Discrimination of the enantiomers of electroactive chiral molecules in voltammetry is a fascinating frontier target. Of course the necessary condition to achieve it is that the two enantiomers undergo electron transfer in energetically different conditions. Since in an achiral context they would have identical physico chemical properties and thus also identical voltammetry features, this requires the implementation at the electrode|solution interphase of a suitable enantiopure chiral selector. The so far most popular strategy consists in working on chiral electrode surfaces, and an impressive variety of approaches has been proposed [1,2]. However, working on achiral electrodes with chirality implemented in the medium has also been proposed [1], and very recent experiments have highlighted that this approach can yield outstanding discrimination in terms of potential differences for the enantiomers of chiral electroactive probes, when working in media of high structural order at the charged interphase, like ionic liquids ILs [3-7] and deep eutectic solvents DESs [8], implemented with chirality [3,4,8] or, even better, inherent chirality [5-7]. Such achievements will be comparatively presented and commented in terms of IL and DES structural order at the interphase (also compared to classical media and to ionic liquids / ionic liquid crystals [9]) as well as of possibility of probe/selector specific interactions. Support to our chiral electroanalysis research line by Fondazione Cariplo/Regione Lombardia as well as by Università degli Studi di Milano is gratefully acknowledged. [1] S. Arnaboldi, M. Magni, P.R. Mussini, Enantioselective selectors for chiral electrochemistry and electroanalysis: Stereogenic elements and enantioselection performance, Curr. Opin. Electrochem. 8 (2018) 60-72. (minireview) [2] S. Arnaboldi, M. Magni, S. Grecchi, P.R. Mussini, Electroactive chiral oligo- and polymer layers for electrochemical recognition, Curr. Opin. Electrochem. 7 (2018) 188-189. (minireview) [3] M. Longhi, S. Arnaboldi, E. Husanu, S. Grecchi, I. FrancoBuzzi, R. Cirilli, S. Rizzo, C. Chiappe, P. R. Mussini, L. Guazzelli, A family of chiral ionic liquids from the natural pool: Relationships between structure and functional properties and electrochemical enantiodiscrimination tests, Electrochim. Acta 298 (2019) 194-209. [4] S. Grecchi, C. Ferdeghini, M. Longhi, A. Mezzetta, L. Guazzelli, S. Khawthong, F. Arduini, C. Chiappe, A. Iuliano, P. R. Mussini, Chiral biobased ionic liquids with cations or anions including bile acid building blocks as chiral selectors in voltammetry, ChemElectroChem accepted March 2021. [5] S. Rizzo, S. Arnaboldi, V. Mihali, R. Cirilli, A. Forni, A. Gennaro, A. A. Isse, M. Pierini, P. R. Mussini, F. Sannicolò, “Inherently Chiral” Ionic‐Liquid Media: Effective Chiral Electroanalysis on Achiral Electrodes, Angew. Chem. Int. Ed. 56 (2017) 2079 –2082. [6] S. Rizzo, S. Arnaboldi, R. Cirilli, A. Gennaro, A. A. Isse, F. Sannicolò, P. R. Mussini, An “inherently chiral” 1,1′-bibenzimidazolium additive for enantioselective voltammetry in ionic liquid media, Electrochem. Commun. 89 (2018), 57-61 [7] F. Fontana, G. Carminati, B. Bertolotti, P. R. Mussini, S. Arnaboldi, S. Grecchi, R. Cirilli, L. Micheli, S. Rizzo, Helicity: A Non-Conventional Stereogenic Element for Designing Inherently Chiral Ionic Liquids for Electrochemical Enantiodifferentiation, Molecules 26 (2021) 311-324. [8] S. Arnaboldi, A. Mezzetta, S. Grecchi, M. Longhi, E. Emanuele, S. Rizzo, F. Arduini, L. Micheli, L. Guazzelli, P. R. Mussini, Natural-based chiral task-specific deep eutectic solvents: a novel, effective tool for enantiodiscrimination in electroanalysis, Electrochim. Acta accepted March 2021. [9] S. Grecchi, S. Arnaboldi, S. Rizzo, P. R. Mussini Advanced chiral molecular media for enantioselective electrochemistry and electroanalysis (minireview), soon to be submitted. NOTA: Si tratta di abstract inviato, che è stato in seguito definito "invited lecture" (e così inserito nel programma) dall'organizzatore del simposio in cui è stato presentato.

Enantiomer discrimination in voltammetry in media of high structural order at the electrochemical interphase implemented with chirality / P.R. Mussini, S. Grecchi, S. Arnaboldi. ((Intervento presentato al 72. convegno Meeting of the International Society of Electrochemistry tenutosi a Jeju Island, South Korea, online nel 2021.

