一种水溶液中裸眼识别HSO3-/SO32-的长波长荧光探针及其应用

doi:10.6023/cjoc202011037

摘要/Abstract

合成了一种(E)-2-(3-氰基-4-(3-甲酰基-4-羟基苯乙烯基)-5,5-二甲基呋喃-2(5H)-亚烷基)丙二腈衍生物CDM, ¹H NMR、¹³C NMR和HRMS验证了其结构. CDM在MeCN/Tris (V∶V=2∶8, pH=7.4)溶液中通过荧光信号“ON-OFF”识别HSO₃^-/SO₃^2-, 颜色由粉色变为无色. 探针CDM具有良好的抗干扰能力和较快的响应速度(200 s), pH适用范围为7~14, 荧光光谱和紫外吸收光谱的检测限分别为6.07和1.59 μmol/L. 实验研究表明, CDM能检测真实水样和糖样中的HSO ₃^-/SO₃^2-, 并能够对活细胞中的HSO₃^-/SO₃^2-进行荧光成像.

关键词: 荧光探针, HSO₃^-/SO₃^2-, 长波长, 裸眼识别, 细胞成像

3-Cyano-4-(3-formyl-4-hydroxystyryl)-5,5-dimethylfuran-2(5H)-alkylene)malononitrile derivative CDM was synthesized. The correctness of its structure was verified by ¹H NMR, ¹³C NMR and HRMS. CDM can recognize HSO₃^-/SO₃^2- with the naked eye through the fluorescent signal “ON-OFF” in MeCN/Tris ( V∶V=2∶8, pH=7.4) solution, and the color changes from pink to colorless. The probe CDM has good anti-interference ability and fast response speed (200 s), the pH applicable range is 7~14, and the detection limits of the fluorescence and UV absorption spectrum are 6.07 and 1.59 μmol/L. The experimental research shows that CDM can detect HSO₃^-/SO₃^2- in real water samples and sugar samples and, can perform fluorescent image HSO₃^-/SO₃^2- in living cells.

Key words: fluorescent probe, HSO₃^-/SO₃^2-, long wavelength, naked eye recognition, cell imaging

引用此文

王超, 王鑫, 钟克利, 侯淑华, 燕小梅, 边延江, 汤立军. 一种水溶液中裸眼识别HSO₃^-/SO₃^2-的长波长荧光探针及其应用[J]. 有机化学, 2021, 41(6): 2417-2423.

Chao Wang, Xin Wang, Keli Zhong, Shuhua Hou, Xiaomei Yan, Yanjiang Bian, Lijun Tang. A Long-Wavelength Fluorescent Probe for Naked Eye Recognition of HSO₃^-/SO₃^2- in Aqueous Solution and Its Application[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2417-2423.

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图/表 12

图示1. 探针CDM的合成路线

Scheme 1. Synthetic route of probe CDM

图1. CDM (10 μmol/L)的MeCN/Tris (V∶V=2∶8, pH=7.4) 溶液中加入各种阴离子后的荧光光谱(a)和紫外吸收光谱(b)变化(λ em=610 nm, λ ex=550 nm)

Figure 1. Fluorescence (a) and UV absorption spectrum (b) of CDM (10 μmol/L) in MeCN/Tris (V∶V=2:8, pH=7.4) solution upon addition of different anions (λ em=610 nm, λ ex=550 nm)

图2. CDM (10 μmol/L)的MeCN/Tris (V∶V=2∶8, pH=7.4) 溶液中加入不同浓度的HSO 3–(0~150 μmol/L)后的荧光光谱(a)和紫外吸收光谱(b)变化(λ ex=550 nm)

Figure 2. Fluorescence (a) and UV absorption spectrum (b) changes of CDM (10 μmol/L) in MeCN/Tris (V∶V=2∶8, pH=7.4) solution upon addition different concentration of HSO 3– (0~150 μmol/L) (λ ex=550 nm)

图3. 探针CDM的荧光强度之比(a)和紫外吸收强度之比(b)随log[HSO3–]变化的线性关系

Figure 3. Plot of the fluorescence (a) and UV absorption intensity (b) of CDM with different concentration of log [HSO3–]

图4. CDM (10 μmol/L)分别加入各种阴离子(150 μmol/L)(白色)及再加入HSO 3– (150 μmol/L)(红色)后的荧光强度变化

Figure 4. Changes in fluorescence intensity of CDM (10 μmol/ L) in the presence of different anions (white) and further addition of HSO 3– (150 μmol/L) (red)

图5. CDM对HSO3–(150 μmol/L)的时间依赖性荧光强度变化

Figure 5. Time-dependent fluorescence intensity change of CDM to HSO3–(150 μmol/L)

