掺氮碳量子点的制备及对偶氮类色素的荧光检测
Preparation of nitrogen-doped carbon quantum dots and application to fluorescent detection of azo dyes
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摘要: 以苯酚为碳源、乙二胺为氮源，采用一步水热法制备了水溶性的掺氮碳量子点（N-CQDs），用于偶氮类色素的荧光检测.首先对N-CQDs的形貌、组成和荧光特性进行了表征，然后研究了色素柠檬黄和胭脂红对N-CQDs体系显著的荧光猝灭效应，优化了实验条件.结果表明，该氮掺杂方法当苯酚-乙二胺摩尔比接近1：1时，在N-CQDs表面可形成大量强供电子基团，有效提高了其荧光效率；柠檬黄、胭脂红对N-CQDs的荧光猝灭在5min内达到平衡，在磷酸盐缓冲溶液（pH=7.5）的条件下荧光猝灭效率最高，且均为静态猝灭.最佳条件下，柠檬黄浓度[Q]在0-80 nmol·L-1范围内与N-CQDs体系的荧光猝灭程度（lgF0/F）呈现良好的线性关系：lg F0/F=0.0047[Q]-0.015，R2=0.994，检出限为8.20 nmol·L-1；胭脂红浓度[Q]在0-40 nmol·L-1范围内与N-CQDs体系的荧光猝灭程度（lg F0/F）也呈现良好的线性关系：lg F0/F=0.0252[Q]-0.0052，R2=0.996，检出限为1.54 nmol·L-1.本研究为简便、快捷、灵敏地检测废水中偶氮类色素柠檬黄和胭脂红提供了新的方法.Abstract: New water-soluble nitrogen-doped carbon quantum dots (N-CQDs) were facilely synthesized by one-step hydrothermal method using hybrid carbon and nitrogen sources of phenol and ethylenediamine, and were applied to fluorescent detection of Azo dyes. The surface morphology, composition and fluorescence properties of the as-prepared N-CQDs were characterized, and the remarkable fluorescence quenching effects of tartrazine and ponceau 4R dyes on N-CQDs were investigated along with experimental condition optimization. Experimental results showed that the fluorescence efficiency of N-CQDs was effectively improved owing to the formation of large amount of strong electron-donating groups on the N-CQDs surface when the molar ratio of phenol-ethylenediamine approached 1:1. Other two main parameters were optimized as the reaction incubation time at 5 min and reaction medium in phosphate buffer (pH=7.5), and hence the highest quenching efficiency was obtained. The quenching mechamism for the two dyes belonged to static quenching. Under the optimum conditions, excellent linear relationship between the ratio of fluorescence intensities (lgF0/F) and the dye concentration was attained in the range of 0-80 nmol·L-1 for tartrazine (lg F0/F=0.0047[Q]-0.015, R2=0.994) and 0-40 nmol·L-1 for ponceau 4R (lg F0/F=0.0252[Q]-0.0052, R2=0.996). The detection limits were down to 8.20 nmol·L-1 and 1.54 nmol·L-1 for tartrazine and ponceau 4R, respectively. It was demonstrated that such N-CQDs system can provide an effective fluorescence sensing platform for the simple, fast and sensitive determination of azo dyes (such as tartrazine and ponceau 4R) in waste water samples.
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[1] ZHANG J, DOMG L, YU S H. A selective sensor for cyanide ion (CN) based on the inner filter effect of metal nanoparticles with photoluminescent carbon dots as the fluorophore[J]. Sci Bull, 2015, 60:785-791. [2] CAO L, WANG X, MEZIANI M J, et al. Carbon dots for multiphoton bioimaging[J]. Journal of the American Chemical Society, 2007, 129(37):11318-11319. [3] 傅鹏,周丽华,唐连凤,等. 碳量子点的制备及其在能源与环境领域应用进展[J]. 应用化学, 2016, 33(7):742-755. FU P, ZHOU L H, TANG L F, et al. Progress in preparation of carbon quantum dots and its application in the fields of energy and environment[J]. Chinese Journal of Applied Chemistry, 2016, 33(7):742-755(in Chinese).
[4] ZHAO Q L, ZHANG Z L, HUANG B H, et al. Facile preparation of low cytotoxicity fluorescent carbon nanocrystals by electrooxidation of graphite[J]. Chemical Communications, 2008, 41(41):5116-5118. [5] SAHU S, BEFERA B, MAITI T K, et al. Simple one-step synthesis of highly luminescent carbon dots from orange juice:Application as excellent bio-imaging agents[J]. Chemical Communications, 2012, 48(70):8835-8837. [6] HSU P C,CHANG H T. Synthesis of high-quality carbon nanodots from hydrophilic compounds:Role of functional groups[J].Chemical Communications, 2012, 48(33):3984-3986. [7] ZHANG Y Q, MA D K, ZHUANG Y, et al. One-pot synthesis of N-doped carbon dots with tunable luminescence properties[J]. J. Materials Chemistry, 2012, 22(33):16714-16718. [8] TALASKA G, AL-ZOUGHOOL M. Aromatic amines and biomarkers of human exposure[J]. J. Environmental Science and Health. Part C, Environmental Carcinogenesis & Ecotoxicology Reviews, 2003, 21(2):133-164. [9] 刘胜男, 张国庆, 王素方, 等. 高效液相色谱法同时测定果蔬汁饮料中20种禁限用食品添加剂[J]. 轻工学报, 2016, 31(4):23-29. LIU S N, ZHANG G Q, WANG S F, et al. Simultaneous determination of 20 restricted food additives in fruit and vegetable juice beverage by HPLC[J]. Journal of Light Industry, 2016, 31(4):23-29(in Chinese).
