Chirality Discrimination at the Single Molecule Level by Using a Cationic Supermolecule Quasi-Gated Organic Field Effect Transistor.

Abstract

Achieving rapid and highly sensitive small molecule chiral discrimination is a great challenge in modern-day analytical sciences. Herein, an organic field effect transistors (OFET) is developed by employing an imidazolium 3,5-dimethylphenylcabamoylated-β-cyclodextrin (Im+-Ph-β-CD) as both the recognition unit and a quasi gate, which induces a secondary accumulation channel of electrons in the n-type transistor to achieve the signal transduction and amplification via field effect. The charge of the imidazolium group is partially shielded due to its self-inclusion in the CD cavity, and this shielding effect is reduced at varying degrees in the existence of isomers due to the competitive inclusion. Consequently, the different weak intermolecular interactions related to the target-induced CD-enantiomer complexation with different geometry and stabilization energy for each isomer can be transformed to electronic signals based on the variety of Im+-Ph-β-CD's effective charge rather than the intrinsic charge of analytes, hence leading to chiral differentiation, and the hydrogen-bonding network of Im+-Ph-β-CD membrane further magnifies the signal. This working strategy even allows chiral discrimination of electrically neutral analytes. The as-prepared sensor affords rapid and real-time discrimination to small molecule enantiomers at single molecule level with a limit of detection of 8.1 × 10-19 M in a 200 μL volume (about 100 small molecules). Moreover, we prove the great potential of the chiral organic field effect transistor in quantitative analysis of commercial medicines.