发光学报, 2017, 38 (8): 1109, 网络出版: 2017-08-30  

氧化偶氮苯双席夫碱化合物对Cu2+的比色识别

Highly Selective Colorimetric Recognition of Copper Ions Based on Bis-Schiff Base Containing An Azoxy Group
作者单位
吉林大学 化学学院, 吉林 长春130012
摘要
为得到简便地识别Cu2+的传感器, 设计合成了氧化偶氮苯双席夫碱化合物。采用紫外吸收光谱法研究了化合物对Cu2+的配合作用及对As3+、Mo6+、Mn2+、Zn2+、Fe3+、Pb2+、Al3+、Hg2+、Ni2+、Pt4+、Mg2+、Be2+、Sr2+、Cs+、Os4+、Cd2+、Se4+、Cr6+、Co2+、Rb+、Ba2+、V6+、Ca2+等23种金属离子的干扰作用。采用等摩尔的连续变化法(Job-plot), 研究了化合物与Cu2+形成配合物的配比。用红外光谱法研究了配合机理。同时研究了在EDTA存在时, 化合物对Cu2+的“off-on”性质。结果表明, 合成的化合物具有大共轭体系, 结构新颖且稳定。化合物可以克服23种金属离子的干扰, 对Cu2+的选择性很高。化合物与Cu2+形成1∶1型强发光配合物, 可以达到比色(裸眼)识别。在1.32~13.0 μmol·L-1范围内,化合物紫外光谱吸光度值与Cu2+浓度呈现良好的线性关系, 线性范围宽, 最低检出限为2.6×10-7 mol·L-1。在EDTA存在时, 该配合物释放出Cu2+, 表现出对Cu2+的“off-on”模式, 红外光谱法研究明确了化合物与Cu2+的结合位点。研究结果表明, 所合成的氧化偶氮苯双席夫碱化合物可以对Cu2+实现简便易行的比色(裸眼)识别。
Abstract
In order to obtain copper ion sensors, a bis-Schiff base containing an azoxy group was synthesized. The complexation effect of the compound on Cu2+ was studied, and the interference of 23 metal ions such as As3+, Mo6+, Mn2+, Zn2+, Fe3+, Pb2+, Al3+, Hg2+, Ni2+, Pt4+, Mg2+, Be2+, Sr2+, Cs+, Os4+, Cd2+, Se4+, Cr6+, Co2+, Rb+, Ba2+, V6+, Ca2+ was also studied in MeOH-H2O by UV-Vis spectroscopy. Job-plot method was used to study the ratio of the Cu2+ complex with the compound. The cooperation mechanism was studied by infrared spectrometry, and the “off-on” nature of the compound with copper ion was studied in EDTA. The results indicate that the bis-Schiff base has a large conjugated system, the structure is novel and stable. The bis-Schiff base shows a highly selective response to Cu2+. A clear color change from colorless to yellow is observed upon the addition of Cu2+ to the solution of the receptor in MeOH by naked-eyes and a single selectivity colorimetric recognition. The Job-plot shows that the bis-Schiff base coordinates with Cu2+ to form 1∶1 stable luminescent complex. The UV absorbance of the system shows a good linear relationship with Cu2+ concentration within 1.32-13.0 μmol·L-1, and the detection limit is 2.6×10-7 mol·L-1. The sensing of Cu2+ by this sensor is found to be reversible with the Cu2+ induced color being lost upon the addition of EDTA. The process of titrating Compound 1 with Cu2+ is reversible, and Compound 1 can be used as an off-on switch chemosensor. The complexation mechanism of Compound 1 and Cu2+ was studied by IR spectroscopy, and the binding sites of compound 1 and Cu2+ were identified.

吕蕾, 盛野, 郑松志, 苏冉, 安胜姬. 氧化偶氮苯双席夫碱化合物对Cu2+的比色识别[J]. 发光学报, 2017, 38(8): 1109. LYU Lei, SHENG Ye, ZHENG Song-zhi, SU Ran, AN Sheng-ji. Highly Selective Colorimetric Recognition of Copper Ions Based on Bis-Schiff Base Containing An Azoxy Group[J]. Chinese Journal of Luminescence, 2017, 38(8): 1109.

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