图6. CDM和CDM+HSO3–在不同pH下的荧光强度变化

Figure 6. Fluorescence intensity changes of CDM and CDM+HSO3–at different pH

Sample	Added/ (μmol•L^–1)	Found/ (μmol•L^–1)	Recovery rate/%	CV (n=3)
Tap water	50	49.95	99.9	0.38
	70	69.75	99.6	0.61
	90	90.05	100.0	0.49
Lake water	50	51.35	102.7	0.93
	70	71.05	101.5	0.64
	90	89.56	99.5	1.08
River water	50	49.40	98.8	2.12
	70	71.49	102.1	0.96
	90	90.51	100.6	0.77

表1. 实际水样中HSO3–的检测结果

Table 1. Detection results of HSO3– in actual water samples

Sample	Added/ (μmol•L^–1)	Found/ (μmol•L^–1)	Recovery rate/%	CV (n=3)
Sugar 1	70	72.12	103.03	2.09
	90	91.50	101.67	1.70
	110	113.66	103.33	2.48
Sugar 2	70	71.36	101.94	0.91
	90	91.79	101.99	1.98
	10	109.86	99.87	1.65

表2. 实际糖样中HSO3–的检测结果a

Table 2. Detection results of HSO3– in actual sugar samples

图7. CDM预处理的MCF-7细胞与不同浓度的HSO3– (0、10、50、100和150 μmol/L)孵育30 min的白色通道、红色通道和叠加通道

Figure 7. White channel, white channel and merge channel of MCF-7 cells pretreated with CDM (10 µmol/L) incubation with HSO 3– (0, 10, 50, 100, 150 µmol/L) for 30 min

