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Homochiral Eu3+@MOF Composite for the Enantioselective Detection and Separation of (R/S)-Ornidazole
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-04-28 , DOI: 10.1021/acs.inorgchem.1c03695
Mingyuan Lei 1 , Xiaohe Wang 1 , Tianjun Zhang 1 , Yang Shi 1 , Jinghong Wen 1 , Qingfu Zhang 1
Affiliation  

The development of homochiral materials for the enantioselective detection and separation of chiral drugs is in high demand for the pharmaceutical industry. Herein, an anionic homochiral metal–organic framework (HMOF) with in situ generated [Me2NH2]+ counterions, {[Me2NH2]2[Zn2(d-L)2(HCO2)(OH)]·5H2O}n (HMOF-1), was synthesized using a d-camphorate-derived enantiopure dicarboxylate ligand, 4,4′-[[(1R,3S)-1,2,2-trimethylcyclopentane-1,3-dicarbonyl]bis(azanediyl)]dibenzoic acid (d-H2L) via a simple solvothermal method. Interestingly, HMOF-1 could be used as a parent framework to encapsulate Eu3+ cations via an ion-exchange process, yielding an Eu3+@HMOF-1 composite with dual-luminescent centers. The obtained Eu3+@HMOF-1 has high chemical stability and good luminescence stability in water. Importantly, Eu3+@HMOF-1 exhibits enhanced enantioselectivity and sensitivity in the detection of an important chiral nitroimidazole antibiotic, (R/S)-ornidazole (ONZ) in comparison to HMOF-1 under the same aqueous conditions. The enantiomeric excess (ee) value of the ONZ enantiomers can be accurately determined by the ratio of dual emission from the ligand and Eu3+. In addition, Eu3+@HMOF-1 shows the enantioselective separation of racemic ONZ enantiomers with an ee value of 86.6%. This work provides a simple strategy for the preparation of LnIII-incorporated HMOF composite materials for the simultaneous enantioselective detection and separation of chiral drugs.

中文翻译:

用于(R/S)-奥硝唑对映选择性检测和分离的手性Eu3+@MOF复合物

用于手性药物的对映选择性检测和分离的纯手性材料的开发是制药行业的高需求。在此,一种阴离子纯手性金属有机骨架 (HMOF)原位产生 [Me 2 NH 2 ] +抗衡离子,{[Me 2 NH 2 ] 2 [Zn 2 ( d -L) 2 (HCO 2 )(OH)] ·5H 2 O} n (HMOF- 1 ), 是使用d-樟脑酸酯衍生的对映纯二羧酸配体 4,4'-[[(1 R ,3 S)-1,2,2-trimethylcyclopentane-1,3-dicarbonyl]bis(azanediyl)]dibenzoic acid ( d -H 2 L) 通过简单的溶剂热法。有趣的是,HMOF- 1可用作母体框架,通过离子交换过程封装 Eu 3+阳离子,产生具有双发光中心的 Eu 3+ @HMOF - 1复合材料。得到的Eu 3+ @HMOF- 1在水中具有较高的化学稳定性和良好的发光稳定性。重要的是,Eu 3+ @HMOF- 1在检测重要的手性硝基咪唑抗生素时表现出增强的对映选择性和灵敏度,( R / S)-奥硝唑 (ONZ) 与 HMOF- 1在相同水性条件下的比较。ONZ 对映体的对映体过量 (ee) 值可以通过配体和 Eu 3+的双重发射的比率来准确确定。此外,Eu 3+ @HMOF- 1显示了外消旋 ONZ 对映体的对映选择性分离,ee 值为 86.6%。这项工作为制备掺入 Ln III的 HMOF 复合材料提供了一种简单的策略,用于同时对映选择性检测和分离手性药物。
更新日期:2022-04-28
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