Chiral voltammetry: strategies and tools for a quantum leap in electrochemical recognition

Chiral voltammetry: strategies and tools for a quantum leap in electrochemical recognition [Lezione/Conferenza in inglese in scuola scientifica internazionale su tematica avanzata che costituisce una delle mie linee di ricerca. Riporto la sequenza di argomenti trattati] Enantiodiscrimination: the highest degree of selectivity in electroanalysis Most desirable transduction mode? Enantiodiscrimination rationale Features of an ideal chiral selector Natural or artificial selectors? Strategies based on chiral electrode surfaces Strategies based on chiral media Target not yet fully achieved: possible weaknesses A breakthrough: exploiting inherently chiral selectors Our strategies for implementing (inherent) chirality at electrode|solution interphases: confined solid network vs expanded semisolid network Inherent chirality in confined solid networks: electrode surfaces consisting of electroactive inherently chiral oligomer films Proof of concept case: electrode modified with BT2T4 oligomer films Feasibility of ernantiomer excess evaluation Of which species do the electrodeposited films consist? Electrodeposited film morphology at increasing magnification Exploiting the deposited films as self standing membranes From bibenzothiophene- to bisindole-based atropoisomeric cores: enhancing Enantiodiscrimination by Core Functionalization with Additional Coordination Elements; same concept with variously functionalized Ferrocenyl Probes on oligo-BT2T4 Helicene-based inherently chiral surfaces The parallel strategy: chiral media of high local order at the interphase with a charged achiral electrode Advanced chiral media features: a rationalization Enantiodiscrimination in biobased chiral ionic liquids: Enantiodiscrimination with terpenoid-based chiral IL media/selectors (also in EIS tests; Enantiodiscrimination with bile-acid-based chiral IL media/selectors; Enantiodiscrimination in ionic liquid with tweezer additives Enantiodiscrimination in inherently chiral ionic liquid media i) of axial stereogenicity bipyridinium based/bibenzimidazolium based. Long-chain inherently chiral 3,3’-bicollidinium salts: ionic liquids or additives/supporting electrolytes. Short-chain inherently chiral 3,3’-bicollidinium salts: additives/supporting electrolytes. Inherently chiral 1,1’-bibenzimidazolium salts as additives in CV tests in achiral ionic liquid. 1,1’-bibenzimidazolium salts: enantioselectivity test as chiral additives in oligomerizations ii) of helical stereogenicity: a thiahelicene-based inherently chiral selector; a monoazahelicene-based inherently chiral selector; diazahelicene-based inherently chiral selectors: molecular structure effect A new frontier: enantiodiscrimination in chiral deep eutectic solvents. Chiral deep eutectic solvents, a promising new frontier! The chiral DESs investigated in a first proof of concept study: comparative DES tests with model ferrocenyl chiral probe; a DES test with D- and L-Tryptophan. Enantioselective Voltammetry vs Electronic Chiroptical Spectroscopy: Exploring Intriguing Analogies and Connections. Investigation of redox sites in Voltammetry/chromophores in UV-vis Spectroscopy: well known analogies and connections. Upgrading to a superior selectivity level: discriminating between enantiomers of electrochemically and spectroscopically active molecules: Chiral Voltammetry and Chiroptical Spectroscopy Conditions and guidelines to achieve the enantiorecognition experiment: Strategy comparison in Chiroptical Spectroscopy and in Chiral Voltammetry. CISS effect and spintronics Substituting one of the two truly chiral entities with an externally applied magnetic field: spectroscopy case vs voltammetry case. An intriguing magnetoelectrochemistry experiment. Inherently chiral molecular selectors: analogies between chiroptical spectroscopy and chiral voltammetry. Interacting equivalent redox centres resulting in twin CV peak system in voltammetry vs interacting equivalent chromophores resulting in "Davidov splitting"in spectroscopy Conclusion: a fascinating network with attractive symmetries worthy to be explored!