一种连续识别Cu2+和草甘膦荧光探针的合成及应用研究

doi:10.6023/cjoc202109049

摘要/Abstract

以7-(4-甲氧基苯基)乙炔基香豆素为荧光基团, 设计并合成了一种香豆素酰腙类荧光探针L. 在探针L的二甲基亚砜(DMSO)/H₂O [V:V=7:3, 4-羟乙基哌嗪乙磺酸(HEPES) 10 mmol/L, pH=7.4]溶液中加入Cu²⁺, 可以通过肉眼观察到颜色由黄色变为浅棕色和明显的荧光猝灭效应. 该探针不受其他金属离子和阴离子的干扰, 检测限为5.6×10^–8 mol/L. 同时, L-Cu²⁺体系通过配体置换的方式实现了对草甘膦的特异性检测, 具有良好的选择性和抗干扰性、较高的灵敏度、较宽的pH适用范围(5~9)和较低的检测限(11.3 ng/mL). 此外, L-Cu²⁺体系可应用于实际水样中草甘膦的检测, 在环境监测等领域具有良好的应用前景.

关键词: 香豆素酰腙, 荧光探针, 连续识别, 草甘膦

A novel fluorescent probe L based on coumarin-derived acylhydrazone was designed and synthesized by using 7-(4-methoxyphenyl)ethynyl coumarin as report group. The probe L showed high selectivity and good anti-interference ability towards Cu²⁺ ion through the color of solution changed from light brown to yellow for naked-eye detection and significant fluorescence intensity quenched in the dimethyl sulfoxide (DMSO)/H₂O [V:V=7:3, 2-[4-(2-hydroxyethyl)piperazin-1- yl]ethanesulfonic acid (HEPES) 10 mmol/L, pH=7.4] solution, and the detection limit of probe L to Cu²⁺ could reach 5.6×10^–8 mol/L. Meanwhile, the L-Cu²⁺ system has high selectivity, good sensitivity, wide pH range (5~9) and low detection limit (11.3 ng/mL) for the detection of glyphosate by ligand replacement method. In addition, glyphosate detection was assessed within the actual water samples for testing the L-Cu²⁺actual application and the method was expected to the detection in environmental samples.

Key words: coumarin-derived acylhydrazone, fluorescent probe, sequential recognition, glyphosate

引用此文

吴绵园, 喻艳超, 刘洋, 由君, 武文菊, 刘波. 一种连续识别Cu²⁺和草甘膦荧光探针的合成及应用研究[J]. 有机化学, 2022, 42(3): 803-811.

Mianyuan Wu, Yanchao Yu, Yang Liu, Jun You, Wenju Wu, Bo Liu. Synthesis and Application of a Novel Fluorescent Probe for Sequential Recognition Cu²⁺ and Glyphosate[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 803-811.

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图/表 13

图式1. 探针L的合成路线

Scheme 1. Synthetic route of probe L

图1. 不同金属阳离子(50 μmol/L)存在下探针L (10 μmol/L)的荧光发射光谱(a)和紫外-可见吸收光谱(b) (λex=435 nm)

Figure 1. Fluorescence intensity (a) and UV-Vis absorption spectra (b) of probe L (10 μmol/L) in the presence of different metal ions (50 μmol/L) (λex=435 nm) Inset: visual color changes observed in solution of probe L (left) and L+Cu2+ (right) after addition of Cu2+ ion

图2. (a)不同浓度的Cu2+ (0~20 μmol/L)加入到探针L (10 μmol/L)的荧光光谱和(b)探针L在550 nm处荧光强度与Cu2+浓度的线性关系

Figure 2. (a) Fluorescence spectra of probe L (10 μmol/L) upon addition of different concentrations of Cu2+ (0~20 μmol/L) and (b) linear relationship between the fluorescence intensity at 550 nm and the concentration of Cu2+ (0~15 μmol/L) Inset: fluorescence intensity at 550 nm of probe L (10 μmol/L) upon addition of different concentrations of Cu2+ (0~20 μmol/L)

图3. 在金属离子(a)或阴离子(b) (50 μmol/L)存在下探针L (10 μmol/L)对Cu2+ (50 μmol/L)识别的抗干扰能力

Figure 3. Anti-interference ability of probe L (10 μmol/L) recognition for Cu2+ (50 μmol/L) in the presence of various metal ions (a) or anions (b) (50 μmol/L)

