Porphyrins Through the Looking Glass: Spectroscopic and Mechanistic Insights in Supramolecular Chirogenesis of New Self-Assembled Porphyrin Derivatives.

Manuela Stefanelli,Marco Savioli,Stefano Superchi,Mariano Venanzi,Sandra Belviso,Corrado Di Natale,Francesca Zurlo,Giulia Marsico,Gabriele Magna,Roberto Paolesse,Donato Monti

doi:10.3389/fchem.2020.587842

Manuela Stefanelli, Marco Savioli + Show 9 more

Open Access

https://doi.org/10.3389/fchem.2020.587842

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Abstract

The solvent driven aggregation of porphyrin derivatives, covalently linked to a L- or D-prolinate enantiomer, results in the stereospecific formation of species featuring remarkable supramolecular chirality, as a consequence of reading and amplification of the stereochemical information stored in the proline-appended group. Spectroscopic, kinetic, and topographic SEM studies gave important information on the aggregation processes, and on the structures of the final chiral architectures. The results obtained may be the seeds for the construction of stereoselective sensors aiming at the detection, for example, of novel emergent pollutants from agrochemical, food, and pharmaceutical industry.

Highlights

Porphyrin-based chiral supramolecular systems are of great importance owing to their potential application in wide fields of science and technology (Cui et al, 2015; Paolesse et al, 2017; Lee et al, 2018), and for the implication on the emergence of homochirality in Life (Guijarro and Yus, 2009)
As a part of our studies dedicated to the construction of chiral porphyrin aggregates (Monti et al, 2010; Zelenka et al, 2011), we investigated the self-assembly behavior of intrinsically chiral zinc-tetraphenylporphyrin derivatives, characterized by the presence of covalently linked enantiomers of L- or D-prolinate groups on the molecular frame (Scheme 1)
Synthesis of the title porphyrins has been accomplished by following the path reported in Scheme 1, which relies on straightforward procedures used in peptide chemistry

Summary

INTRODUCTION

Porphyrin-based chiral supramolecular systems are of great importance owing to their potential application in wide fields of science and technology (Cui et al, 2015; Paolesse et al, 2017; Lee et al, 2018), and for the implication on the emergence of homochirality in Life (Guijarro and Yus, 2009). In the former case, the stereochemical course of the self-assembling process is governed by the presence of chiral groups linked on the porphyrin peripheral frame (Oliveira-González et al, 2015; van der Weegen et al, 2017) In the latter issue, final chiral suprastructures are obtained by interaction of achiral substrates with external physical effectors, such as hydrodynamic directional forces (Sorrenti et al, 2012; Arteaga et al, 2016); magnetic fields (Micali et al, 2012); LB and LS techniques (Chen et al, 2011), or chiral molecular templates, such as surfactants (El-Hachemi et al, 2008), chiral polymeric matrices (D’Urso et al, 2012), chiral ligands (Borovkov and Inoue, 2006; Berova et al, 2007) or carboxylic acids (Castriciano et al, 2011). For example, that hybrid organic-inorganic materials, constituted by ZnO nanoparticles covalently linked to a porphyrin enantiomer studied in detail in the present work, are able to selectively detect the different enantiomers of chiral analytes, such as limonene and other terpenes (Stefanelli et al, 2019)

RESULTS AND DISCUSSION

CONCLUSIONS AND FUTURE PERSPECTIVES

DATA AVAILABILITY STATEMENT