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Spatial Organization of Multi-Porphyrins for Pre-Defined Properties

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (30 September 2019) | Viewed by 28808

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Special Issue Editors

Dr. Nathalie Solladié

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Guest Editor

LCC (Laboratoire de Chimie de Coordination) - CNRS, Université de Toulouse, CNRS, 205 Route de Narbonne, 31077 Toulouse CEDEX 4, France
Interests: porphyrins; peptides; oligonucleotides; self-assembling; molecular recognition; chirality
Special Issues, Collections and Topics in MDPI journals

Dr. Regis Rein

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Co-Guest Editor

Special Issue Information

Dear Colleagues,

In Nature, many systems contain structurally organized porphyrinoids including various enzymes, dedicated to oxygen transport, oxidation processes etc., or the light harvesting antennae and the reaction center involved in the photosynthetic processes. This observation opens the route to new challenges of synthesizing molecular architectures of growing size and structural complexity, for instance as potential models of the light harvesting complexes, but also as photonic and electronic wires. It rapidly appeared crucial to organize in space the chromophores in a way appropriate to induce the desired properties in the designed molecular architectures. For this purpose, both the structure of the molecules and their conformation need to be controlled. When interactions and recognition processes between one or more molecular architectures take place, all the rules of supramolecular chemistry are relevant to achieve the desired goal.

The present Special Issue, “Spatial Organization of Multi-Porphyrins for Pre-Defined Properties”, aims to collect and to disseminate some of the most significant and recent contributions in the very wide and highly interdisciplinary area. The scope is broad and includes covalently linked and self-assembled devices, as well as more sophisticated systems obtained when covalent linkage and supramolecular chemistry can work together. Furthermore, since chirality plays a pivotal role in the structural organization of vast majority of natural assemblies including photosynthesis owing to asymmetry of amino acids, the importance of chirality in some systems will also be covered in this issue.

Dr. Nathalie Solladié
Dr. Regis Rein
Guest Editor

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Keywords

porphyrins
self-assembling
molecular recognition
chirality
photo-physical properties

Published Papers (7 papers)

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Research

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12 pages, 4732 KiB

Open AccessArticle

Amphiphilic Porphyrin Aggregates: A DFT Investigation

by Federica Sabuzi, Manuela Stefanelli, Donato Monti, Valeria Conte and Pierluca Galloni

Molecules 2020, 25(1), 133; https://doi.org/10.3390/molecules25010133 - 29 Dec 2019

Cited by 9 | Viewed by 3495

Abstract

Owing to the attractive potential applications of porphyrin assemblies in photocatalysis, sensors, and material science, studies presently concerning porphyrin aggregation are widely diffused. π–π stacking, H-bonding, metal coordination, hydrophobic effect, and electrostatic forces usually drive porphyrin interaction in solution. However, theoretical studies of such phenomena are still limited. Therefore, a computational examination of the different porphyrin aggregation approaches is proposed here, taking into account amphiphilic [5-{4-(3-trimethylammonium)propyloxyphenyl}-10,15,20-triphenylporphyrin] chloride, whose aggregation behavior has been previously experimentally investigated. Different functionals have been adopted to investigate the porphyrin dimeric species, considering long-range interactions. Geometry optimization has been performed, showing that for the compound under analysis, H-type and cation–π dimers are the most favored structures that likely co-exist in aqueous solution. Of note, frontier orbital delocalization showed an interesting interaction between the porphyrin units in the dimer at the supramolecular level. Full article

(This article belongs to the Special Issue Spatial Organization of Multi-Porphyrins for Pre-Defined Properties)

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13 pages, 2624 KiB

Open AccessArticle

Arginine-Induced Self-Assembly of Protoporphyrin to Obtain Effective Photocatalysts in Aqueous Media Under Visible Light

by Mahmood D. Aljabri, Nilesh M. Gosavi, Lathe A. Jones, Pranay P. Morajkar, Duong D. La and Sheshanath V. Bhosale

Molecules 2019, 24(22), 4172; https://doi.org/10.3390/molecules24224172 - 18 Nov 2019

