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Homochiral Eu 3+ @MOF Composite for the Enantioselective Detection and Separation of ( R / S )-Ornidazole.

Mingyuan LeiXiaohe WangTianjun ZhangYang ShiJinghong WenQingfu Zhang
Published in: Inorganic chemistry (2022)
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 [Me 2 NH 2 ] + counterions, {[Me 2 NH 2 ] 2 [Zn 2 (d-L) 2 (HCO 2 )(OH)]·5H 2 O} n (HMOF- 1 ), was synthesized using a d-camphorate-derived enantiopure dicarboxylate ligand, 4,4'-[[(1 R ,3 S )-1,2,2-trimethylcyclopentane-1,3-dicarbonyl]bis(azanediyl)]dibenzoic acid (d-H 2 L) via a simple solvothermal method. Interestingly, HMOF- 1 could be used as a parent framework to encapsulate Eu 3+ cations via an ion-exchange process, yielding an Eu 3+ @HMOF- 1 composite with dual-luminescent centers. The obtained Eu 3+ @HMOF- 1 has high chemical stability and good luminescence stability in water. Importantly, Eu 3+ @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 Eu 3+ . In addition, Eu 3+ @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 Ln III -incorporated HMOF composite materials for the simultaneous enantioselective detection and separation of chiral drugs.
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