基于碳点-铕的比率荧光探针可视化检测四环素

doi:10.7503/cjcu20190379

摘要/Abstract

摘要：

结合四环素对碳点(CDs)的荧光猝灭及对铕离子(Eu ³⁺)的荧光增强作用, 建立了一种肉眼可辨的比率荧光分析方法用于水样中四环素残留的便捷检测. 通过优化CDs/Eu ³⁺比例、溶液pH值等实验条件, 使检测体系对四环素的荧光响应呈现由蓝色→粉色→红色的颜色转变过程, 易于通过肉眼进行分辨和半定量分析. 实验结果表明, 2种荧光探针响应比(I₆₁₈/I₄₄₀)的对数值与四环素的浓度在20~100 nmol/L范围内呈线性关系, 方法的检出限为1 nmol/L. 将该方法应用于江水样品中四环素的加标检测, 获得了较好结果.

关键词: 碳点, 铕, 比率荧光分析, 可视化检测, 四环素

Abstract:

On combination of the fluorescence quenching effect of tetracycline on carbon dots(CDs) with the fluorescence enhancement effect of tetracycline on europium ions(Eu ³⁺), a visual ratiometric fluorescence assay was developed for the convenient detection of tetracycline residues. By optimizing the CDs/Eu ³⁺ ratio, pH and other experimental conditions, the detection system exhibited a distinct chang of fluorescence color(blue→pink→red) in response to tetracycline, leading to a convenient identification and semi-quantitation by the naked eye. The results showed that the logarithmic values of I₆₁₈/I₄₄₀ was linearly related to the concentration of tetracycline in the range of 20—100 nmol/L, and the detection limit of this work was 1 nmol/L. Recovery experiment suggested the proposed method fine results for the determination of tetracycline in water samples.

Key words: Carbondots, Europium, Ratiometric fluorescence assay, Visual detection, Tetracycline

中图分类号:

O657.3

TrendMD:

杨伟强, 张桂云, 林华, 倪建聪, 黄玲凤. 基于碳点-铕的比率荧光探针可视化检测四环素. 高等学校化学学报, 2019, 40(11): 2294.

YANG Weiqiang, ZHANG Guiyun, LIN Hua, NI Jiancong, HUANG Lingfeng. Ratiometric Fluorescence Assay for Visual Detection of Tetracycline Residues based on the Complex of Carbon Dots and Europium ^†. Chem. J. Chinese Universities, 2019, 40(11): 2294.

图/表 7

Fig.1 Fluorescence quenching effect of tetracycline on CDs(A) and fluorescence enhancement effect of tetracycline on Eu3+ (B) c(Tetracycline)/(nmol·L-1): a. 0; b. 20; c. 40; d. 60; e. 80; f. 100. ρ(CDs)=1 μg/mL, c(Eu3+)=20 μmol/L. The NaOH-H3BO3 buffer solution concentration was 20 mmol/L with pH=9.0. Insets are the linear relationships between the fluorescence intensities of CDs(A) and Eu-TC(B) and the concentration of tetracycline, respectively.

Fig.2 Schematic diagram for the visual detection of tetracycline residues based on the ratiometric fluorescent probe of CDs-Eu3+

Fig.3 Effect of mass concentration ratio of CDs/Eu3+ on the fluorescence assay(A) and effect of pH on the fluorescence of CDs and Eu-TC(B) (A) c(Tetracycline)=50 nmol/L, ρ(CDs)=1—3 μg/mL, c(Eu3+)=6—60 μmol/L. The NaOH-H3BO3 buffer solution concentration was 20 mmol/L(pH=9.0); (B) c(tetracycline)=100 nmol/L, ρ(CDs)=1 μg/mL, c(Eu3+)=20 μmol/L. The NaOH-H3BO3 buffer solution concentration was 20 mmol/L.

Fig.4 Fluorescence spectrum of CDs-Eu3+ probe varying with the concentration of tetracycline(A) and linear relationship between the lg(I618/I440) and the concentration of tetracycline(B) (A) The inset was the fluorescence color change of the solution. c(Tetracycline)/(nmol·L-1): a. 0; b. 20; c. 40; d. 60; e. 80; f. 100. ρ(CDs)=1 μg/mL; ρ(Eu3+)=20 μmol/L. The NaOH-H3BO3 buffer solution concentration was 20 mmol/L with pH=9.0.

Fig.5 Fluorescence response of CDs-Eu3+ probe to different antibiotics The concentration of tetracycline(TC), oxytetracycline(OTC), chlorotetracycline(CTC) and doxycycline(DOX) were 100 nmol/L; and the concentration of penicillin(PCN), erythromycin(ERY), ciprofloxacin(CIP), sulfadiazine(SD) and chloramphenicol(CAP) were 1 μmol/L.