图8. CDM识别HSO3–的机理

Figure 8. Mechanism of CDM sensing HSO3–

图9. CDM+HSO3–的高分辨质谱图

Figure 9. HRMS spectrum of compound CDM+HSO3–

参考文献 54

[1]	Iwasawa, S.; Kikuchi, Y.; Nishiwaki, Y.; Omae, K. J. Occup. Health 2009, 51,47.
[2]	Zhu, J.; Zhang, H.; Liu, M.; Liu, J.; Liao, Y.; Quan, Z.; Wang, X. Chin. J. Org. Chem. 2020, 40,1049(in Chinese).
	(朱继华, 张浩, 刘敏, 刘旌江, 廖原, 权正军, 王喜存, 有机化学, 2020, 40,1049.)
[3]	Sang, N.; Yun, Y.; Li, H.; Hou, L. Toxicol. Sci. 2010, 114,236.
[4]	Niknahad, H.; O’Brien, P. J. Chem. Biol. Interact. 2008, 174,154.
[5]	Li, J.; Li, R.; Meng, Z. Q. Eur. J. Pharmacol. 2010, 645,50.
[6]	Feng, G.; Du, Y. Anal. Lett. 2019, 53,13.
[7]	Finkel, T.; Holbrook, N. J. Nature 2000, 408,247.
[8]	Wang, Y.; Meng, Q.; Zhang, R.; Jia, H. Org. Biomol. Chem. 2017, 15,2739.
[9]	Rhee, S. G. Science 2006, 312,1883.
[10]	Wang, Y.; Meng, Q.; Zhang, R.; Jia, H. J. Lumin. 2017, 192,302.
[11]	Ally, H. V.; Misso, N. L. A.; Madan, V. Clin. Exp. Allergy 2009, 39,1651.
[12]	Cheng, X.; Jia, H.; Feng, J.; Qin, J. Sens. Actuators, B 2013, 184,280.
[13]	Xu, J.; Pan, J.; Jiang, X.; Qin, C. Biosens. Bioelectron. 2016, 77,732.
[14]	Liu, Y.; Li, K.; Xie, K.; Li, L. Chem. Commun. 2016, 52,3433.
[15]	Palraj, K.; Jan, T.; Ulrike, K.; Jason, J. D.; Paul, V. B. Anal. Chem. 2010, 82,7374.
[16]	Kamaljot, K.; Savita, C.; Sukhjinder, S.; Mehta, S. K. J. Lumin 2015, 14,28.
[17]	Cheng, X.; Jia, H.; Feng, J.; Qin, J.; Li, Z. Sens. Actuators, B 2013, 184,80.
[18]	Koch, M.; Koeppen, R.; Siegel, D. J. Agric. Food Chem. 2010, 58,9467.
[19]	Kaur, V.; Aulakh, J. S.; Malik, A. K. Anal. Chim. Acta 2007, 603,44.
[20]	Altunay, N.; Gurkan, R. Anal. Methods 2016, 8,352.
[21]	Theisen, S.; Hansch, R.; Kothe, L.; Leist, U. Biosens. Bioelectron. 2010, 26,181.
[22]	Beitollahi, H.; Tajik, S.; Biparva, P. Measurement 2014, 56,177.
[23]	Zhang, Y.; Guan, L.; Yu, H.; Yan, Y. Anal. Chem. 2016, 88,4431.
[24]	Van, Meel, K.; Smekens, A.; Behets, M.; Kazandjian, P.; Van, Grieken, R. Anal. Chem. 2007, 79,6383.
[25]	Zhong, K.; Zhou, L.; Deng, L.; Tang, L. Chin. J. Org. Chem. 2020, 40,1256(in Chinese).
	(钟克利, 周璐璐, 邓隆隆, 汤立军, 有机化学, 2020, 40,1256.)
[26]	Meng, H.; Wu, F. W.; He, Z. K.; Zeng, Y. E. Talanta 1999, 48,577.
[27]	Zhang, G.; Ji, R.; Kong, X. RSC Adv. 2019, 9,1150.
[28]	Situmorang, M.; Gooding, J. J.; Hibbert, D. B.; Barnett, D. Analyst 1999, 124,1779.
[29]	Kaur, V.; Aulakh, J. S.; Malik, A. K. Anal. Chim. Acta 2007, 603,44.
[30]	Locatelli, C.; Melucci, D.; Torsi, G. Anal. Bioanal. Chem. 2005, 382,1567.
[31]	Tang, L.; Xia, J.; Zhong, K.; Tang, Y.; Gao, X.; Li, J. Dyes Pigm. 2020, 178,108379.
[32]	Tang, L.; Zhou, L.; Yan, X.; Zhong, K.; Gao, X.; Li, J. J. Photochem. Photobiol. A 2020, 387,112160.
[33]	Tang, L.; Zhou, L.; Yan, X.; Zhong, K.; Gao, X.; Liu, X.; Li, J. Dyes Pigm. 2020, 182,108644.
[34]	Zhong, K.; Zhao, J.; Li, Q.; Hou, S.; Tang, Y.; Bian, Y.; Tang, L. Chin. J. Org. Chem. 2018, 38,1786(in Chinese).
	(钟克利, 赵杰, 李秋莹, 侯淑华, 汤轶伟, 边延江, 汤立军, 有机化学, 2018, 38,1786.)
[35]	Gao, J.; Wang, C.; Tan, H. J. Mater. Chem. B 2017, 5,7700.
[36]	Yang, X.; Cui, Y.; Li, Y. Spectrochim. Acta B 2015, 137,1060.
[37]	Zeng, R. F.; Lan, J. S.; Wu, T. Food Chem. 2020, 318,126358.
[38]	Albrecht, M.; Gossage, R. A.; Lutz, M.; Spek, A. L.; Koten, G. V. Chem.-Eur. J. 2000, 6,1445.
[39]	Hassan, S. S. M.; Hamza, M. S. A.; Mohamed, A. H. K. Anal. Chim. Acta 2006, 570,239.
[40]	Choi, M. G.; Hwang, J. Y.; Eor, S. Y.; Chang, S. K. Org. Lett. 2010, 12,5627.
[41]	Chen, S.; Hou, P.; Wang, J.; Song, X. RSC Adv 2012, 2,10873.
[42]	Gu, X.; Liu, C.; Zhu, Y.; Zhu, Y.; Agric, J. Food Chem. 2011, 59,11939.
[43]	Leontiev, A. V.; Rudkevich, D. M. J. Am. Chem. Soc. 2005, 127,14127.
[44]	Sun, Y. M.; Zhong, C.; Gong, R.; Mu, H. L.; Fu, E. Q. J. Org. Chem. 2009, 74,7946.
[45]	Yang, X. F.; Zhao, M.; Wang, G. Sens. Actuators, B 2011, 152,13.
[46]	Chen, S.; Hou, P.; Wang, J. X.; Song, X. Z. RSC Adv. 2012, 2,10873.
[47]	Qiang, S. Y.; Wang, P.; Liu, J.; Zhang, J. Y.; Guo, W. Analyst 2012, 137, 3433.
[48]	Wu, H.; Yang, X.; Men, J.; Zhang, H.; Zhou, J. Anal. Sci. 2019, 35,1305.
[49]	Yan, P.; Wang, T.; Zhang, D.; Ma, X. Chin. J. Org. Chem. 2019, 39,928(in Chinese).
	(闫沛沛, 王婷, 张丹, 马晓雪, 有机化学, 2019, 39,928.)
[50]	Zhong, K.; Guo, B.; Sun, X.; Zhou, X.; Zhang, Q.; Tang, L.; Zhang, X. 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.)
[51]	Zhong, K.; Chen, L.; Yan, X. Dyes Pigm. 2020, 182,108656.
[52]	Zhang, L.; Wang, L.; Zhang, X. J. Photochem. Photobiol. A 2020, 395,112498.
[53]	Zhou, F.; Feng, H.; Li, H. ACS Omega 2020, 10,5459.
[54]	Huo, F.; Zhang, Y.; Yue, Y.; Chao, J. Dyes Pigm. 2017, 143,275.

一种水溶液中裸眼识别HSO₃^-/SO₃^2-的长波长荧光探针及其应用

A Long-Wavelength Fluorescent Probe for Naked Eye Recognition of HSO₃^-/SO₃^2- in Aqueous Solution and Its Application

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