Electrochemical identification of reductive enantiomers in wood channels: A low-cost and scalable platform for chiral sensing.

ABSTRACT

Chirality, an inherent characteristic of natural substances (such as sugars, peptides, proteins, and nucleic acid), plays a vital role in human metabolism and exerts substantial impacts. In general, chiral drugs can display diverse pharmacological and pharmacokinetic properties. One enantiomer may exhibit therapeutic effects, while the other could cause adverse reactions. Selective recognition of enantiomers is thus a significant task in the biomolecular and pharmaceutical fields. Despite the development of several chiral identification techniques, low-cost enantioselective sensing methods remain highly desirable. Here, we designed and developed an electrochemical sensing device for reductive enantiomer identification using natural wood channels as the substrate. The wood channels were endowed with oxidase-like activity through the in-situ growth of cerium oxide nanoparticles (CeO2). Chiral recognition capability was further introduced by incorporating a layer of chiral ZIF-8 (L-ZIF) as the chiral selector. To demonstrate the enantioselective sensing performance, 3,4-dihydroxyphenylalanine (DOPA) enantiomers were employed as model analytes. Due to the oxidase-like activity and the confinement effect of the proposed channels, the captured DOPA enantiomers were effectively oxidized to their quinone structure, and the Ce(IV) in CeO2 was reduced to Ce(III). These changes led to alterations in the surface charge of the channels, thereby modulating their ionic transport properties. This sensing mechanism also proved useful for the identification of other reductive enantiomers. The limits of detection for l-DOPA and d-DOPA were determined as 2.41 nM and 1.56 nM, respectively. The resulting wood channel-based sensing device not only can be used for the recognition and detection of reductive enantiomers, but also is expected to be applied to the non-electochemically active substances. Moreover, this study offers a novel type of solid-state channel material with low cost, reproducibility, and easy accessibility for electrochemical chiral sensing.