Three-dimensional (3D) printing technology has attracted great attention for prototyping different electrochemical sensor devices. However, chiral recognition remains a crucial challenge for electrochemical sensors with similar physicochemical properties such as enantiomers. In this work, a magnetic covalent organic framework (COF) and bovine serum albumin (BSA) (as the chiral surface) functionalized 3D-printed electrochemical chiral sensor is reported for the first time. The characterization of the chiral biomolecule-COF 3D-printed constructure was performed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDX). A tryptophan (Trp) enantiomer was chosen as the model chiral molecule to estimate the chiral recognition ability of the magnetic COF and BSA-based 3DE (Fe3O4@COF@BSA/3DE). We have demonstrated that the Fe3O4@COF@BSA/3DE exhibited excellent chiral recognition to l-Trp as compared to d-Trp. The chiral protein-COF sensing interface was used to determine the concentration of l-Trp in a racemic mixture of d-Trp and l-Trp. This strategy of on-demand fabrication of 3D-printed protein-COF-modified electrodes opens up new approaches for enantiomer recognition.

Department of Chemical and Biomolecular Engineering Yonsei University 50 Yonsei ro Seodaemungu Seoul 03722 Korea

Department of Chemistry and Biochemistry Mendel University in Brno Zemedelska 1 CZ 613 00 Brno Czech Republic

Department of Medical Research China Medical University Hospital China Medical University No 91 Hsueh Shih Road Taichung Taiwan

Future Energy and Innovation Laboratory Central European Institute of Technology Brno University of Technology Purkyňova 123 61200 Brno Czech Republic

School of Pharmacy Southwest Medical University Luzhou 646000 Sichuan China

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