Chiral UiO-MOFs based QCM sensors for enantioselective discrimination of hazardous biomolecule

Abstract

Developments of enantioselective devices for discriminating bio-enantiomers is of significant importance. Due to the vital role of Cysteine (Cys) in biological processes and the hazardous effect of its D-enantiomer, discriminating Cys enantiomers without auxiliary enzyme is highly wanted. In this work, a pair of UiO-MOF enantiomers (UiO-tart) have been fabricated through post-modification, which could be further fabricated into enantiomeric sensing devices (UiO-tart@Au). By employing the Quartz Crystal Microbalance (QCM) technology, gravimetric discrimination of Cys enantiomers could be achieved. UiO-tart@Au is highly enantioselective, and the afforded enantioselective factor (5.97 ± 0.54) represents the best performance reported ever. In the fabricated device, MOF layer acts as the chiral selector for specific Cys enantiomer, and the reaction between the captured Cys enantiomer and Au results in the mass growth of the system. Solid-phase extraction (SPE) gives an e.e. value of 71.6 ± 3.8%, substantially confirming the chiral-selector role of UiO-tart. DFT calculations indicate that enantiomeric H-bonding effect and greater reaction enthalpy should be the reason. To the best of our knowledge, this work represents the first example of chiral tartaric acid derived MOF sensors for enantioselective discrimination of Cys, suggesting a promising potential of developing chiral MOFs based devices for enhanced enantioselective application.