Electroactive chiral oligo- and polymer layers for electrochemical enantiorecognition

A family of chiral ionic liquids from the natural pool: Relationships between structure and functional properties and electrochemical enantiodiscrimination tests

“…Such explanations could also apply to both the previous ICIL and the present CIL case; however, by analogy with the chiral film examples [20,32], the inherently chiral additives should be particularly efficient on account of (a) the chirality source coinciding with the whole main cation backbone, rather than in localized stereocentres, (b) the high regioregularity granted by the cation C 2 axial symmetry, which should enhance its structure ordering ability. It was however important and overdue to verify whether similar effects, albeit possibly smaller, could be observed using chiral, rather than inherently chiral, ionic liquids as chiral selectors, particularly concentrating on chiral cations and bistriflimide anions (used to obtain the above ICILs).…”

Widening the Scope of “Inherently Chiral” Electrodes: Enantiodiscrimination of Chiral Electroactive Probes with Planar Stereogenicity

“…Particularly attractive are voltammetric measurements based on electron transfers at suitable enantiopure chiral interphases resulting in different potentials for the enantiomers of chiral probes. [2,3, The relation between current and concentration could also allow for the determination of the enantiomer concentration, and even, in favorable cases, the estimation of the enantiomeric excess directly in solution. In this frame, chirality can be implemented at the interphase either by electrode surface modification with a high variety of selectors, [2][3][4][5] or by choosing a chiral medium or medium component, such as the solvent, the supporting electrolyte, or more effectively, a chiral ionic liquid or even an ionic liquid with chiral additives.…”

“…[2,3, The relation between current and concentration could also allow for the determination of the enantiomer concentration, and even, in favorable cases, the estimation of the enantiomeric excess directly in solution. In this frame, chirality can be implemented at the interphase either by electrode surface modification with a high variety of selectors, [2][3][4][5] or by choosing a chiral medium or medium component, such as the solvent, the supporting electrolyte, or more effectively, a chiral ionic liquid or even an ionic liquid with chiral additives. [2] In particular, outstanding discrimination ability, in terms of large peak potential differences between chiral probe enantiomers, has been recently observed when "inherently chiral" selectors were adopted for the above task.…”

Self‐Standing Membranes Consisting of Inherently Chiral Electroactive Oligomers: Electrosynthesis, Characterization and Preliminary Tests in Potentiometric Setups

“…Concerning design of synthetic membranes, different stereogenic elements can be considered to endow them with chirality, the most common ones being localized stereocenters. However, it was recently observed for different kinds of chiral selectors, including chiral electroactive oligomer films, that much better enantioselection performances can be obtained by implementation of the “inherent chirality” strategy . In “inherently chiral” polyconjugated molecular materials both chirality and key functional properties originate from the same structural element, which can coincide with the whole main molecular scaffold, featuring a tailored torsion with an energy barrier too high to be overcome at room temperature; regioregularity enables propagating such property into foldamer‐/helical‐like macro‐ or supramolecular structures .…”

“…However, it was recently observed for different kinds of chiral selectors, including chiral electroactive oligomer films, that much better enantioselection performances can be obtained by implementation of the “inherent chirality” strategy . In “inherently chiral” polyconjugated molecular materials both chirality and key functional properties originate from the same structural element, which can coincide with the whole main molecular scaffold, featuring a tailored torsion with an energy barrier too high to be overcome at room temperature; regioregularity enables propagating such property into foldamer‐/helical‐like macro‐ or supramolecular structures . Large potential differences have been observed between enantiomers of various chiral probes in voltammetry experiments implementing inherent chirality at electrode|solution interphases by modifying achiral electrodes with enantiopure inherently chiral electroactive films electrodeposited from different heterocycle‐based monomers with atropoisomeric cores ( i. e .…”