基于氮掺杂碳点的荧光增强简便、快速而准确地检测环丙沙星

doi:10.11944/j.issn.1000-0518.2020.07.190318

摘要/Abstract

摘要： 以苹果酸为碳源,磷酸铵提供氮源,采用固态热解法一步合成一种水溶性的、氮掺杂的蓝色荧光碳点(N-CDs)。所得到的碳点荧光量子产率高达20.7%,形貌近似球形,平均粒径约为3.3 nm。基于环丙沙星(CIP)对碳点的荧光增强作用,建立了一种CIP的定量检测方法。最佳实验参数为:碳点浓度为7.5 μg/mL,pH值为5.9,孵化时间为5 min。在此实验条件下,碳点的荧光强度增加值(ΔF)和CIP的浓度在0.39~40.00 μmol/L范围内呈良好的线性关系,方法的检出限为0.12 μmol/L,相对标准偏差(n=5)为4.2%。干扰实验结果指出,除了铜离子具有明显的影响外,其它共存物质的干扰可以忽略不计,而铜离子的干扰可通过加入草酸铵来掩蔽。最后利用所构建的荧光传感器对实际样品中CIP进行检测,回收率在93%~107%之间。本研究为CIP定量分析提供了一种简单、快速、灵敏度高、选择性好而有效的测定方法。

关键词: 氮掺杂荧光碳点, 环丙沙星, 荧光探针, 荧光增强

Abstract: Nitrogen doped fluorescence carbon dots (N-CDs) were successfully synthesized by a facile one step solid phase pyrolysis treatment using malic acid as the carbon source and ammonium phosphate as the nitrogen source. The fluorescence quantum yield of the obtained N-CDs reaches 20.7% and the N-CDs have approximately spherical morphology with an average diameter of 3.3 nm. The as prepared N-CDs were used as the fluorescent probe to detect ciprofloxacin (CIP) based on the enhancement of N-CDs fluorescence upon adding CIP. The optimal experimental mass conditions are 7.5 μg/mL of N-CDs, pH=5.91, and 5 min of incubation time for the detection of CIP. The enhancement of N-CDs fluorescence exhibits a good linear relationship with the concentration of CIP ranged from 0.39 μmol/L to 40.0 μmol/L under the optimal conditions. The linear regression equation is ΔF=1.61×10⁷[CIP]-3.28 with a correlation coefficient R²=0.994. The detection limit and relative standard deviation (n=5) are estimated to be 0.12 mol/L and 4.2%, respectively. The interference experiments indicate that potential coexistence substances (except copper ions) have ignorable effects on the detection of CIP, and the interference of copper ions could be masked with 4% ammonium oxalate solution. Finally, the proposed sensor was successfully applied to analyze real samples with satisfactory results.

Key words: nitrogen doped carbon dots, ciprofloxacin, fluorescence probe, fluorescence enhancement

徐丽萍, 刘清士, 董芷辰, 郭兴家, 董微. 基于氮掺杂碳点的荧光增强简便、快速而准确地检测环丙沙星[J]. 应用化学, 2020, 37(7): 830-838.

XU Liping, LIU Qingshi, DONG Zhichen, GUO Xingjia, DONG Wei. Simple, Fast and Accurate Detection of Ciprofloxacin Based on Fluorescence Enhancement of Nitrogen-Doped Carbon Dots[J]. Chinese Journal of Applied Chemistry, 2020, 37(7): 830-838.

