1. 海南大学教育部热带多糖资源利用工程研究中心，海南省精细化工重点实验室，海南 海口 570228 2. 江苏大学化学化工学院，江苏 镇江 212013 3. Department of Biomedical Engineering, Case Western Reserve University, Cleveland, Ohio 44106-7207, USA
Synthesis and Spectroscopic Study of a Chemosensor for Naked Eye Recognition of Cu2+ and Hg2+
CAO Li1, QIAN Ya-ao1, HUANG Yan2, CAO Juan2, JIA Chun-man1, LIU Chun-ling1, ZHANG Qi1,2*, Lü Zheng-rong3
1. Key Study Center of Ministry of Education for Tropical Resources Utilization/Hainan Provincial Key Lab of Fine Chemicals, Hainan University, Haikou 570228, China 2. College of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China 3. Department of Biomedical Engineering, Case Western Reserve University, Cleveland, Ohio 44106-7207, USA
Abstract：Compound L, as the procedural sensor for the detection of Cu2+ and Hg2+, was designed and synthesized based on the coumarin-modified rhodamine derivative. The structure of compound L was characterized by NMR, high resolution mass spectrometry and infrared method. Its sensing behavior toward various metal ions was investigated with absorbance methods. The study found that L had good selectivity and sensitivity for Cu2+. When addition of various metal ions (Zn2+, Hg2+, Cu2+, Fe3+, Cd2+, Co2+, Ni2+, Mg2+, Ca2+, Al3+, La3+, K+, Na+, Mn2+, Pb2+and Ag+), only Cu2+ could induce a visible change of solution from colourless to pink and a new absorption band centered at 534 nm appear, which indicated that compound L could be used for the naked eye detection of Cu2+. From UV titration, the detection limit was about 1.9×10-8 mol·L-1. Test strips based on L were fabricated, and this test strips could act as a convenient and efficient Cu2+ test kit. The binding ratio of the complex of L-Cu2+ was 1∶1 according to the Job’s plot and high resolution mass spectrometer (HRMS) experiments. Moreover, Upon addition of 1 equiv. EDTA to the mixture of L and Cu2+ in DMSO solution, colour changed from pink to almost colourless, indicating that the EDTA replaced the receptor L to coordinate with Cu2+. Therefore, L could be classified as a reversible sensor for Cu2+. In addition, when adding Hg2+ to L-Cu2+ complexes, a visible change of solution from pink to colourless was observed，while other metal ions didn’t cause this change. Thus, L-Cu2+ complex also could be used for the naked eye recognition of Hg2+, and the detection limit was calculated about 2.9×10-7 mol·L-1 according to the UV titration. Consequently, this procedural sensor L could be use for the orderly naked eye recognition of Cu2+ and Hg2+.
Key words：Sensor;Naked eye recognition;Sequential recognition;Copper ion;Mercury ion
曹 丽1，钱亚骜1，黄 燕2，曹 娟2，贾春满1，刘春玲1，张 岐1,2*，吕正荣3 . 一种裸眼识别Cu2+和Hg2+传感器的合成与性质研究 [J]. 光谱学与光谱分析, 2015, 35(07): 1797-1801.
CAO Li1, QIAN Ya-ao1, HUANG Yan2, CAO Juan2, JIA Chun-man1, LIU Chun-ling1, ZHANG Qi1,2*, Lü Zheng-rong3 . Synthesis and Spectroscopic Study of a Chemosensor for Naked Eye Recognition of Cu2+ and Hg2+. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2015, 35(07): 1797-1801.
[1] Orvig C, Abrams M J. Chem. Rev., 1999, 99: 2201. [2] Bargossi C, Fiorini M C, Montalti M, et al. Coord. Chem. Rev., 2000, 208: 17. [3] Forzani E S, Zhang H, Chen W, et al. Environ. Sci. Technol., 2005, 39: 1257. [4] Frank E L, Hughes M P, Bankson D D, et al. Clin. Chem., 2001, 47: 1109. [5] Brown D R, Kozlowski H. Dalton Trans., 2004, 13：1907. [6] Tchounwou P B, Ayensu W K, Ninashvili N, et al. Environ. Toxicol., 2003, 18: 149. [7] ZHANG Yong, LI Wei, WANG Qiang, et al(张 勇，李 伟，王 强，等). Acta Chimica Sinica(化学学报)，2013, 71: 1496. [8] Jiang W, Wang W. Chem. Commun., 2009, 3913. [9] Kim J H, Noh J Y, Hwang I H, et al. Tetrahedron Lett., 2013, 54: 4001. [10] YI Wei-guo, ZHANG Rong, GU Zheng, et al(易卫国, 张 荣, 顾 峥，等). Acta Chimica Sinica(化学学报)，2011, 69: 1024. [11] Huang W, Zhu X, Wu D Y, et al. Dalton Trans., 2009, 47：10457. [12] Zhao Y, Zhang X B, Han Z X, et al. Anal. Chem., 2009, 81: 7022. [13] Li T R, Yang Z Y, Li Y, et al. Dyes Pigments., 2011, 88: 103. [14] Ma Q J, Zhang X B, Zhao X H, et al. Anal. Chem. Acta, 2010, 663: 85. [15] Huang W, Zhou P, Yan W B, et al. J. Environ. Monit., 2009, 11: 330. [16] Zhang X, Shiraishi Y, Hirai T. Tetrahedron Lett., 2007, 48: 5455. [17] Kumari N, Dey N, Bhattacharya S. RSC Adv., 2014, 4: 4230. [18] Zeng X, Dong L, Wu C, et al. Sens. Actuators B, 2009, 141: 506. [19] Wang L N, Qin W W, Tang X L, et al. J. Org. Biomol. Chem., 2010, 8: 3751.
