Fabrication of Homochiral Metal-Organic Frameworks in TiO2 Nanochannels for In Situ Identification of 3,4-Dihydroxyphenylalanine Enantiomers.

Abstract

Enantioselective identification of chiral molecules is important for biomedical and pharmaceutical research. However, owing to identical molecular formulas and chemical properties of enantiomers, signal transduction and amplification are still the two major challenges in chiral sensing. In this study, we developed an enantioselective membrane by integrating homochiral metal-organic frameworks (MOFs) with nanochannels for the sensitive identification and quantification of chiral compounds. The membrane was designed using a TiO2 nanochannel membrane (TiNM) as the metal ion precursor of MOFs (using MIL-125(Ti)) and incorporating l-glutamine (l-Glu) into the framework of MIL-125(Ti). Using 3,4-dihydroxyphenylalanine (DOPA) as the model analyte, the as-prepared homochiral l-Glu/MIL-125(Ti)/TiNM exhibits a remarkable chiral recognition to d-DOPA than l-DOPA. More importantly, benefiting from the highly enlarged surface area and confinement effect provided by the MOFs-in-nanochannel architecture, the discrimination for chiral recognition is largely amplified through the chelation interaction of Fenton-like activity of Fe3+ onto DOPA. Using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as the substrate, the positively charged ABTS•+ product via Fenton-like reaction induces significant ionic transport changes in nanochannels, which in turn provides information about chiral recognition. This innovative signal amplification strategy on homochiral nanochannels might pave a new way for sensitive monitoring and chiral recognition.