Chirality transfer across length scales

Chiral electrochemistry, including enantioselective electroanalysis and enantioselective electrosynthesis, is a quite explored area of research, but with a huge applicative potential yet to be studied. Considering that chirality makes electrochemical processes smarter and applicable to issues of much higher added value we focused our attention on the characterization of new classes of inherently chiral materials. Inherent chirality is an intrinsic property of a molecule, propagating in the 2D and 3D space, which provides specific characteristics to the resulting material, obtained after depositing it on an electrode surface or after adding it as a chiral additive in a solution. Employing such molecules in enantioselective analysis, we have obtained for the first time a separation between the enantiomers of chiral probes (even drugs in complex matrix) in terms of peak potential values, testing racemic mixtures of the enantiomers of chiral drugs, and evaluating the enantiomeric excesses [1]. Starting from this point, by the optimization of the experimental conditions, several inherently chiral compounds with chemically different atropoisomeric scaffold and stereogenic elements, were synthetized and characterized, in order to be exploited in different fields (i.e. chiral electroanalysis, spintronics). Recently, the attractive and far unexplored potentialities of these systems, were also exploited in the field of bipolar electrochemistry, allowing to correlate a dynamic macro and microscopic event with the concentration of the enantiomers present in solution [2-5]. The efficient combination of the two approaches, the molecular static event with the macroscopic dynamic one, allowed me to be awarded with the prestigious ERC StG with the acronym “CHEIR”, a project funded by European Committee for five years. The global aim of such project is to achieve with unprecedented efficiency the propagation of chiral information along different length scales, based on the synergy of well-chosen molecular ingredients and physicochemical engineering. Such ambitious aim will be realized developing cargo-towing (synthetic) electro-pumps based on chiral conducting polymers for targeted drug-delivery applications. [1] Arnaboldi, S.; Benincori, T.; Cirilli, R.; Kutner, W.; Magni, M.; Mussini, P. R.; Noworyta, K.; Sannicolò, F. Chem. Sci. 2015, 6, 1706. [2] Arnaboldi, S.; Gupta, B.; Benincori, T.; Bonetti, G.; Cirilli, R.; Kuhn, A. Anal. Chem. 2020, 92, 10042. [3] Arnaboldi, S.; Salinas, G.; Bonetti, G.; Cirilli, R.; Benincori, T.; Kuhn, A. Biosens. and Bioelectron. 2022, 218, 114740. [4] Arnaboldi, S.; Salinas, G.; Karajic, A.; Garrigue, P.; Benincori, T.; Cirilli, R.; Bichon, S.; Gounel, S.; Mano, N.; Kuhn, A. Nat. Chem. 2021, 13, 1241. [5] Arnaboldi, S.; Salinas, G.; Bonetti, G.; Garrigue, P.; Cirilli, R.; Benincori, T.; Kuhn, A. Angew. Chem. 2022, 134, e202209098. This work has been funded by the European Research Council (ERC) under the HORIZON-ERC-2021 program (grant agreement no 101040798, ERC Starting Grant CHEIR)