A boronic acid functionalized terbium metal-organic framework for fluorescence detection and adsorption of gallic acid.

Yulin Wang, Jixuan Chen, Kailian Zhou, Jinting Chen, Jiaqiuzi Zhang, Yongbiao Hua, Jiayao Chen, Huishi Guo, Xiuzhen Qiu
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Abstract

Gallic acid (GA) is widely applied as an antioxidant in foods and pharmaceuticals. In this study, a boronic acid functionalized metal-organic framework (Tb-MOF) is developed for fluorescence detection and adsorption of GA. Tb-MOF is constructed by coordination polymerization of terbium ions (Tb3+) with 3,5-dicarboxyphenylboronic acid (BBDC). The resulted Tb-MOF exhibits green fluorescence emission at 546 nm under an excitation of 280 nm. However, the green emission of Tb-MOF decreases in the presence of GA due to the formation of borate esters between phenolic hydroxyl groups of GA and hydroxyl groups of Tb-MOF. Under optimized conditions (40 mmol·L-1 Tris-HCl buffer solution of pH = 6.2 and reaction time of 25 min), the sensor shows a wide detection range of 5 ∼ 200 μmol·L-1 with a correlation coefficient (R2) of 0.9950. Meanwhile, Tb-MOF shows good selectivity and sensitivity to GA (the limit of detection (LOD) is 0.44 μmol·L-1). Additionally, Tb-MOF is used to investigate GA adsorption. The corresponding adsorption data can be suitably described by Langmuir isotherm and pseudo-second-order models with a maximum adsorption capacity of 6.03 mg·g-1. The above results demonstrate the potential of prepared Tb-MOF in integrating GA detection and adsorption in water samples.

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用于没食子酸荧光检测和吸附的硼酸功能化铽金属有机框架。
没食子酸(GA)作为一种抗氧化剂被广泛应用于食品和药品中。本研究开发了一种用于荧光检测和吸附没食子酸的硼酸功能化金属有机框架(Tb-MOF)。Tb-MOF 由铽离子(Tb3+)与 3,5-二羧基苯硼酸(BBDC)配位聚合而成。在 280 纳米波长的激发下,生成的 Tb-MOF 在 546 纳米波长处发出绿色荧光。然而,由于 GA 的酚羟基与 Tb-MOF 的羟基之间形成了硼酸酯,因此在 GA 存在的情况下,Tb-MOF 的绿色发射会降低。在优化条件下(40 mmol-L-1 Tris-HCl 缓冲溶液,pH = 6.2,反应时间 25 分钟),传感器的检测范围为 5 ∼ 200 μmol-L-1,相关系数(R2)为 0.9950。同时,Tb-MOF 对 GA 具有良好的选择性和灵敏度(检测限为 0.44 μmol-L-1)。此外,Tb-MOF 还可用于研究 GA 的吸附。相应的吸附数据可以用 Langmuir 等温线和伪二阶模型进行适当描述,最大吸附容量为 6.03 mg-g-1。上述结果证明了制备的 Tb-MOF 在整合水样中 GA 的检测和吸附方面的潜力。
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