Table 1 Interference investigation of this assay for tetracycline detection

Interference	Concentration of interference/(μmol·L^-1)	Error(%)	Interference	Concentration of interference/(μmol·L^-1)	Error(%)
LAS	50.0	3.58	Al³⁺	5.0	-2.67
CPC	50.0	2.89	Fe³⁺	5.0	3.16
Tween-80	20.0	3.77	Cu²⁺	10.0	2.53
Ca²⁺	50.0	-0.83	Zn²⁺	50.0	1.12
Mg²⁺	50.0	-0.15	Pb²⁺	20.0	0.45

Table 2 Determinations of tetracycline spiked in water samples

Sample	Add/(nmol·L^-1)	Found^*/(nmol·L^-1)	Recovery(%)	RSD(%, n=3)
1	5.0	5.33	106.6	4.7
2	20.0	20.33	101.7	3.9
3	80.0	78.21	97.8	2.5

参考文献 31

[1]	Chopra I., Roberts M., Microbiol. Mol.Biol.Rev., 2001,65, 232— 260
[2]	Zhang X., Chen Z., Deng H., Yang K., Gong S., Lu W., Lan H., Asian J . Ecotoxicol., 2016,11, 44— 52
[3]	Liu X., Huang D., Lai C., Zeng G., Qin L., Zhang C., Yi H., Li B., Deng R., Liu S., Zhang Y., Trends Anal.Chem., 2018,109, 260— 274
[4]	Virolainen N. E., Pikkemaat M. G., Elferink J. W. A., Karp M. T., J. Agric. Food Chem., 2008,56, 11065— 11070
[5]	Chen Y., Kong D., Liu L., Song S., Hua K., Xu C., Food Anal. Method, 2015,9, 1— 10
[6]	Önal A., ., Food Chem 2011,127, 197— 203
[7]	Yang X., Zhu S., Dou Y., Zhuo Y., Luo Y., Feng Y ., Talanta, 2014,122, 36— 42
[8]	Sun X., Lei Y., Trends Anal.Chem., 2017,89, 163— 180
[9]	Gao X., Du C., Zhuang Z., Chen W ., J. Mater. Chem. C, 2016,4, 6927— 6945
[10]	Li Y. K., Yang T., Chen M. L., Wang J. H ., Talanta, 2018,180, 18— 24
[11]	Shamsipur M., Molaei K., Molaabasi F., Hosseinkhani S., Alizadeh N., Alipour M., Moassess S ., . Sens Actuators B, 2018,257, 772— 782
[12]	Jin H., Gui R., Sun J., Wang Y ., Talanta, 2018,176, 277— 283
[13]	Yan X., Song Y., Zhu C., Li H., Du D., Su X., Lin Y., Anal.Chem., 2018,90, 2618— 2624
[14]	Shi X., Wei W., Fu Z., Gao W., Zhang C., Zhao Q., Deng F., Lu X ., Talanta, 2019,194, 809— 821
[15]	Chen C., Zhao J., Lu Y., Sun J., Yang X., Anal. Chem., 2018,90, 3505— 3511
[16]	Zhong D., Yang K., Wang Y., Yang X ., Talanta, 2017,175, 217— 223
[17]	Ruiz-Palomero C., Benitez-Martinez S., Soriano M. L., Valcarcel M., . Anal. Chim. Acta, 2017,974, 93— 99
[18]	Feng Y., Zhong D., Miao H., Yang X ., Talanta, 2015,140, 128— 133
[19]	Shi W., Guo F., Han M., Yuan S., Guan W., Li H., Huang H., Liu Y., Kang Z ., J. Mater. Chem. B, 2017,5, 3293— 3299
[20]	Qian S Qiao L. n., Xu W., Jiang K., Wang Y., Lin H., ., Talanta, 2019,194, 598— 603
[21]	Heffern M. C., Matosziuk L. M., Meade T. J., Chem. Rev., 2014,114, 4496— 4539
[22]	Tan H., Ma C., Song Y., Xu F., Chen S., Wang L., Biosens. Bioelectron., 2013,50, 447— 452
[23]	Zhou Z., Li X., Gao J., Tang Y., Wang Q ., J. Agric. Food Chem., 2019,67, 3871— 3878
[24]	Li X., Ma H., Deng M., Iqbal A., Liu X., Li B., Liu W., Li J., Qin W ., J. Mater. Chem. C, 2017,5, 2149— 2152
[25]	Shen Z., Zhang C., Yu X., Li J., Wang Z., Zhang Z., Liu B ., J. Mater. Chem. C, 2018,6, 9636— 9641
[26]	Xu J., Shen X., Jia L., Zhou T., Ma T., Xu Z., Cao J., Ge Z., Bi N., Zhu T., Guo S., Li X ., J. Hazard. Mater., 2018,342, 158— 165
[27]	Gui R., Jin H., Bu X., Fu Y., Wang Z., Liu Q., ., Coord. Chem. Rev 2019,383, 82— 103
[28]	Zhou Y., Huang X., Liu C., Zhang R., Gu X., Guan G., Jiang C., Zhang L., Du S., Liu B., Han M. Y., Zhang Z ., Anal. Chem., 2016,88, 6105— 6109
[29]	He W., Gui R., Jin H., Wang B., Bu X., Fu Y ., Talanta, 2018,178, 109— 115
[30]	Li J. Y., Liu Y., Shu Q. W., Liang J. M., Zhang F., Chen X. P., Deng X. Y., Swihart M. T., Tan K. J., Langmuir., 2017,33, 1043— 1050
[31]	Tan H., Chen Y ., Sens. Actuators B, 2012,173, 262— 267