Università degli Studi di Milano
Dipartimento di Chimica
Gruppo di Elettrochimica
per lo studio della materia e della reattività
March 25, 2020 – 09:30
Amphi Grandjean – Build. 10 B
Beaulieu Campus
Serena Arnaboldi is a Post-Doc researcher at the Università degli Studi di Milano in Analytical Chemistry. She obtained her position after a Ph.D. with Professor Patrizia R. Mussini at the Università degli Studi di Milano. In 2016 she won the International Dropsens Award for the best reserach in Analytical Chemistry. From October 2019 to April 2020 she is a visiting researcher in the group of Prof. A.Kuhn at NSysA (University of Bordeaux). Her current research focuses on chiral electrochemistry and chiral electroanalysis employing smart inherently chiral materials both as electrodic surfaces and media with outstanding potentialities in the field of chiral discrimination. Now she is extending her reserch also on chiral deep euthectic solvents (CDESs).
New Insights and Perspectives in the Enantiodiscrimination at Electrochemical Interphases through Implementation of Inherently Chiral Selectors
To achieve enantioselective electrochemistry and electroanalysis, electron transfer processes at the electrochemical interphase require the presence of a suitable enantiopure chiral selector, resulting in energetically different diastereoisomeric conditions for the two probe enantiomers. A groundbreaking strategy was recently proposed, based on the use of molecular selectors endowed with "inherently chirality", i.e. with chirality and key functional properties originating from the same structural element, which in our case identifies with the main molecular backbone, featuring a tailored torsion with a racemization energy barrier too high to be overcome at room temperature [1]. In such conditions, large peak potential differences have been observed in voltammetry for the enantiomers of even very different chiral probes either (i) working in achiral media, on electrode surfaces modified with thin films of inherently chiral electroactive oligomers [2] or (ii) working on achiral electrodes, implementing inherent chirality in the medium, particularly in ionic liquids ILs, either chiral themselves, or modified by a chiral additive, exploiting the peculiar IL high order at the interphase with a charged electrode [3].
Both strategies are being now extended and refined, particularly aiming to collect clues for the elucidation of the recognition mechanism, as well as to highlight attractive applications.
A wide palette of selectors (films or media) and/or probes are being investigated, encompassing four classes of stereogenic elements, i.e. corresponding to stereocentre-based chirality, axial chirality, helical chirality and planar chirality.
Finally, the outstanding enantiodiscrimination ability of the new selectors is being considered beyond molecular chiral probes, i.e. towards polarized light components (in terms of circular dichroism and circularly polarized luminescence) and electron spins (in magnetoelectrochemistry experiments).
[1] S. Arnaboldi, M. Magni, P. R. Mussini, Curr. Opin. Electrochem., 2018, 8, 60-72
[2] F. Sannicolò, S. Arnaboldi, T. Benincori, V. Bonometti, R. Cirilli, L. Dunsch, W. Kutner, G. Longhi, P. R. Mussini, M. Panigati, M. Pierini, S. Rizzo, Angew. Chem. Int. Ed., 2014, 53, 2623-2627.
[3] S. Rizzo, S. Arnaboldi, V. Mihali, R. Cirilli, A. Forni, A. Gennaro, A. A. Isse, M. Pierini, P. R. Mussini, F. Sannicolò, Angew. Chem. Int. Ed., 2017, 56, 2079-2082.
