光谱学与光谱分析, 2015, 35 (7): 1797, 网络出版: 2015-09-08  

一种裸眼识别Cu2+和Hg2+传感器的合成与性质研究

Synthesis and Spectroscopic Study of a Chemosensor for Naked Eye Recognition of Cu2+ and Hg2+
作者单位
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
摘要
设计合成了一种香豆素修饰的罗丹明类衍生物L,用作程序型Cu2+与Hg2+检测传感器.采用核磁共振谱、高分辨质谱、红外光谱对其结构进行了表征.利用紫外光谱考察L对不同金属离子的识别作用,研究发现L可以高选择性和高灵敏度识别Cu2+.向L溶液中加入不同的金属离子时(Zn2+,Hg2+,Cu2+,Fe3+,Cd2+,Co2+,Ni2+,Mg2+,Ca2+,Al3+,La3+,K+,Na+,Mn2+,Pb2+和Ag+),只有Cu2+的加入会使溶液由无色变为粉色,并且在534 nm出现一个新的吸收峰,说明传感器L可以裸眼识别Cu2+.通过紫外滴定得到L可以识别Cu2+的最低检测限为1.9×10-8 mol·L-1.制备了基于L的Cu2+检测试纸,该试纸可以方便快捷的检测水中的Cu2+.通过Job’s曲线和高分辨质谱确定了配合物L-Cu2+之间的结合比为1∶1.另外,若向L-Cu2+的DMSO溶液中加入1 equiv.EDTA,溶液瞬间由粉色变为无色,说明EDTA可以取代L并与Cu2+结合,因此传感器L识别Cu2+是可逆的.另外,向L-Cu2+的配合物中加入Hg2+,溶液会由粉色变为无色(而加入其他阳离子没有明显变化),这可顺序实现对Hg2+的裸眼识别.通过紫外滴定计算出L-Cu2+ 识别Hg2+的最低检测限为2.9×10-7 mol·L-1.因此该程序型传感器L可以有序的裸眼识别Cu2+和Hg2+.
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+.

曹丽, 钱亚骜, 黄燕, 曹娟, 贾春满, 刘春玲, 张岐, 吕正荣. 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(7): 1797. CAO Li, QIAN Ya-ao, HUANG Yan, CAO Juan, JIA Chun-man, LIU Chun-ling, ZHANG Qi, Lv Zheng-rong. Synthesis and Spectroscopic Study of a Chemosensor for Naked Eye Recognition of Cu2+ and Hg2+[J]. Spectroscopy and Spectral Analysis, 2015, 35(7): 1797.

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