参考文献

[1] Resch-Genger U,Grabolle M,Cavalierejaricot S,et al. Quantum Dots versus Organic Dyes as Fluorescent Labels[J]. Nat Methods,2008,5(9):763-775.
[2] Sun W,Du Y X,Wang Y Q,et al. Study on Fluorescence Properties of Carbogenic Nanoparticles and Their Application for the Determination of Ferrous Succinate[J]. J Lumin,2010,130(8):1463-1469.
[3] Hou J,Zhang F S,Yan X,et al. Sensitive Detection of Biothiols and Histidine Based on the Recovered Fluorescence of the Carbon Quantum Dots-Hg(II) System[J]. Anal Chim Acta,2015,859:72-78.
[4] CHE Wangyuan,LIU Changjun,YANG Kun,et al. Research Progress in Preparation, Property and Application of Fluorescent Carbon Dots[J]. Acta Mater Compos Sin,2016,33(3):431-450(in Chinese).
车望远,刘长军,杨焜,等. 荧光碳点的制备和性质及其应用研究进展[J]. 复合材料学报,2016,33(3):431-450.
[5] Huang S,Yang E L,Yao J D,et al. Red Emission Nitrogen, Boron, Sulfur Co-doped Carbon Dots for “On-Off-On” Fluorescent Mode Detection of Ag⁺ Ions and L-Cysteine in Complex Biological Fluids and Living Cells[J]. Anal Chim Acta,2018,1035:192-202.
[6] Shi B F,Su Y B, Zhang L L,et al. Nitrogen and Phosphorus Co-doped Carbon Nanodots as a Novel Fluorescent Probe for Highly Sensitive Detection of Fe³⁺ in Human Serum and Living Cells[J]. ACS Appl Mater Interfaces,2016,8(17):10717-10725.
[7] Liu Y,Gong X J,Dong W J,et al. Nitrogen and Phosphorus Dual-doped Carbon Dots as a Label-Free Sensor for Curcumin Determination in Real Sample and Cellular Imaging[J]. Talanta,2018,183:61-69.
[8] ZHANG Xiaozhe,ZHANG Wenjun,ZHANG Zhuxing,et al. One Step Preparation of N-Doped Carbon Dots with High Fluorescence Yield for Selective Detection of Mercury Ion[J]. Chinese J Inorg Chem,2015,31(1):1-6(in Chinese).
张筱喆,张文君,张祖星,等. 掺氮高荧光碳点的一步法制备及对痕量Hg(Ⅱ)离子的选择性检测[J]. 无机化学学报,2015,31(1):1-6.
[9] Huan Y,Li H,Shuang P,et al. Nitrogen-Doped Fluorescent Carbon Dots for Highly Sensitive and Selective Detection of Tannic Acid[J]. Spectrochim Acta Part A,2019,210:111-119.
[10] Yang M M,Li H,Liu J,et al. Convenient and Sensitive Detection of Norfloxacin with Fluorescent Carbon Dots[J]. J Mater Chem B,2014,2(45):7964-7970.
[11] Chin N X,Neu H C. Ciprofloxacin, a Quinolone Carboxylic Acid Compound Active Against Aerobic and Anaerobic Bacteria[J]. Antimicrob Agents Chemother,1984,25(3):319-326
[12] Turiel E,Martín-Esteban A,Tadeo J L. Multiresidue Analysis of Quinolones and Fluoroquinolones in Soil by Ultrasonic-Assisted Etraction in Small Columns and HPLC-UV[J]. Anal Chim Acta,2006,562:30-35.
[13] Pascual-Reguera M,Parras G P,DíAz A M,et al. Solid-Phase UV Spectrophotometric Method for Determination of Ciprofloxacin[J]. Microchem J,2004,77(1):79-84.
[14] Maya M T,Gonçalves N J,Silva N B. Simple High-Performance Liquid Chromatographic Assay for the Determination of Ciprofloxacin in Human Plasma with Ultraviolet Detection[J]. J Chromatogr B,2001,755(1/2):305-309.
[15] Hao A J,Guo X J,Wu Q,et al. Exploring the Interactions Between Polyethyleneimine Modified Fluorescent Carbon Dots and Bovine Serum Albumin by Spectroscopic Methods[J]. J Lumin,2016,170:90-96.
[16] Baig M M F,Chen Y C. Bright Carbon Dots as Fluorescence Sensing Agents for Bacteria and Curcumin[J]. J Colloid Interface Sci,2017,501:341-349.
[17] Kundu A,Nandi S,Das P,et al. Facile and Green Approach to Prepare Fluorescent Carbon Dots:Emergent Nanomaterial for Cell Imaging and Detection of Vitamin B₂[J]. J Colloid Interface Sci,2016,468:276-283.
[18] LIU Cuige,XU Yizhuang,WEI Yongju,et al. Spectral Properties, Protonation and Fluorescence Quantum Yield of Ciprofloxacin[J]. Spectrosc Spectr Anal,2005,25(9):1446-1450(in Chinese).
刘翠格,徐怡庄,魏永巨,等. 环丙沙星的光谱性质、质子化作用与荧光量子产率[J]. 光谱学与光谱分析,2005,25(9):1446-1450.
[19] Hernández M,Aguilar C,Borrull F,et al. Determination of Ciprofloxacin, Enrofloxacin and Flumequine in Pig Plasma Samples by Capillary Isotachophoresis-Capillary Zone Electrophoresis[J]. J Chromatogr B Anal Technol Biomed Life Sci,2002,772(1):163-172.