一步水热法合成荧光碳点检测锰(Ⅶ)
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摘要
以苦杏仁酸和脯氨酸为碳源和氮掺杂剂,采用一步水热法合成氮掺杂的蓝色荧光水溶性碳点(CDs),通过透射电镜、红外光谱、X射线光电子能谱、紫外可见吸收光谱和荧光光谱法等手段进行表征。合成的CDs粒径均匀,尺寸约为(2.62±0.20) nm,表面存在氨基、羟基、羧基、CC等官能团。最大激发和发射波长分别为360和450 nm,具有典型的激发波长依赖性,相对量子产率为7.86%,稳定性好。基于荧光共振能量转移(FRET)原理,CDs的荧光可被MnⅦ有效猝灭。在1～100μmol/L (即0.055～5.500 mg/L)范围内,MnⅦ浓度与CDs的荧光猝灭程度呈线性关系,相关系数(R~2)为0.9986,检出限为0.04μmol/L (2.20μg/L),具有高灵敏度和良好的选择性。此CDs可进入HepG2细胞内,发出蓝光,且胞内荧光强度与MnⅦ浓度大致呈线性关系。将此碳点用于环境水样和细胞内MnⅦ含量的检测,结果良好。
A convenient and green strategy was developed for the synthesis of water-soluble carbon dots(CDs) with blue fluorescence by one-step hydrothermal synthesis method using mandelic acid and proline as carbon precursor and nitrogen dopant, respectively. The synthesized CDs were characterized by transmission electron microscope(TEM), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), ultraviolet visible spectroscopy(UV) and fluorescence, respectively. The CDs were quasi spherical nano-particles with perfect monodispersity, and the average size was 2.62 ± 0.20 nm. They possessed crystal structures and the distinct lattice spacing was 0.21 nm. Abundant groups like CC, hydroxyl, carboxylic and amine groups, etc, were linked on the surface of the synthesized CDs. The CDs showed typical excitation-dependent photoluminescent behavior with the maximum excitation and emission wavelengths of 360 nm and 450 nm, respectively. The effects of ionic strength, pH and storage time on the fluorescence intensity of the CDs were slight, which demonstrated the perfect fluorescence stability of the CDs. Based on fluorescence resonance energy transfer(FRET) mechanism between donor CDs and acceptor Mn(Ⅶ), the fluorescence of CDs could be effectively quenched by Mn(Ⅶ). On the basis of this, a method was developed for detection of Mn(Ⅶ). The method showed a linear range of 1-100 μmol/L(i.e., 0.055-5.500 mg/L) with a correlation coefficient(R~2) of 0.9986. The limit of detection was 0.04 μmol/L(i.e., 2.20 μg/L), showing excellent sensitivity and selectivity. Due to low toxicity and excellent biocompatibility of CDs, HepG2 cells emitted blue fluorescence after incubated with CDs, and intracellular fluorescence intensities were roughly linear with Mn(Ⅶ) concentration, which enabled the potential applications of CDs in Mn(Ⅶ) biosensing. In brief, the CDs were designed as successful fluorescent sensors for direct determination of MnⅦ content in aqueous solution and living cell.
A convenient and green strategy was developed for the synthesis of water-soluble carbon dots(CDs) with blue fluorescence by one-step hydrothermal synthesis method using mandelic acid and proline as carbon precursor and nitrogen dopant, respectively. The synthesized CDs were characterized by transmission electron microscope(TEM), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), ultraviolet visible spectroscopy(UV) and fluorescence, respectively. The CDs were quasi spherical nano-particles with perfect monodispersity, and the average size was 2.62 ± 0.20 nm. They possessed crystal structures and the distinct lattice spacing was 0.21 nm. Abundant groups like CC, hydroxyl, carboxylic and amine groups, etc, were linked on the surface of the synthesized CDs. The CDs showed typical excitation-dependent photoluminescent behavior with the maximum excitation and emission wavelengths of 360 nm and 450 nm, respectively. The effects of ionic strength, pH and storage time on the fluorescence intensity of the CDs were slight, which demonstrated the perfect fluorescence stability of the CDs. Based on fluorescence resonance energy transfer(FRET) mechanism between donor CDs and acceptor Mn(Ⅶ), the fluorescence of CDs could be effectively quenched by Mn(Ⅶ). On the basis of this, a method was developed for detection of Mn(Ⅶ). The method showed a linear range of 1-100 μmol/L(i.e., 0.055-5.500 mg/L) with a correlation coefficient(R~2) of 0.9986. The limit of detection was 0.04 μmol/L(i.e., 2.20 μg/L), showing excellent sensitivity and selectivity. Due to low toxicity and excellent biocompatibility of CDs, HepG2 cells emitted blue fluorescence after incubated with CDs, and intracellular fluorescence intensities were roughly linear with Mn(Ⅶ) concentration, which enabled the potential applications of CDs in Mn(Ⅶ) biosensing. In brief, the CDs were designed as successful fluorescent sensors for direct determination of MnⅦ content in aqueous solution and living cell.
