基于聚乙烯亚胺碳纳米点的桑色素比率型荧光探针

doi:10.7503/cjcu20200018

摘要/Abstract

摘要：

利用水热合成法制备了一种基于聚乙烯亚胺的荧光碳纳米点, 用光谱方法研究了其对桑色素的识别作用. 结果表明, 该碳纳米点对桑色素具有比率型荧光响应, 且响应速度快、选择性和灵敏度高、抗干扰能力强. 将桑色素加入到碳纳米点溶液中后, 碳纳米点自身的荧光(460 nm)立即被猝灭, 同时在555 nm处出现新的荧光发射峰并逐渐增强; 其新发射峰(555 nm)与原发射峰(460 nm)的强度比值在此过程中呈线性增加. 基于此, 在1.0×10^-6~4.0×10^-5 mol/L浓度范围内, 可实现对桑色素的检测, 该比率荧光响应非常灵敏, 检出限可达3.0×10^-8 mol/L. 另外, 该碳纳米点与常见金属离子、氨基酸及其它具有类似桑色素结构的黄酮醇均不反应, 显示出对桑色素的高选择性. 该检测方法的荧光强度随桑色素浓度的增加而逐渐增强, 并伴随着由蓝色到黄色的荧光颜色变化, 可实现对桑色素的可视化检测; 同时该碳纳米点还可用于稀释胎牛血清中桑色素的定量检测.

关键词: 碳纳米点, 桑色素, 荧光增强, 比率型探针, 快速响应

Abstract:

A blue-emitting carbon dots(CDs) based on polyethyleneimines(PEI) was prepared by hydrothermal synthesis method, which is applied to detect morin with a ratiometric fluorescence response. The detection method has very fast response speed, high selectivity and sensitivity, and strong anti-interference. The fluorescence emission of CDs is quenched and a new emission peak centered at 555 nm appears and enhances gradually in the presence of morin. The fluorescence intensity ratio of the new emission peak(555 nm) to the original emission peak(460 nm) increases linearly in the range from 1.0×10^-6 to 4.0×10^-5 mol/L. In particular, the ratio response is very sensitive with an extremely low detection limit of 3.0×10^-8 mol/L. The proposed probe shows no response to other commercial available flavonol with similar structure, common metal ions and amino acids, which indicates a high selectivity toward morin. In addition, the fluorescent color was changed from blue to yellow in the presence of morin, which displays a visual detection method. And the CDs can be applied to detect morin in diluted fetal calf serum either. Therefore, the present study supplies a cost-effective, fast and easily performed approach to detect morin with high selectivity and sensitivity.

Key words: Carbon dots, Morin, Fluorescent enhancement, Ratiometric, Fast response

中图分类号:

O657.3

TrendMD:

薛雅荣, 李洪伟, 吴玉清. 基于聚乙烯亚胺碳纳米点的桑色素比率型荧光探针. 高等学校化学学报, 2020, 41(7): 1531.

XUE Yarong, LI Hongwei, WU Yuqing. Carbon Dots Based-on Polyethyleneimines as a Ratiometric Fluorescent Sensor of Morin^†. Chem. J. Chinese Universities, 2020, 41(7): 1531.

图/表 6

Fig.1 Fluorescence spectra of CDs(0.30 mg/L) in the absence and presence of different amounts of morin in HEPES-NaOH buffer(pH=7.4)(A) and the related ratio changes of fluorescence intensity at 555 nm to 460 nm(B) (A) a. Without morin; b.—p. concentrations of morin are 1.0, 2.0, 3.0, 4.0, 5.0, 7.5, 10, 20, 30, 40, 50, 100, 150, 200, 250 μmol/L, respectivly. (B) λex=345 nm.

Table 1 Comparison of the analytical performance of different methodologies towards morin detection

Material	Methodology	Detection limit	Linear range/(μmol·L^-1)	Ref.
Carbon Dots	Fluorometric, turn off	0.6 μmol/L	0—300	[19]
PEDT-Au/rGO/GCE electrode	Amperometric, turn on	8.3 nmol/L	1—150	[20]
V₂O₅ NF/GCE	Amperometric, turn on	9 nmol/L	0.05—10.93	[21]
Metal-organic coordination polymer	Fluorometric, turn on	8.7 nmol/L	0.03—1.8	[22]
Carbon Dots	Fluorometric, turn off	0.12 μmol/L	0.4—60	[23]
f-CNF/Tb2Se2/GCE	Amperometric, turn on	0.6 μmol/L	2.5—158	[24]
HypersilBDS C18 column	HPLC	0.4 μmol/L	22.2—2241	[25]
Carbon Dots	Fluorometric, ratiometric	30 nmol/L	1.0—40	This work

Scheme 1 Schematic representation of the preparation of CDs and application in morin detection

Fig.2 Fluorescence spectra of CDs(0.30 mg/L) in the presence of different kinds of metal ions, amino acids(100 μmol/L) and other flavonols in HEPES-NaOH buffer(pH=7.4)(A) and corresponding intensity ratios at 555 nm and 460 nm(B) 1. Blank; 2. Ca2+; 3. Fe3+; 4. K+; 5. Na+; 6. myricetin; 7. tea polyphenol; 8. quercetin; .9 morin; 10. apigenin; 11. glycine; 12. alanine; 13. valine; 14. leucine; 15. isoleucine; 16. phenylalanine; 17. tryptophan; 18. tyrosine; 19. aspartic acid; 20. asparagine; 21. glutamic acid; 22. lysine; 23. glutamine; 24. methionine; 25. serine; 26. threonine; 27. cysteine; 28. proline; 29. histidine; 30. arginine.

Fig.3 Photographs showing the color changes of CDs test paper in the absence and presence of different amounts of morin under UV light(A) and sunlight(B)

Fig.4 Fluorescence spectra of CDs(0.30 mg/L) in the absence and presence of different amounts of morin in a diluted fetal calf serum(1% in HEPES-NaOH buffer, pH=7.4)(A) and the related ratio changes of fluorescence intensity at 555 nm to 460 nm(λex=345 nm)(B) a. Without morin; b.—p. concentrations of morin are 1.0, 2.0, 3.0, 4.0, 5.0, 7.5, 10, 20, 30, 40, 50, 100, 150, 200, 250 μmol/L, respectivly.

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