Page 74 - 《精细化工》2021年第10期

第 38 卷第 10 期 精 细 化 工 Vol.38, No.10
2021 年 10 月 FINE CHEMICALS Oct. 2021

功能材料
香豆素基金属-有机笼对氨基葡萄糖的识别

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李亚楠，赵 亮 ，蔡俊凯，段春迎
（大连理工大学 精细化工国家重点实验室，辽宁 大连 116024）

摘要：将发光性质优异的香豆素基团作为荧光信号单元引入有机配体 H 3 L，与过渡金属离子 Zn(Ⅱ)配位自组装，
构建了一例金属-有机笼状化合物 Zn-L，利用主客体氢键弱作用实现了对氨基葡萄糖的选择性识别。高分辨质谱
和紫外-可见吸收光谱结果显示，金属-有机笼状化合物 Zn-L 结构可能为 M 6 L 4 的八面体构型，12 个香豆素基团
均匀分布在笼状结构的顶点，空腔带有窗口，允许尺寸合适的客体分子自由进出。主客体核磁滴定显示，氨基
葡萄糖通过多重氢键作用与笼状结构相结合；高分辨质谱测试表明，笼状结构与氨基葡萄糖形成了物质的量比
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为 1∶2 的主客体包合物。荧光滴定光谱拟合结果显示，络合常数为 1.6×10 L /mol ，证实主客体间具有较强的
络合作用，有利于笼状结构对氨基葡萄糖的选择性识别。氨基葡萄糖分子对 Zn-L 荧光强度淬灭高达 93%，最低
检测限为 0.23 μmol/L，而其他 9 种常见生物糖类小分子只能淬灭 5%~20%，Zn-L 对氨基葡萄糖分子具有选择性
荧光响应，且可以应用于活细胞中氨基葡萄糖的荧光成像。
关键词：金属-有机笼；主客体作用；氨基葡萄糖；荧光响应；选择性识别；功能材料
中图分类号：TQ630 文献标识码：A 文章编号：1003-5214 (2021) 10-2004-08

Coumarin-based metal-organic cage for recognition of glucosamine

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LI Ya′nan, ZHAO Liang , CAI Junkai, DUAN Chunying
（State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China）

Abstract: A metal-organic cage compound Zn-L was constructed by introducing coumarin group with
excellent luminescent properties as fluorescence signal unit into organic ligand H 3L and self-assembling
with transition metal ion Zn (Ⅱ). Compound Zn-L realized selective recognition of glucosamine via weak
host-guest hydrogen bonding interaction. The results of high-resolution mass spectroscopy and UV-Vis
absorption spectroscopy showed that the metal-organic cage compound had a M 6 L 4 octahedral structure,
with twelve coumarin groups uniformly distributed at the vertical positions of the cage, and a large
cavity with opening windows that allowed free ingress and egress of the guest molecules with suitable
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size. HNMR titration indicated that glucosamine was combined with cage structure through multiple
hydrogen bonding. High resolution mass spectrometry test suggested that a molar ratio of 1∶2
host-guest inclusion complex was formed between metal-organic cage Zn-L and glucosamine. The
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results of fluorescence titration spectra fitting showed that the complexation constant was 1.6×10 L /mol ,
confirming the strong complexation between host and guest, which was conducive to the selective
recognition of glucosamine by the cage structure. Glucosamine molecules quenched up to 93% of the
fluorescence intensity of Zn-L, and the detection limit was 0.23 μmol/L, while the other nine common
biological carbohydrate molecules could only quench 5%~20% of the fluorescence intensity, indicating
that Zn-L had a highly selective fluorescence response to glucosamine molecules and could be used for
fluorescence imaging of glucosamine in living cells.
Key words: metal-organic cage; host-guest interaction; glucosamine; fluorescence response; selective
recognition; functional materials

收稿日期：2021-04-18; 定用日期：2021-06-10; DOI: 10.13550/j.jxhg.20210402
基金项目：国家自然科学基金（21890381, 21820102001）
作者简介：李亚楠（1997—），女，硕士生，E-mail：1yanan1997@163.com。联系人：赵 亮（1984—），男，副教授，E-mail：zhaol@dlut.
edu.cn。