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Special Issue "Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018"

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

Deadline for manuscript submissions: closed (31 January 2019).

Special Issue Editors

Prof. Dr. M. Graça P. M. S. Neves
Website1 Website2
Guest Editor
Department of Chemistry and LAQV-REQUIMTE , University of Aveiro, 3810-193 Aveiro, Portugal
Interests: Organic synthesis; tetrapyrrolic macrocycles; functionalization of porphyrins and analogues via metal-catalyzed processes and cycloaddition reactions; development of molecules with structural features to be considered as sensors, catalysts, dyes for photovoltaic cells and for medicinal and environmental applications
Special Issues and Collections in MDPI journals
Prof. Dr. M. Amparo F. Faustino
Website SciProfiles
Guest Editor
Department of Chemistry and LAQV-REQUIMTE, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: synthesis, reactivity, and characterization of tetrapyrrolic macrocycles; functionalization of porphyrins and related derivatives via cycloaddition reactions (Diels-Alder, 1,3-dipolar and 1,5-electrocyclizations); development of molecules with structural features to be considered in medical and environmental applications, namely, photodynamic therapy of neoplastic tissues, microorganism photoinactivation (including antibiotic-resistant strains, viruses, and spores) and water disinfection; improvement of photochemical techniques to develop environmentally friendly approaches for wastewater treatment
Special Issues and Collections in MDPI journals
Dr. Nuno M. M. Moura
Website
Guest Editor
Department of Chemistry and LAQV-REQUIMTE, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal
Interests: Current research interests are focused on the development of new technologies for pollutants removal and photodynamic processes. Namely, preparation and functionalization of porphyrinic derivatives and analogous for medicinal and environmental applications; design of multifunctional hybrid materials containing porphyrinic derivatives and study of their chemosensory and photocatalyst properties; study of beta-functionalized porphyrinic derivatives and analogous as photosensitizers in the photodynamic inactivation of microorganisms, namely bacteria, fungi and viruses, and in photodynamic therapy against tumour cells
Special Issues and Collections in MDPI journals

Special Issue Information

Dear Colleagues,

Natural and synthetic macrocycles, such as porphyrins, corroles, phthalocyanines, and others, are considered strong candidates to be used in different fields, such as catalysis sensing, medicine, development of advanced biomimetic models, and materials science.

All these applications, strongly-dependent on the availability of compounds with adequate and specific structural features, can justify the high investment of different researcher groups to synthesize and modify natural and synthetic porphyrin derivatives or analogs. This Special Issue, following the success of the first one in 2016, aims to provide a forum for the dissemination of the latest information on the synthesis and functionalization of tetrapyrrolic macrocycles and their potential applications.

Prof. Dr. M. Graça P. M. S. Neves
Prof. Dr. M. Amparo F. Faustino
Dr. Nuno M. M. Moura
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • tetrapyrrolic macrocycles
  • porphyrins and analogues
  • synthesis
  • functionalization
  • application

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Published Papers (14 papers)

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Editorial

Jump to: Research, Review

Open AccessEditorial
Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018
Molecules 2020, 25(3), 433; https://doi.org/10.3390/molecules25030433 - 21 Jan 2020
Cited by 1
Abstract
Natural and synthetic macrocycles like porphyrins, corroles and phthalocyanines are considered strong candidates to be used in different fields, such as catalysis, sensing, medicine, materials science, or in the development of advanced biomimetic models. All these applications are strongly dependent on the availability [...] Read more.
Natural and synthetic macrocycles like porphyrins, corroles and phthalocyanines are considered strong candidates to be used in different fields, such as catalysis, sensing, medicine, materials science, or in the development of advanced biomimetic models. All these applications are strongly dependent on the availability of compounds with adequate and specific structural features. This Special Issue has collected 13 contributions which consolidate and expand our knowledge on the application of these macrocycles in different fields accompanied by innovative synthetic methodologies to afford and to functionalize this type of compounds. Full article

