Strategies for High Enantioselectivity on Achiral Electrode Surfaces: Implementing Inherent Chirality in Electrode|(Ionic Liquid) Interfaces (original) (raw)

Enantioselective voltammetry in chiral ionic liquid media

2018

1 Università degli Studi di Milano, Dip. di Chimica, Via Golgi 19, 20133 Milano, Italy 2 Istituto di Scienze e Tecnologie Molecolari, CNR, via Golgi 19, 20133 Milano, Italy 3 Università degli Studi di Milano, Dip. di Biotecnologie Mediche e Medicina Traslazionale, Via Fratelli Cervi 93, 20090 Segrate (MI), Italy 4 Università degli Studi di Padova, Dip.di Scienze Chimiche, Via Marzolo 1, 35131 Padova, Italy 5 Università degli Studi di Pisa, Dip. di Farmacia, via Bonanno 33, 56126 Pisa, Italy. *patrizia.mussini@unimi.it

Helicity: A Non-Conventional Stereogenic Element for Designing Inherently Chiral Ionic Liquids for Electrochemical Enantiodifferentiation

Molecules

Configurationally stable 5-aza[6]helicene (1) was envisaged as a promising scaffold for non-conventional ionic liquids (IL)s. It was prepared, purified, and separated into enantiomers by preparative HPLC on a chiral stationary phase. Enantiomerically pure quaternary salts of 1 with appropriate counterions were prepared and fully characterized. N-octyl-5-aza[6]helicenium bis triflimidate (2) was tested in very small quantities as a selector in achiral IL media to perform preliminary electrochemical enantiodifferentiation experiments on the antipodes of two different chiral probes. The new organic salt exhibited outstanding enantioselection performance with respect to these probes, thus opening the way to applications in the enantioselective electroanalysis of relevant bioactive molecules.

Chiral electrochemistry : introducing the inherent chirality Concept in ionic liquids

2015

1 Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy; 2 Istituto di Scienze e tecnologie Molecolari, CNR, via Golgi 19, 20133 Milano, Italy; 3 Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy; 4 Dip. del Farmaco, Ist. Superiore di Sanità, Viale Regina Elena 299, 00161 Roma, Italy; 5 Università di Roma “La Sapienza”, Dipartimento di Chimica e Tecnologie del Farmaco, Piazzale Aldo Moro 5, 00185 Roma, Italy. serena.arnaboldi@unimi.it

Inherently chiral electrodes: the tool for chiral voltammetry

Chem. Sci., 2015

ABSTRACT 2,2′-Bis[2-(5,2′-bithienyl)]-3,3′-bithianaphthene oligomers are a model case of electroactive films endowed with “inherent chirality”, originating from a stereogenic element coinciding with the whole electroactive backbone, thus resulting in impressive manifestations. This study highlights their applicative potentialities as low-cost and easy-to-prepare artificial enantiopure electrode surfaces, which display an unprecedented ability to pronouncedly separate voltammetry peaks of enantiomers of quite different chiral probes of applicative interest, concurrently with linear dynamic ranges for peak currents, affording enantiomer excess determination. Thus inherently chiral enantiopure electrodes can indeed be regarded as a key to chiral voltammetry.