Kinetic and spectroscopic studies on the chiral self-aggregation of amphiphilic zinc and copper (<scp>l</scp>)-prolinate-tetraarylporphyrin derivatives in different aqueous media

Caroleo, Fabrizio; Stefanelli, Manuela; Venanzi, Mariano; Paolesse, Roberto; Sennato, Simona; Carbone, Marilena; Monti, Donato

doi:10.1039/c8ob02689k

Cited by 12 publications

(13 citation statements)

References 47 publications

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“…As far as the overall aggregation process is concerned, we recently found an analogous two-step process in the aggregation of related cationic L-proline-porphyrin derivatives in analogous aqueous media (Lorecchio et al, 2014;Caroleo et al, 2019), and also in the study of the interaction of a chiral Zn-porphyrin derivative with chiral anionic surfactants in water, that results in the rapid formation of small sized aggregates, followed by a slower step in which the initial species rearrange in more ordered and specific structures driven by Zn-coordination (Simoncini et al, 2014). Same phenomenon has been also observed by others in organic solvent (Feldborg et al, 2011), in the case of water-soluble tetrapyrrolic macrocycles (El-Hachemi et al, 2016) or, amazingly, even in solid state (Borovkov et al, 2003).…”

Section: Spectroscopic Investigationsmentioning

confidence: 99%

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

et al. 2020

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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.

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Section: Spectroscopic Investigationsmentioning

confidence: 99%

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

et al. 2020

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“…Very recently, Monti et al reported the possibility of forming chiral suprastructures starting from Zn and Cu cationic ( l )-prolinate-tetraarylporphyrin complexes in different aqueous media (Figure 8a) [42]. As reported by the authors in previous works, the appended-proline group provides the chiral information to read during the aggregation process, and directly determines the chiral features of the formed assemblies, together with other boundary experimental parameters like solvent composition, monomer concentration, charge of the proline unit, and the metal ion coordinated.…”

Section: Solvent-driven Aggregation Protocolmentioning

confidence: 99%

The Assembly of Porphyrin Systems in Well-Defined Nanostructures: An Update

et al. 2019

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The interest in assembling porphyrin derivatives is widespread and is accounted by the impressive impact of these suprastructures of controlled size and shapes in many applications from nanomedicine and sensors to photocatalysis and optoelectronics. The massive use of porphyrin dyes as molecular building blocks of functional materials at different length scales relies on the interdependent pair properties, consisting of their chemical stability/synthetic versatility and their quite unique physicochemical properties. Remarkably, the driven spatial arrangement of these platforms in well-defined suprastructures can synergically amplify the already excellent properties of the individual monomers, improving conjugation and enlarging the intensity of the absorption range of visible light, or forming an internal electric field exploitable in light-harvesting and charge-and energy-transport processes. The countless potentialities offered by these systems means that self-assembly concepts and tools are constantly explored, as confirmed by the significant number of published articles related to porphyrin assemblies in the 2015–2019 period, which is the focus of this review.

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“…For many years, we have focused on the possibility to build up chiral porphyrin suprastructures by assembling inherently chiral porphyrin derivatives having single or multiple stereogenic centers peripherally located on the macrocycle thanks to the conjugation with diverse biomolecules, as amino acids, glucosides or steroids [ 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 ]. The self-aggregation of these compounds was induced in organic/aqueous mixtures by the so-called “good-bad” solvent protocol, in which porphyrins solubilization in a “good” solvent is followed by the addition of the proper amount of a “bad” one, where typically the macrocycle is insoluble, even at low concentrations.…”

Section: Introductionmentioning

confidence: 99%

The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates

et al. 2020

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An overview of the solvent-driven aggregation of a series of chiral porphyrin derivatives studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, conferring amphiphilicity and solubility in aqueous media to the primarily hydrophobic porphyrin platform. Aggregation of the macrocycles is driven by a change in bulk solvent composition, forming architectures with supramolecular chirality, steered by the stereogenic centers on the porphyrin peripheral positions. The aggregation behavior and chiroptical properties of the final aggregated species strongly depend on the number and stereogenicity of the ancillary groups that dictate the mutual spatial arrangement of the porphyrin chromophores and their further organization in larger structures, usually detectable by different microscopies, such as AFM and SEM. Kinetic studies are fundamental to understand the aggregation mechanism, which is frequently found to be dependent on the substrate concentration. Additionally, Molecular Mechanics calculations can give insights into the intimate nature of the driving forces governing the self-assembly process. The critical use of these combined methods can shed light on the overall self-assembly process of chirally-functionalized macrocycles, with important implications on the development of chiral porphyrin-based materials.

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Kinetic and spectroscopic studies on the chiral self-aggregation of amphiphilic zinc and copper (l)-prolinate-tetraarylporphyrin derivatives in different aqueous media

Abstract: The chiral self-aggregation of (l)-proline porphyrin derivatives depends on both the nature of the media and the coordinated metal ion.

Cited by 12 publications

References 47 publications

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

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

The Assembly of Porphyrin Systems in Well-Defined Nanostructures: An Update

The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates

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