A family of inherently chiral electroactive selectors based on the 2,2’-biindole atropisomeric scaffold, of easy synthesis and modulable functional properties, is studied in cascade in two enantioselection contexts. They are at first investigated as probes in enantioselective HPLC, studying molecular structure and temperature effects, and achieving very efficient semipreparative enantioseparation. The enantiomers thus obtained, of remarkable chiroptical features (optical rotation as well as circular dichroism), are successfully applied as selectors in chiral voltammetry in different media for discrimination of the enantiomers of chiral electroactive probes, either by conversion into enantiopure electroactive electrode surfaces by electrooligomerization on glassy carbon substrate (the two monomers with shorter alkyl chains), or as chiral additive in achiral ionic liquid (the monomer with longest alkyl chains). Discrimination is conveniently and reproducibly achieved in terms of significant potential differences for the two enantiomers, specularly inverting either probe or selector configuration. In one case successful discrimination is also observed with the two probe enantiomers concurrently present, either as racemate or with enantiomeric excesses, neatly accounted for by the peak current ratios.

Modulating the Enantiodiscrimination Features of Inherently Chiral Selectors by Molecular Design : A HPLC and Voltammetry Study Case with Atropisomeric 2,2’-Biindole-Based Monomers and Oligomer Films / L. Scapinello, S. Grecchi, S. Rossi, F. Arduini, S. Arnaboldi, A. Penoni, R. Cirilli, P.R. Mussini, T. Benincori. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 27:52(2021 Sep 15), pp. 13190-13202. [10.1002/chem.202101170]

Modulating the Enantiodiscrimination Features of Inherently Chiral Selectors by Molecular Design : A HPLC and Voltammetry Study Case with Atropisomeric 2,2’-Biindole-Based Monomers and Oligomer Films

Sara Grecchi;Sergio Rossi;Serena Arnaboldi;Patrizia Romana Mussini;
2021-09-15

Abstract

A family of inherently chiral electroactive selectors based on the 2,2’-biindole atropisomeric scaffold, of easy synthesis and modulable functional properties, is studied in cascade in two enantioselection contexts. They are at first investigated as probes in enantioselective HPLC, studying molecular structure and temperature effects, and achieving very efficient semipreparative enantioseparation. The enantiomers thus obtained, of remarkable chiroptical features (optical rotation as well as circular dichroism), are successfully applied as selectors in chiral voltammetry in different media for discrimination of the enantiomers of chiral electroactive probes, either by conversion into enantiopure electroactive electrode surfaces by electrooligomerization on glassy carbon substrate (the two monomers with shorter alkyl chains), or as chiral additive in achiral ionic liquid (the monomer with longest alkyl chains). Discrimination is conveniently and reproducibly achieved in terms of significant potential differences for the two enantiomers, specularly inverting either probe or selector configuration. In one case successful discrimination is also observed with the two probe enantiomers concurrently present, either as racemate or with enantiomeric excesses, neatly accounted for by the peak current ratios.
additives; chiral; electrochemistry; electrodes; enantioselective HPLC; oligomers
Settore CHIM/01 - Chimica Analitica
Settore CHIM/06 - Chimica Organica
Settore CHIM/02 - Chimica Fisica
25-giu-2021
CHEMISTRY-A EUROPEAN JOURNAL
Article (author)
File in questo prodotto:
File Dimensione Formato  
chem.202101170.pdf

accesso aperto

Descrizione: articolo principale online first
4.94 MB Adobe PDF Visualizza/Apri
chem202101170-sup-0001-misc_information.pdf

accesso aperto

Descrizione: Supporting Information
5.9 MB Adobe PDF Visualizza/Apri
chem.202101170.pdf

accesso aperto

4.7 MB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/864551
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 2
  • ???jsp.display-item.citation.isi??? 2
social impact