图4. 探针L与Cu2+的Job’s plot图

Figure 4. Job’s plot of probe L with Cu2+

图5. 不同有机磷农药(50 μmol/L)存在下L-Cu2+的荧光发射光谱(a)和紫外-可见吸收光谱(b)

Figure 5. Fluorescence intensity (a) and UV-Vis absorption spectra (b) of L-Cu2+ in the presence of different organophosphorus pesticides (50 μmol/L) Inset: visual color changes observed in solution of L-Cu2+ (left) and L-Cu2++Glyphosate (right) after addition of Glyphosate

图6. (a)不同浓度的草甘膦(0~20 μmol/L)加入到L-Cu2+溶液的荧光光谱和(b) L-Cu2+溶液在550 nm处荧光强度与草甘膦浓度的线性关系

Figure 6. (a) Fluorescence spectra of L-Cu2+ upon addition of different concentrations of Glyphosate (0~20 μmol/L) and (b) linear relationship between the fluorescence intensity at 550 nm and the concentration of Glyphosate (0~16 μmol/L) Inset: fluorescence intensity at 550 nm of L-Cu2+ upon addition of different concentrations of Glyphosate (0~20 μmol/L)

图7. 在其他有机磷农药(a)或阴离子(b) (50 μmol/L)存在下L-Cu2+对草甘膦识别的抗干扰能力

Figure 7. Anti-interference ability of L-Cu2+ recognition for Glyphosate (50 μmol/L) in the presence of various OPs (a) or anions (b) (50 μmol/L)

图8. L-Cu2+与草甘膦的Job’s plot图

Figure 8. Job’s plot of L-Cu2+ with Glyphosate

图式2. 探针L连续识别Cu2+和草甘膦的原理

Scheme 2. Proposed sequential recognition mechanism of probe L with Cu2+ and Glyphosate

图9. 探针L、探针L+Cu2+和L-Cu2++草甘膦在不同pH时荧光强度的变化

Figure 9. Fluorescence intensity change of probe L, probe L+Cu2+ and L-Cu2++Glyphosate in different pH

图10. 探针L及其在Cu2+和/或草甘膦存在时的荧光发射光谱(A)及INHIBIT逻辑门的真值表及逻辑电路图(B)

Figure 10. Fluorescence spectra of probe L without or with the addition of Cu2+ and/or Glyphosate (A) and the truth table and scheme for the INHIBIT logic gate (B)

Sample	Added/(μg•mL^–1)	Found/(μg•mL^–1)	Recovery rate/%	RSD/% (n=3)
Tap water	—	—	—	0.49
	0.25	0.253	101.2	2.26
	0.5	0.492	98.4	2.51
	1.0	0.978	97.8	1.84
	2.0	2.072	103.6	2.30
Songhua River water	—	—	—	1.62
	0.25	0.242	96.8	2.11
	0.5	0.494	98.8	2.98
	1.0	1.025	102.5	1.34
	2.0	1.982	99.1	1.87