[10] YOSHIOKA N, ICHIHASHI K. Determination of 40 synthetic food colors in drinks and candies by high-performance liquid chromatography using a short column with photodiode array detection[J]. Talanta, 2008, 74(5):1408-1413. [11] 宋丹萍, 张宏, 李琪. 国内外食用色素标准的比较及检测方法的研究进展[J]. 食品科学, 2014,35(3):295-300. SONG D P, ZHANG H, LI Q. Comparison of national standards for edible pigments between china and foreign countries and progress on analytical techniques[J]. Food Science, 2014, 35(3):295-300(in Chinese).
[12] 杨熙,吴惠勤,黄芳,等. 高效液相色谱-串联质谱法同时测定粉条中6种人工合成色素[J].分析实验室, 2015,34(6):672-676. YANG X,WU H Q, HUANG F, et al. Determination of six kinds of synthetic pigments in starch noodles by HPLC-MS/MS[J].Chinese Journal of Analysis Laboratory, 2015,34(6):672-676(in Chinese).
[13] 王雪莲, 马博雅, 王首忠, 等. 高效液相色谱-串联质谱法同时测定食品中9种人工色素[J]. 食品安全质量检测学报,2018,9(1):128-134. WANG X L, MA B Y, WANG S Z, et al. Simultaneous determination of 9 kinds of synthetic colorants in food by high performance liquid chromatography-tandem mass spectrometry[J]. Journal of Food Safety and Quality, 2018, 9(1):128-134(in Chinese).
[14] 朱振宝, 张亚莉, 贾玮, 等. 超高效液相色谱-四极杆/静电场轨道离子阱质谱测定植物提取物中的7种合成色素[J]. 食品科学, 2017, 38(24):196-201. ZHU Z B, ZHANG Y L, JIA W, et al. Determination of 7 artificial dyes in plant extracts by ultra-performance liquid chromatography-quadrupole/electrostatic field orbit trap high-resolution mass spectrometry[J]. Food Science, 2017, 38(24):196-201(in Chinese).
[15] WANG Y Q, ZHANG H M, ZHANG G C, et al. Interaction of the flavonoid hesperidin with bovine serum albumin:A fluorescence quenching study[J]. Journal of Luminescence, 2007, 126:211-218. [16] PAPADOPOULOU A, GREEN R J, FRAZIER R A. Interaction of flavonoids with bovine serum albumin:A fluorescence quenching study[J]. Journal of Agricultural and Food Chemistry, 2005, 53(1):158-163. [17] 班睿,李玉美,杜海军,等. 基于Mn:ZnS量子点荧光共振能量转移法测定水体中孔雀石绿[J]. 环境化学,2014, 33(4):684-688. BAN R, LI Y M, DU H J, et al. Fluorescence resonance energy transfer base on Mn-doped ZnS quantum dots for the determination of Malachite Green in Water[J]. Environmental Chemistry, 2014, 33(4):684-688(in Chinese).
[18] 邓小燕, 李佳渝, 谭克俊. 基于碳量子点荧光分光光度法检测叶酸[J]. 分析化学, 2014, 42(4):542-546. DENG X Y,LI J Y,TAN K J. Carbon quantum dots-based fluorescence spectrophotometric assay of folic acid[J]. Journal of Instrumental Analysis,2014, 42(4):542-546(in Chinese).
[19] XU H, YANG X P, LI G, et al. Green synthesis of fluorescent carbon dots for selective detection of tartrazine in food samples[J]. Journal of Agricultural and Food Chemistry, 2015, 63(30):6707-6714. [20] ZHAO H W, GE M, ZHANG Z X, et al. Spectroscopic studies on the interaction between riboflavin and albumins[J]. Spectrochim. Acta Part A:Molecular and Biomolecular Spectroscopy, 2006, 65(3-4):811-817. [21] DONG Y Q, ZHANG J, XING Y, et al. Quantification of ponceau 4R in foods by indirect competitive enzyme-linked immunosorbent assay (icELISA)[J]. Journal of Agricultural and Food Chemistry, 2015, 63(28):6338-6345. [22] 马康, 蒋孝雄, 赵敏, 等.高效液相色谱法同时测定软饮料中20种食品添加剂[J]. 分析化学, 2012,40(11):l661-1667. MA K, JIANG X X, ZHAO M, et al. Simultaneous determination of 20 food additives in drinks by high performance liquid chromatography coupled with photo-diode array detector[J]. Journal of Agricultural and Food Chemistry, 2012,40(11):l661-1667(in Chinese).
[23] LI W J, ZHOU X, TONG S S, et al. Poly(N-isopropylacrylamide-co-N,N'-methylene bisacrylamide) monolithic column embedded with γ-alumina nanoparticles microextraction coupled with high-performance liquid chromatography for the determination of synthetic food dyes in soft drink samples[J]. Talanta, 2013,105:386-392. [24] ZHANG Y Y, HU L T, LIU X, et al. Highly-sensitive and rapid detection of ponceau 4R and tartrazine in drinks using alumina microfibers-based electrochemical sensor[J]. Food Chemistry, 2015, 166:352-357. [25] DENG K Q, LI C X, LI X F, et al. Simultaneous detection of sunset yellow and tartrazine using the nanohybrid of gold nanorods decorated graphene oxide[J]. Journal of Electroanalytical Chemistry, 2016, 780:296-302. [26] ALTIN Z S, TOPTAN S. Determination of tartrazine and ponceau-4R in various food Samples by Vierordt's Method and ratio spectra first-order derivative UV spectrophotometry[J]. Journal of Food Composition and Analysis, 2002, 15(6):667-683. -
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