Wang, M.; Shan, D. D.; Wen, S. J.; Zhu, J. L. Spectrochim. Acta, Part A 2019, 210, 105. doi: 10.1016/j.saa.2018.11.006
[42]	Kumar, V.; Kumar, P.; Kumar, S.; Singhal, D.; Gupta, R. Inorg. Chem. 2019, 58, 10364. pmid: 31342750

一种基于香豆素骨架的荧光化学传感器于水溶液中实现对Al³⁺和焦磷酸根(PPi)的连续识别

A Fluorescent Chemosensor Based on Coumarin for Squential Recognition of Al³⁺ and Pyrophosphate (PPi) in Aqueous Solution

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