表1. 实际水样中草甘膦的检测结果

Table 1. Detection results of Glyphosate in actual water samples

参考文献 37

[1]	Elcin, S.; Deligoz, H.; Bhatti, A. A.; Oguz, M.; Karakurt, S.; Yilmaz, M. Sens. Actuators, B 2016, 234, 345. doi: 10.1016/j.snb.2016.04.155
[2]	Sunnapu, O.; Kotla, N. G.; Maddiboyina, B.; Marepally, S.; Shanmugapriya, J.; Sekar, K.; Singaravadivel, S.; Sivaraman, G. Anal. Chem. 2017, 2, 7654.
[3]	He, J. W.; Xie, Z. F.; Xue, S. S.; Liu, Y. C.; Shi, W.; Chen, X. Chin. J. Org. Chem. 2021, 41, 2839. (in Chinese) doi: 10.6023/cjoc202102013
	(何佳伟, 解正峰, 薛松松, 刘宇程, 石伟, 陈鑫, 有机化学, 2021, 41, 2839.) doi: 10.6023/cjoc202102013
[4]	Viles, J. H. Coord. Chem. Rev. 2012, 256, 2271. doi: 10.1016/j.ccr.2012.05.003
[5]	Fasea, K. D.; Abolaji, A. O.; Faloye, T. R.; Odunsi, A. Y.; Oyetayo, B. O.; Enya, J. I.; Rotimi, J. A.; Akinyemi, R. O.; Whitworth, A. J.; Aschner, M. J. Trace Elem. Med. Biol. 2021, 67, 126779. doi: 10.1016/j.jtemb.2021.126779
[6]	Mezzaroba, L.; Alfieri, D. F.; Simao, A. C.; Reiche, E. M. Neurotoxichology 2019, 74, 230.
[7]	Keep, K. P.; Squitti, R. Coord. Chem. Rev. 2019, 397, 168. doi: 10.1016/j.ccr.2019.06.018
[8]	Lei, M. M.; Zhou, Q. H.; Yang, L.; Xu, Z. H.; Yang, F. L. Chin. J. Org. Chem. 2020, 40, 2798. (in Chinese) doi: 10.6023/cjoc202005084
	(雷萌萌, 周起航, 杨莉, 许志红, 杨凤岭, 有机化学, 2020, 40, 2798.) doi: 10.6023/cjoc202005084
[9]	Fang, R.; Ding, X.; Luo, W.; Hong, C. Chin. J. Org. Chem. 2020, 40, 2949. (in Chinese) doi: 10.6023/cjoc202004007
	(房茹, 丁旭, 罗稳, 洪琛, 有机化学, 2020, 40, 2949.) doi: 10.6023/cjoc202004007
[10]	Beckie, H. J.; Flower, K. C.; Ashworth, M. B. Plants 2020, 9, 96. doi: 10.3390/plants9010096
[11]	Heymann, A. K.; Schnabel, K.; Billenkamp, F.; Bühler, S.; Frahm, J.; Kersten, S.; Hüther, L.; Meyer, U.; Soosten, D. V.; Trakooljul, N.; Teifke, J. P.; Dänicke, S. Plos One 2021, 16, e0246679. doi: 10.1371/journal.pone.0246679
[12]	Tu, Q.; Yang, T. X.; Qu, Y. Q.; Gao, S. Y.; Zhang, Z. Y.; Zhang, Q. M.; Wang, Y. L.; Wang, J. Y.; He, L. L. Analyst 2019, 144, 2017. doi: 10.1039/C8AN02473A
[13]	Cao, Y.; Wang, L. N.; Shen, C.; Wang, C. Y.; Hu, X. Y.; Wang, G. X. Sens. Actuators, B 2019, 283, 487. doi: 10.1016/j.snb.2018.12.064
[14]	Aguirre, M. C.; Urreta, S. E.; Gomez, C. G. Sens. Actuators, B 2019, 284, 675. doi: 10.1016/j.snb.2018.12.124
[15]	Gandhi, K.; Khan, S.; Patrikar, M.; Markad, A.; Kumar, N.; Choudhari, A.; Sagar, P.; Indurkar, S. Environ. Challenges 2021, 4, 100149. doi: 10.1016/j.envc.2021.100149
[16]	Mesnage, R.; Defarge, N.; Vendomis, J. S.; Seralini, G. E. Food Chem. Toxicol. 2015, 84, 133. doi: 10.1016/j.fct.2015.08.012 pmid: 26282372
[17]	Benedetti, A. L.; Vituri, C. L.; Trentin, A. G.; Dominues, M. A.; Silva, M. A. Toxicol. Lett. 2004, 153, 227. pmid: 15451553
[18]	Jasper, R.; Locatelli, G. O.; Pilati, C.; Locatelli, C. Interdiscip. Toxicol. 2012, 5, 133. doi: 10.2478/v10102-012-0022-5