Cited by 9 | Viewed by 4230

Abstract

The fabrication of controlled supramolecular nanostructures via self-assembly of protoporphyrin IX (PPIX) was studied with enantiomerically pure l-arginine and d-arginine, and we have shown that stoichiometry controlled the morphology formed. The nanostructure morphology was mainly influenced by the delicate balance of π-π stacking interactions between PPIX cores, as well as H-bonding between the deprotonated acidic head group of PPIX with the guanidine head group of arginine. PPIX self-assembled with l-/d-arginine to create rose-like nanoflower structures for four equivalents of arginine that were 5–10 μm in length and 1–4 μm diameter. We employed UV-vis, fluorescence spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), dynamic light scattering (DLS) and Fourier transform infrared spectroscopy (FT-IR) techniques to characterize the resulting self-assembled nanostructures. Furthermore, we investigated the catalytic activity of PPIX and arginine co-assembled materials. The fabricated PPIX–arginine nanostructure showed high enhancement of photocatalytic activity through degradation of rhodamine B (RhB) with a decrease in dye concentration of around 78–80% under simulated visible radiation. Full article

(This article belongs to the Special Issue Spatial Organization of Multi-Porphyrins for Pre-Defined Properties)

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11 pages, 2937 KiB

Open AccessArticle

Polyethersulfone Mats Functionalized with Porphyrin for Removal of Para-nitroaniline from Aqueous Solution

by Chiara Maria Antonietta Gangemi, Mario Iudici, Luca Spitaleri, Rosalba Randazzo, Massimiliano Gaeta, Alessandro D’Urso, Antonino Gulino, Roberto Purrello and Maria Elena Fragalà

Molecules 2019, 24(18), 3344; https://doi.org/10.3390/molecules24183344 - 14 Sep 2019

Cited by 25 | Viewed by 3537

Abstract

The dispersion of para-nitroaniline (p-NA) in water poses a threat to the environment and human health. Therefore, the development of functional adsorbents to remove this harmful compound is crucial to the implementation of wastewater purification strategies, and electrospun mats represent a versatile and cost-effective class of materials that are useful for this application. In the present study, we tested the ability of some polyethersulfone (PES) nanofibers containing adsorbed porphyrin molecules to remove p-NA from water. The functional mats in this study were obtained by two different approaches based on fiber impregnation or doping. In particular, meso-tetraphenyl porphyrin (H₂TPP) or zinc(II) meso-tetraphenyl porphyrin (ZnTPP) were immobilized on the surface of PES fiber mats by dip-coating or added to the PES electrospun solution to obtain porphyrin-doped PES mats. The presence of porphyrins on the fiber surfaces was confirmed by UV–Vis spectroscopy, fluorescence measurements, and XPS analysis. p-NA removal from water solutions was spectrophotometrically detected and evaluated. Full article

(This article belongs to the Special Issue Spatial Organization of Multi-Porphyrins for Pre-Defined Properties)

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15 pages, 3007 KiB

Open AccessArticle

Self-Assembly of Covalently Linked Porphyrin Dimers at the Solid–Liquid Interface

by Thomas Habets, Dennis Lensen, Sylvia Speller and Johannes A.A.W. Elemans

Molecules 2019, 24(16), 3018; https://doi.org/10.3390/molecules24163018 - 20 Aug 2019

Cited by 6 | Viewed by 3540

Abstract

The synthesis and surface self-assembly behavior of two types of metal-porphyrin dimers is described. The first dimer type consists of two porphyrins linked via a rigid conjugated spacer, and the second type has an alkyne linker, which allows rotation of the porphyrin moieties with respect to each other. The conjugated dimers were equipped with two copper or two manganese centers, while the flexible dimers allowed a modular built-up that also made the incorporation of two different metal centers possible. The self-assembly of the new porphyrin dimers at a solid–liquid interface was investigated at the single-molecule scale using scanning tunneling microscopy (STM). All dimers formed monolayers, of which the stability and the internal degree of ordering of the molecules depended on the metal centers in the porphyrins. While in all monolayers the dimers were oriented coplanar with respect to the underlying surface (‘face-on’), the flexible dimer containing a manganese and a copper center could be induced, via the application of a voltage pulse in the STM setup, to self-assemble into monolayers in which the porphyrin dimers adopted a non-common perpendicular (‘edge-on’) geometry with respect to the surface. Full article

