中位取代苯硼酸的含稠合外环的硼-二吡咯亚甲基染料类单糖荧光探针的合成与性能

doi:10.3724/SP.J.1095.2014.30591

摘要/Abstract

摘要： 以环己烯为起始原料，首先经过两步改进的合成方法制备出2-乙氧羰基-3,4-四亚甲基吡咯，并用过量氢化铝锂将其高温还原得到2-甲基-3,4-四亚甲基吡咯，后者与被保护的4-甲醛基苯硼酸在三氟乙酸的催化作用下发生缩合反应，用2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)氧化并依次用三乙胺和三氟化硼-乙醚处理后，得到一种新型的中位取代苯硼酸的含稠合外环的硼-二吡咯亚甲基类(BDP)染料衍生物。通过紫外-可见吸收光谱及荧光光谱滴定方法，研究了该染料在特定pH值下对D-果糖、D-半乳糖、D-葡萄糖等3种单糖的响应能力，上述3种单糖与BDP染料衍生物的键合既表现在吸收光谱上，也表现在荧光发射光谱上，并且通过对荧光滴定数据的非线性拟合分析，BDP染料衍生物1与D-果糖、D-半乳糖、D-葡萄糖的结合常数分别为1045、445和130 L/mol。因此该染料衍生物作为单糖的荧光探针，具有灵敏度高、选择性较好等优点；另外，还初步探讨了该荧光探针的传感机理。

关键词: 硼-二吡咯亚甲基染料, 荧光探针, 单糖, 稠合外环, 苯硼酸

Abstract: 2-Ethoxycarbonyl-3,4-tetramethylenepyrrole prepared from cyclohexene through an improved two-step procedure was treated with excess lithium aluminum hydride at high temperature to give 2-methyl-3,4-tetramethylenepyrrole. Further condensation with protected 4-formylphenylboronic acid in the presence of trifluoroacetic acid as catalyst, followed by oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone(DDQ) and treatment with triethylamine and boron trifluoride etherate， gives a novel exocyclic ring-fused boron-dipyrromethene(BDP) dye derivative substituted with phenylboronic ester subunit at the meso-position. The UV-Vis absorption titration and fluorescence titration measurements for BDP dye derivative were carried out to examine its responsibility to D-fructose, D-galactose, and D-glucose at specific pH. The influence of covalent interactions of BDP dye derivative with monosaccharides on its spectroscopic properties can be selectively recognized by both absorption and fluorescence spectra. By the nonlinear curve-fitting analysis of the fluorescence titration data, the association constants Ks of BDP derivative 1 with monosaccharide such as D-fructose, D-galactose, and D-glucose are 1045, 445 and 130 L/mol, respectively. Thus BDP derivative 1 can be used as a sensitive and selective fluorescent probe for monosaccharides. Moreover, the sensing mechanism of the fluorescent probe was also preliminarily discussed.

Key words: boron dipyrromethene dye, fluorescent probe, monosaccharide, fused exocyclic rings, phenylboronic acid

中图分类号:

O623

徐海云, 刘起峰, 宋胜梅. 中位取代苯硼酸的含稠合外环的硼-二吡咯亚甲基染料类单糖荧光探针的合成与性能[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30591.

XU Haiyun*, LIU Qifeng, SONG Shengmei. Synthesis and Properties of Fluorescent Probe for Monosaccharides Based on Exocyclic Ring-Fused Boron Dipyrromethene Dye Substituted with Phenylboronic Ester[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30591.

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