Research

Jump to: Editorial, Review

Open AccessArticle
A Convenient Synthesis of Pentaporphyrins and Supramolecular Complexes with a Fulleropyrrolidine
Molecules 2019, 24(17), 3177; https://doi.org/10.3390/molecules24173177 - 01 Sep 2019
Cited by 1
Abstract
A simple and straightforward synthesis of diporphyrins and pentaporphyrins is reported here. The supramolecular interactions of the new porphyrin derivatives with C60 and PyC60 (a pyridyl [60]fulleropyrrolidine) were evaluated by absorption and fluorescence titrations in toluene. While no measurable modifications of [...] Read more.
A simple and straightforward synthesis of diporphyrins and pentaporphyrins is reported here. The supramolecular interactions of the new porphyrin derivatives with C60 and PyC60 (a pyridyl [60]fulleropyrrolidine) were evaluated by absorption and fluorescence titrations in toluene. While no measurable modifications of the absorption and fluorescence spectra were observed upon addition of C60 to the porphyrin derivatives, the addition of PyC60 to the corresponding mono-Zn(II) porphyrins resulted in the formation of Zn(porphyrin)–PyC60 coordination complexes and the binding constants were calculated. Results show that the four free-base porphyrin units in pentaporphyrin 6 have a significant contribution in the stabilization of the 6–PyC60 complex. The crystal and molecular features of the pentaporphyrin Zn5 were unveiled using single-crystal X-ray diffraction studies. Full article
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Open AccessArticle
Isomers of β,β-Dinitro-5,10,15,20-tetraphenylporphyrin Derivatives: Valuable Starting Materials for Further Transformations
Molecules 2019, 24(5), 838; https://doi.org/10.3390/molecules24050838 - 27 Feb 2019
Cited by 2
Abstract
The synthesis, chromatographic isolation, and structure elucidation of β,β-substituted isomers of dinitro-5,10,15,20-tetraphenylporphyrin complexes are described. meso-Tetraphenyl-porphyrin chelates (CuII, NiII, CoII) upon reaction wit e.g., nitric acid (yellow HNO3, d = 1.52, [...] Read more.
The synthesis, chromatographic isolation, and structure elucidation of β,β-substituted isomers of dinitro-5,10,15,20-tetraphenylporphyrin complexes are described. meso-Tetraphenyl-porphyrin chelates (CuII, NiII, CoII) upon reaction wit e.g., nitric acid (yellow HNO3, d = 1.52, diluted to 25–50%) in CHCl3 formed a mixture of nitro-derivatives with combined yields of ca 80%. This nitration (under optimized conditions: 25–30% HNO3, 30–40 min, r.t.) can be carried out selectively to give mainly β,β-dinitro-compounds in yields of up to 73%. From the above mixtures of five possible regioisomers that can be formed, usually two or three of them were isolated, for which the structures were assigned on the basis of 1H NMR spectra including COSY and NOESY measure-ments. These types of products are attractive starting materials for synthesis of potential anticancer PDT agents with unique structures, being practically unavailable by any other alternative method. Full article
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Open AccessFeature PaperArticle
Multicharged Phthalocyanines as Selective Ligands for G-Quadruplex DNA Structures
Molecules 2019, 24(4), 733; https://doi.org/10.3390/molecules24040733 - 18 Feb 2019
Cited by 7
Abstract
The stabilization of G-Quadruplex DNA structures by ligands is a promising strategy for telomerase inhibition in cancer therapy since this enzyme is responsible for the unlimited proliferation of cancer cells. To assess the potential of a compound as a telomerase inhibitor, selectivity for [...] Read more.
The stabilization of G-Quadruplex DNA structures by ligands is a promising strategy for telomerase inhibition in cancer therapy since this enzyme is responsible for the unlimited proliferation of cancer cells. To assess the potential of a compound as a telomerase inhibitor, selectivity for quadruplex over duplex DNA is a fundamental attribute, as the drug must be able to recognize quadruplex DNA in the presence of a large amount of duplex DNA, in the cellular nucleus. By using different spectroscopic techniques, such as ultraviolet-visible, fluorescence and circular dichroism, this work evaluates the potential of a series of multicharged phthalocyanines, bearing four or eight positive charges, as G-Quadruplex stabilizing ligands. This work led us to conclude that the existence of a balance between the number and position of the positive charges in the phthalocyanine structure is a fundamental attribute for its selectivity for G-Quadruplex structures over duplex DNA structures. Two of the studied phthalocyanines, one with four peripheral positive charges (ZnPc1) and the other with less exposed eight positive charges (ZnPc4) showed high selectivity and affinity for G-Quadruplex over duplex DNA structures and were able to accumulate in the nucleus of UM-UC-3 bladder cancer cells. Full article
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Open AccessFeature PaperArticle
Supramolecular Hybrid Material Based on Engineering Porphyrin Hosts for an Efficient Elimination of Lead(II) from Aquatic Medium
Molecules 2019, 24(4), 669; https://doi.org/10.3390/molecules24040669 - 14 Feb 2019
Cited by 4
Abstract