(This article belongs to the Special Issue Spatial Organization of Multi-Porphyrins for Pre-Defined Properties)

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17 pages, 4015 KiB

Open AccessArticle

Zinc Porphyrin-Functionalized Fullerenes for the Sensitization of Titania as a Visible-Light Active Photocatalyst: River Waters and Wastewaters Remediation

by Elzbieta Regulska, Danisha Maria Rivera-Nazario, Joanna Karpinska, Marta Eliza Plonska-Brzezinska and Luis Echegoyen

Molecules 2019, 24(6), 1118; https://doi.org/10.3390/molecules24061118 - 21 Mar 2019

Cited by 34 | Viewed by 3661

Abstract

Zinc porphyrin-functionalized fullerene [C60] derivatives have been synthesized and used to prepare titania-based composites. The electrochemical properties and HOMO and LUMO levels of the photosensitizers were determined by electrochemical measurements. Raman and IR techniques were used to study chemical groups present on the titania surface. Absorption properties of the composites were measured in the solid state by diffuse reflectance UV-Vis spectra (DRS). The zeta potential and aggregate sizes were determined using dynamic light scattering (DLS) and electrophoretic light scattering (ELS) techniques. Surface areas were estimated based on Brunauer–Emmett–Teller (BET) isotherms. The photocatalytic activity of the photocatalysts was tested using two model pollutants, phenol and methylene blue. The composite with the highest photocatalytic potential (1/TiO₂) was used for river and wastewater remediation. The photodegradation intermediates were identified by LC-UV/Vis-MS/MS techniques. Full article

(This article belongs to the Special Issue Spatial Organization of Multi-Porphyrins for Pre-Defined Properties)

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14 pages, 3513 KiB

Open AccessArticle

Metalloporphyrin Dimers Bridged by a Peptoid Helix: Host-Guest Interaction and Chiral Recognition

by Yen Jea Lee, Boyeong Kang and Jiwon Seo

Molecules 2018, 23(11), 2741; https://doi.org/10.3390/molecules23112741 - 24 Oct 2018

Cited by 12 | Viewed by 4348

Abstract

Co-facial porphyrins have been designed to construct porphyrin tweezers with versatile molecular recognition capabilities. In this study, we synthesized metalloporphyrin–peptoid conjugates (MPPCs) displaying two metalloporphyrins on a peptoid scaffold with either achiral unfolded (1) or helical (2 and 3) secondary structures. Host–guest complexation of MPPCs was realized with various guests of different lengths and basicities, and the extent of complexation was measured by UV-vis and circular dichroism (CD) spectroscopic titration. Intermolecular and intramolecular chirality induction were observed on achiral and chiral peptoid backbones, respectively. Spectroscopic data indicated that a broad scope of achiral guests can be recognized by chiral 2; in particular, longer and more flexible guests were seen to bind more tightly on 2. In addition, chiral 2 provided a distinct CD couplet with dl-, d-, or l-Lys-OMe, which was a result of the diastereomeric host–guest complex formation. Our results indicated that MPPCs can recognize, contrast, and analyze various achiral, chiral, or racemic molecules. Based on co-facial metalloporphyrins present on peptoid scaffolds, we developed a novel class of porphyrin tweezers, which can be further utilized in asymmetric catalysis, molecular sensing, and drug delivery. Full article

(This article belongs to the Special Issue Spatial Organization of Multi-Porphyrins for Pre-Defined Properties)

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Review

Jump to: Research

32 pages, 9082 KiB

Open AccessReview

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

by Gabriele Magna, Donato Monti, Corrado Di Natale, Roberto Paolesse and Manuela Stefanelli

Molecules 2019, 24(23), 4307; https://doi.org/10.3390/molecules24234307 - 26 Nov 2019

Cited by 44 | Viewed by 5368

Abstract

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. Full article

(This article belongs to the Special Issue Spatial Organization of Multi-Porphyrins for Pre-Defined Properties)

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