Enantiomer discrimination in voltammetry in media of high structural order at the electrochemical interphase implemented with chirality

P.R. Mussini;S. Grecchi;S. Arnaboldi
2021

Abstract

Discrimination of the enantiomers of electroactive chiral molecules in voltammetry is a fascinating frontier target. Of course the necessary condition to achieve it is that the two enantiomers undergo electron transfer in energetically different conditions. Since in an achiral context they would have identical physico chemical properties and thus also identical voltammetry features, this requires the implementation at the electrode|solution interphase of a suitable enantiopure chiral selector. The so far most popular strategy consists in working on chiral electrode surfaces, and an impressive variety of approaches has been proposed [1,2]. However, working on achiral electrodes with chirality implemented in the medium has also been proposed [1], and very recent experiments have highlighted that this approach can yield outstanding discrimination in terms of potential differences for the enantiomers of chiral electroactive probes, when working in media of high structural order at the charged interphase, like ionic liquids ILs [3-7] and deep eutectic solvents DESs [8], implemented with chirality [3,4,8] or, even better, inherent chirality [5-7]. Such achievements will be comparatively presented and commented in terms of IL and DES structural order at the interphase (also compared to classical media and to ionic liquids / ionic liquid crystals [9]) as well as of possibility of probe/selector specific interactions. Support to our chiral electroanalysis research line by Fondazione Cariplo/Regione Lombardia as well as by Università degli Studi di Milano is gratefully acknowledged. [1] S. Arnaboldi, M. Magni, P.R. Mussini, Enantioselective selectors for chiral electrochemistry and electroanalysis: Stereogenic elements and enantioselection performance, Curr. Opin. Electrochem. 8 (2018) 60-72. (minireview) [2] S. Arnaboldi, M. Magni, S. Grecchi, P.R. Mussini, Electroactive chiral oligo- and polymer layers for electrochemical recognition, Curr. Opin. Electrochem. 7 (2018) 188-189. (minireview) [3] M. Longhi, S. Arnaboldi, E. Husanu, S. Grecchi, I. FrancoBuzzi, R. Cirilli, S. Rizzo, C. Chiappe, P. R. Mussini, L. Guazzelli, A family of chiral ionic liquids from the natural pool: Relationships between structure and functional properties and electrochemical enantiodiscrimination tests, Electrochim. Acta 298 (2019) 194-209. [4] S. Grecchi, C. Ferdeghini, M. Longhi, A. Mezzetta, L. Guazzelli, S. Khawthong, F. Arduini, C. Chiappe, A. Iuliano, P. R. Mussini, Chiral biobased ionic liquids with cations or anions including bile acid building blocks as chiral selectors in voltammetry, ChemElectroChem accepted March 2021. [5] S. Rizzo, S. Arnaboldi, V. Mihali, R. Cirilli, A. Forni, A. Gennaro, A. A. Isse, M. Pierini, P. R. Mussini, F. Sannicolò, “Inherently Chiral” Ionic‐Liquid Media: Effective Chiral Electroanalysis on Achiral Electrodes, Angew. Chem. Int. Ed. 56 (2017) 2079 –2082. [6] S. Rizzo, S. Arnaboldi, R. Cirilli, A. Gennaro, A. A. Isse, F. Sannicolò, P. R. Mussini, An “inherently chiral” 1,1′-bibenzimidazolium additive for enantioselective voltammetry in ionic liquid media, Electrochem. Commun. 89 (2018), 57-61 [7] F. Fontana, G. Carminati, B. Bertolotti, P. R. Mussini, S. Arnaboldi, S. Grecchi, R. Cirilli, L. Micheli, S. Rizzo, Helicity: A Non-Conventional Stereogenic Element for Designing Inherently Chiral Ionic Liquids for Electrochemical Enantiodifferentiation, Molecules 26 (2021) 311-324. [8] S. Arnaboldi, A. Mezzetta, S. Grecchi, M. Longhi, E. Emanuele, S. Rizzo, F. Arduini, L. Micheli, L. Guazzelli, P. R. Mussini, Natural-based chiral task-specific deep eutectic solvents: a novel, effective tool for enantiodiscrimination in electroanalysis, Electrochim. Acta accepted March 2021. [9] S. Grecchi, S. Arnaboldi, S. Rizzo, P. R. Mussini Advanced chiral molecular media for enantioselective electrochemistry and electroanalysis (minireview), soon to be submitted. NOTA: Si tratta di abstract inviato, che è stato in seguito definito "invited lecture" (e così inserito nel programma) dall'organizzatore del simposio in cui è stato presentato.
Settore CHIM/01 - Chimica Analitica
Settore CHIM/02 - Chimica Fisica
Settore CHIM/06 - Chimica Organica
International Society of Electrochemistry
Enantiomer discrimination in voltammetry in media of high structural order at the electrochemical interphase implemented with chirality / P.R. Mussini, S. Grecchi, S. Arnaboldi. ((Intervento presentato al 72. convegno Meeting of the International Society of Electrochemistry tenutosi a Jeju Island, South Korea, online nel 2021.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/867543
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