[19]	Mesnage, R.; Biserni, M.; Wozniak, E.; Xenakis, T.; Mein, C. A.; Antoniou, M. N. Toxicol. Rep. 2018, 5, 819. doi: 10.1016/j.toxrep.2018.08.005 pmid: 30128299
[20]	Topal, A.; Atamanalp, M.; Ucar, A.; Oruc, E.; Kocaman, E. M.; Sulukan, E.; Akdemir, F.; Beydemir, S.; Kilinc, N.; Erdogan, O.; Ceyhun, S. B. Ecotoxicol. Environ. Saf. 2015, 111, 206. doi: 10.1016/j.ecoenv.2014.09.027
[21]	Schnabel, K.; Schmitz, R.; Frahm, J.; Meyer, U.; Breves, G.; Danicke, S. Arch. Anim. Nutr. 2020, 74, 1. doi: 10.1080/1745039X.2019.1687249
[22]	Guyton, K. Z.; Loomis, D.; Grosse, Y.; Ghissassi, F. E.; Tallaa, L. B.; Guha, N.; Scoccianti, C.; Mattock, H.; Straif, K. Lancet Oncol. 2015, 16, 490. doi: 10.1016/S1470-2045(15)70134-8
[23]	Tseng, S. H.; Lo, Y. W.; Chang, P. C.; Chou, S. S.; Chang, H. M. J. Agric. Food Chem. 2004, 52, 4057. doi: 10.1021/jf049973z
[24]	Wang, S.; Liu, B. M.; Yuan, D. X.; Ma, J. Talanta 2016, 161, 700. doi: S0039-9140(16)30695-6 pmid: 27769468
[25]	Liao, Y.; Berthion, J. M.; Colet, I.; Merlo, M.; Nougadere, A.; Hu, R. J. Chromatogr. A 2018, 1549, 31. doi: 10.1016/j.chroma.2018.03.036
[26]	Wumbei, A.; Goeteyn, L.; Lopez, E.; Houbraken, M.; Spanoghe, P. Food Addit. Contam., art B 2019, 12, 231.
[27]	Gendy, K. E.; Mosallam, E.; Ahmed, N.; Aly, N. Anal. Biochem. 2018, 557, 1. doi: 10.1016/j.ab.2018.07.004
[28]	Wang, L.; Bi, Y. D.; Li, Y. J.; Ding, H.; Ding, L. RSC Adv. 2016, 6, 85820. doi: 10.1039/C6RA10115A
[29]	Gui, M. F.; Jiang, J.; Wang, X.; Yan, Y. X.; Li, S. Q.; Xiao, X. L.; Liu, T. B.; Liu, T. G.; Feng, Y. Sens. Actuators, B 2017, 243, 696. doi: 10.1016/j.snb.2016.12.037
[30]	Wang, X. F.; Sakinati, M.; Yang, Y. X.; Ma, Y.; Yang, M.; Luo, H. B.; Hou, C. J. Anal. Methods 2020, 12, 520. doi: 10.1039/C9AY02303H
[31]	Gou, Z. N.; Zhao, S. S.; Zhang, P. Chin. J. Synth. Chem. 2019, 27, 673. (in Chinese)
	(苟珍妮, 赵顺省, 张盼, 合成化学, 2019, 27, 673.)
[32]	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) doi: 10.6023/cjoc201702005
	(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.) doi: 10.6023/cjoc201702005
[33]	Shi, F.; Gui, S. Q.; Liu, H. L.; Pu, S. Z. Dyes Pigm. 2020, 173, 107914. doi: 10.1016/j.dyepig.2019.107914
[34]	Tang, Y.; Li, Y. Y.; Han, J.; Mao, Y. L.; Ni, L.; Wang, Y. Spectrochim. Acta, Part A 2019, 208, 299. doi: 10.1016/j.saa.2018.10.019
[35]	He, G. J.; Liu, X. L.; Xu, J. H.; Yang, L. L.; Fan, A. Y.; Wang, S. J.; Wang, Q. Z. Spectrochim. Acta, Part A 2018, 190, 116. doi: 10.1016/j.saa.2017.09.028
[36]	Paul, K.; Bindal, S.; Luxami, V. Bioorg. Med. Chem. Lett. 2013, 23, 3667.
[37]	Yin, H. J.; Zhang, B. C.; Yu, H. Z.; Zhu, L.; Feng, Y.; Zhu, M. Z.; Guo, Q. X.; Meng, X. M. J. Org. Chem. 2015, 80, 4306. doi: 10.1021/jo502775t

一种连续识别Cu²⁺和草甘膦荧光探针的合成及应用研究

Synthesis and Application of a Novel Fluorescent Probe for Sequential Recognition Cu²⁺ and Glyphosate

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