引文
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28 Dong Y Q,Pang H C,Yang H B,Guo C X,Shao J W,Chi Y W,Li C M,Yu T. Angew. Chem. Int. Edit.,2013,52(30):7800-7804
29 Borse V,Thakur M,Sengupta S,Srivastava R. Sens. Actuators B,2017,248:481-492
30 Yan F Y,Bai Z J,Chen Y,Zu F L,Xing L X,Xu J X,Chen L. Sens. Actuators B,2018,275:86-94
31 Yuan Y S,Jiang J Z,Liu S P,Yang J D,Zhang H,Yan J J,Hu X L. Sens. Actuators B,2017,242:545-553
32 Mhetear Tuerhong,XU Yang,YIN Xue-Bo. Chinese J. Anal. Chem.,2017,45(1):139-150木合塔尔·吐尔洪,徐阳,尹学博.分析化学,2017,45(1):139-150
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2 Gong P W,Sun L,Wang F,Liu X C,Yan Z Q,Wang M Z,Zhang L,Tian Z Z,Liu Z,You J M. Chem. Eng. J.,2019,356:994-1002
3 Huang S,Yang E L,Yao J D,Liu Y,Xiao Q. Anal. Chim. Acta,2018,1035:192-202
4 LYU Piao-Piao,XIE Dan-Dan,ZHANG Zhao-Hui. Chinese J. Anal. Chem.,2018,46(6):917-924吕飘飘,谢丹丹,张朝晖.分析化学,2018,46(6):917-924
5 He J H,Cheng Y Y,Yang T,Zou H Y,Huang C Z. Anal. Chim. Acta,2018,1035:203-210
6 Wang Y Y,He J,Zheng M D,Qin M D,Wei W. Talanta,2019,191:519-525
7 DENG Xiang-Yi,FENG Ya-Li,LI Hao-Ran,DU Zhu-Wei,TENG Qing,KANG Jin-Xing,WANG Hong-Jun. Chinese J.Anal. Chem.,2017,45(10):1497-1503邓祥意,冯雅丽,李浩然,杜竹玮,滕青,康金星,王洪君.分析化学,2017,45(10):1497-1503
8 Deng P,Lu L Q,Cao W C,Tian X K. Spectrochim. Acta,2017,173:578-583
9 Ahmed M J,Islam M T,Hossain F. RSC Adv.,2018,8(10):5509-5522
10 WHO/SDE/WSH/03. 04/104/Rev/1,Manganese in Drinking-water Background Document for Development of WHO Guidelines for Drinking-water Quality. World Health Organization
11 GB5749-85,Sanitary Standard for Drinking Water. National Standards of the People's Republic of China生活饮用水卫生标准.中华人民共和国国家标准. GB5749-85
12 GB 14880-2012,Use Standard for Food Nutrition Enhancer. National Standards of the People's Republic of China食品营养强化剂使用标准.中华人民共和国国家标准. GB 14880-2012
13 Tobiasz A,Soltys M,Kurys E,Domagaa K,Dudek-Adamska D,Walas S. Spectrochim. Acta B,2017,134:11-16
14 Zou D Q,Qing Y,Li Y T,Liu M S,Yang Y L. J. Iran. Chem. Soc.,2014,11(2):415-422
15 Chen S Z,Zhu L,Chen X L,Wang X,Zhou X R. Atom. Spectrosc.,2011,32(1):12-16
16 Khoo S B,Soh M K,Cai Q T,Khan M R,Guo S X. Electroanalalysis,1997,9(1):45-51
17 Kostova D. Russ. J. Inorg. Chem.,2011,56(6):968-974
18 Gong X J,Li Z B,Hu Q,Zhou R X,Shuang S M,Dong C. ACS Appl. Mater. Interfaces,2017,9(44):38761-38772
19 Zhang Y Q,Liu X Y,Fan Y,Guo X Y,Zhou L,Lv Y,Lin J. Nanoscale,2016,8(33):15281-15287
20 Zheng M,Liu S,Li J,Qu D,Zhao H F,Guan X G,Hu X L,Xie Z G,Jing X B,Sun Z C. Adv. Mater.,2014,26(21):3554-3560
21 Amin N,Afkhami A,Hosseinzadeh L,Madrakian T. Anal. Chim. Acta,2018,1030:183-193
22 Li Z H,Guo S,Yuan Z Q,Lu C. Sens. Actuators B,2017,241:821-827
23 Li S H,Jiang J,Yan Y N,Wang P,Huang G,Kim N H,Lee J H,He D N. Mater. Sci. Eng. C,2018,93:1054-1063
24 Gong X J,Lu W J,Liu Y,Li Z B,Shuang S M,Dong C,Choi M M F. J. Mater. Chem. B,2015,3(33):6813-6819
25 Li J F,Zhang L,Li P X,Zhang Y,Dong C. Sens. Actuators B,2017,248:92-100
26 Zheng A Q,Wang N,Chen M L,Shu Y,Wang J H. Talanta,2018,188:788-794
27 Chen X X,Jin Q Q,Wu L Z,Tung C H,Tang X J. Angew. Chem. Int. Edit.,2014,53(46):12542-12547
28 Dong Y Q,Pang H C,Yang H B,Guo C X,Shao J W,Chi Y W,Li C M,Yu T. Angew. Chem. Int. Edit.,2013,52(30):7800-7804
29 Borse V,Thakur M,Sengupta S,Srivastava R. Sens. Actuators B,2017,248:481-492
30 Yan F Y,Bai Z J,Chen Y,Zu F L,Xing L X,Xu J X,Chen L. Sens. Actuators B,2018,275:86-94
31 Yuan Y S,Jiang J Z,Liu S P,Yang J D,Zhang H,Yan J J,Hu X L. Sens. Actuators B,2017,242:545-553
32 Mhetear Tuerhong,XU Yang,YIN Xue-Bo. Chinese J. Anal. Chem.,2017,45(1):139-150木合塔尔·吐尔洪,徐阳,尹学博.分析化学,2017,45(1):139-150
33 Zhang J,Yu S H. Mater. Today,2016,19(7):382-393