Chiral PEDOT-Based Enantioselective Electrode Modification Material for Chiral Electrochemical Sensing: Mechanism and Model of Chiral Recognition

Abstract

The development of electrochemical methods for enantioselective recognition is a focus of research in pharmaceuticals and biotechnology. In this study, a pair of water-soluble chiral 3,4-ethylenedioxythiophene (EDOT) derivatives, (R)-2'-hydroxymethyl-3,4-ethylenedioxythiophene ((R)-EDTM) and (S)-2'-hydroxymethyl-3,4-ethylenedioxythiophene ((S)-EDTM), were synthesized and electrodeposited on the surface of a glassy carbon electrode (GCE) via current-time (I-t) polymerization in an aqueous LiClO electrolyte. These chiral PEDOT polymers were used to fabricate chiral sensors and to investigate the enantioselective recognition of d-/l-3,4-dihydroxyphenylalanine, d-/l-tryptophan, and (R)-/(S)-propranolol enantiomers, respectively. The results indicated that the (R)-PEDTM/GCE sensor showed a higher peak current response toward the levo or (S) forms of the tested enantiomers, while the opposite phenomenon occurred for (S)-PEDTM/GCE. The mechanism of the stereospecific interaction between these enantiomers and the chiral polymers was determined. Therefore, a model of the chiral recognition by the chiral conducting polymer electrodes and an electrochemical method was proposed. The chirality of the enantiomers was confirmed by two parameters: the chirality of the electrode and the peak current response. These findings pave the way for the application of chiral PEDOT as electrode modification material in the electrochemical chiral recognition field.

Extending substrate sensing capabilities of zinc tris(2‐pyridylmethyl)amine‐based stereodynamic probe

“…1 Actually, in a wider perspective, smart chiral receptor systems also find applications in anion recognition, 2 electroanalysis, 3 and modern technologies like spin filters to improve the efficiency of LED/OLED. 1 Actually, in a wider perspective, smart chiral receptor systems also find applications in anion recognition, 2 electroanalysis, 3 and modern technologies like spin filters to improve the efficiency of LED/OLED.…”

“…Chiral sensing is a challenging task in molecular recognition chemistry for its obvious implications in the study of molecules' medicinal activity. 1 Actually, in a wider perspective, smart chiral receptor systems also find applications in anion recognition, 2 electroanalysis, 3 and modern technologies like spin filters to improve the efficiency of LED/OLED. 4 So far, chiral sensing structures have been based on a variety of components, such as vesicles, 5 nanostructures, 6 polymers, 7 and ligands with specific moieties or geometries.…”

Breakdown of chiral recognition of amino acids in reduced dimensions

“…In contrast, the 1l-and 1d-Trp molecules are restricted to the configuration with one Pyr I •••Bz I interaction and one H I •••O C interaction, owing to their steric hindrance. As a result, the energy of the 2l-Trp molecules is lower than that of the 1l-and 1d-Trp molecules, a fact that was postulated as the origin of the chiral recognition [20][21][22][23][24][25][26][27][28][29][39][40][41][42] .…”

Enantiopure polythiophene nanoparticles. Chirality dependence of cellular uptake, intracellular distribution and antimicrobial activity

“…Applications in chiral catalysis, chiral sensing and chiroptical devices have been reported. [1][2][3][4][5][6] Chiral innovative materials are being explored in biology and medicine, [7][8][9][10] as most molecular and supramolecular biological compounds are chiral. The chirality of biomolecules inuences physiological events and through chiral recognition and stereoselective nonbonding interactions the enantiomorphs of chiral nanostructures may interact differently with chiral biomolecules, depending on the sign of chirality.…”