Looking for green synthesis methods is the main direction of MOFs research in the green chemical industry to meet large-scale preparation of modified materials suitable for highly active electrodes. In this study, 1,3,5-benzenetricarboxylic acid (1,3,5-HBTC) and 4,4’-bipyridine (4,4’-Bpy) were used as ligands. The micro-nano structure mixed-ligand Zn-MOFs compounds, [Zn(bpy)(Hbtc)(HO)]·3nHO prepared by ultrasonic and mechanochemical method were marked as Zn-MOF-U and Zn-MOF-M, respectively. The construction of the as-prepared mixed-ligand Zn-MOFs modified carbon paste electrodes (Zn-MOF/CPE) for luteolin (LUT) detection are then studied. Different preparation methods lead to differences in micro-structure, in which lath-shaped Zn-MOF-U has higher electrochemical sensing luteolin activity than bulk-shaped Zn-MOF-M. The current signal of Zn-MOF-U/CPE was linear with the concentration of LUT in the range between 0.005−1.0 and 1.0−10 μM with a sensitivity of 9.70 and 15.6 μA·mM·cm, respectively, with the limit of detection (LOD) of 3 nM. This study provides a green routes for the simple large-scale synthesis of mixed-ligands MOFs materials and the sensitive sensing detection of small biomolecules.

中文翻译：

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超声波与机械化学方法制备混合配体锌基 MOF 的比较，用于电化学测定木犀草素

寻找绿色合成方法是MOFs绿色化工研究的主要方向，以满足大规模制备适用于高活性电极的改性材料。在本研究中，使用1,3,5-苯三甲酸（1,3,5-HBTC）和4,4'-联吡啶（4,4'-Bpy）作为配体。采用超声和机械力化学方法制备的微纳结构混合配体Zn-MOFs化合物[Zn(bpy)(Hbtc)(H2O)]·3nH2O分别标记为Zn-MOF-U和Zn-MOF-M。然后研究了用于木犀草素 (LUT) 检测的混合配体 Zn-MOFs 修饰碳糊电极 (Zn-MOF/CPE) 的构建。不同的制备方法导致微观结构的差异，其中板条状Zn-MOF-U比块状Zn-MOF-M具有更高的电化学传感木犀草素活性。 Zn-MOF-U/CPE的电流信号与LUT浓度在0.005−1.0和1.0−10 μM范围内呈线性关系，灵敏度分别为9.70和15.6 μA·mM·cm，具有检出限(LOD) 为 3 nM。该研究为混合配体MOFs材料的简单大规模合成和生物小分子的灵敏传感检测提供了一条绿色途径。