Porphyrins show great promise for future purification demands. This is largely due to their unique features as host binding molecules that can be modified at the synthetic level, and largely improved by their incorporation into inorganic based materials. In this study, we assessed [...] Read more.
Porphyrins show great promise for future purification demands. This is largely due to their unique features as host binding molecules that can be modified at the synthetic level, and largely improved by their incorporation into inorganic based materials. In this study, we assessed the efficacy of a hybrid material obtained from the immobilization of 5,10,15,20-tetrakis(pentafluorophenyl)-porphyrin on silica surface to remove Pb(II), Cu(II), Cd(II), and Zn(II) ions from water. The new organic-inorganic hybrid adsorbent was fully characterized by adequate techniques and the results show that the hybrid exhibits good chemical and thermal stability. From batch assays, it was evaluated how the efficacy of the hybrid was affected by the pH, contact time, initial metal concentration, and temperature. The adsorption kinetic and isotherms showed to fit the recent developed fractal-like pseudo-second-order model and Langmuir–Freundlich model respectively. The highest adsorption capacities for Pb(II), Cu(II), Cd(II), and Zn(II) ions were 187.36, 125.17, 82.45, and 56.23 mg g−1, respectively, at pH 6.0 and 25 °C. This study also shows that metal cations from real river water samples can be efficient removed in the presence of the new adsorbent material. Full article
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Open AccessCommunication
Synthesis of Meso-Diarylaminocorroles via SNAr Reactions
Molecules 2019, 24(3), 642; https://doi.org/10.3390/molecules24030642 - 12 Feb 2019
Cited by 1
Abstract
A corrole is a tetrapyrrolic macrocycle known as a ring-contracted porphyrinoid. Despite the progress of the synthetic chemistry of meso-aryl-substituted corroles since the early 2000s, meso-heteroatom-substituted corroles have been scarcely reported. Herein we report that the SNAr-type substitution reaction [...] Read more.
A corrole is a tetrapyrrolic macrocycle known as a ring-contracted porphyrinoid. Despite the progress of the synthetic chemistry of meso-aryl-substituted corroles since the early 2000s, meso-heteroatom-substituted corroles have been scarcely reported. Herein we report that the SNAr-type substitution reaction of a meso-chlorocorrole silver complex with diphenylamine or carbazole in the presence of NaH as a base produced meso-aminocorroles. The structures, ultraviolet–visible spectroscopy (UV/Vis), and emission spectra of these meso-aminocorroles were discussed. Furthermore, the oxidation reaction of a meso-diphenylaminocorrole was examined, which resulted in the formation of 10,10-diethoxyisocorrole. Full article
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Open AccessArticle
Novel Hexadeca-Substituted Metal Free and Zinc(II) Phthalocyanines; Design, Synthesis and Photophysicochemical Properties
Molecules 2019, 24(1), 77; https://doi.org/10.3390/molecules24010077 - 26 Dec 2018
Cited by 5
Abstract
The syntheses of a novel 1,4,8,11,15,18,22,25-octahexyloxy-2,3,9,10,16,17,23,24-octa-(4-trifluoromethoxyphenyl) phthalocyanine (3a) and its zinc(II) phthalocyanine derivative (3b) have been described and characterized by elemental analysis,1H NMR, 13C NMR, 19F NMR, mass, UV-Vis and FT-IR. The newly prepared metal-free [...] Read more.
The syntheses of a novel 1,4,8,11,15,18,22,25-octahexyloxy-2,3,9,10,16,17,23,24-octa-(4-trifluoromethoxyphenyl) phthalocyanine (3a) and its zinc(II) phthalocyanine derivative (3b) have been described and characterized by elemental analysis,1H NMR, 13C NMR, 19F NMR, mass, UV-Vis and FT-IR. The newly prepared metal-free phthalocyanine and its zinc(II) counterpart are soluble in most organic solvents. The photophysical and photochemical properties such as aggregation, fluorescence, singlet oxygen generation and photodegradation under light irradiation of these phthalocyanines have been investigated in DMF. The hexadeca-substituted phthalocyanines (3a and 3b) showed longer absorption and emission wavelength values when compared to that of reported phthalocyanine derivatives due to substitution of the all possible positions in the phthalocyanine framework. The zinc(II) phthalocyanine derivative does not only have a good singlet oxygen generation but also has other photophysicochemical properties that enables this phthalocyanine to be useful as a photosensitizer for cancer treatment using photodynamic therapy. Full article
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Open AccessArticle
Bioinspired-Metalloporphyrin Magnetic Nanocomposite as a Reusable Catalyst for Synthesis of Diastereomeric (−)-Isopulegol Epoxide: Anticancer Activity Against Human Osteosarcoma Cells (MG-63)
Molecules 2019, 24(1), 52; https://doi.org/10.3390/molecules24010052 - 24 Dec 2018
Cited by 4
Abstract
In the present study, we developed a green epoxidation approach for the synthesis of the diastereomers of (−)-isopulegol benzyl ether epoxide using molecular oxygen as the oxidant and a hybrid manganese(III)-porphyrin magnetic reusable nanocomposite as the catalyst. High activity, selectivity, and stability were [...] Read more.
In the present study, we developed a green epoxidation approach for the synthesis of the diastereomers of (−)-isopulegol benzyl ether epoxide using molecular oxygen as the oxidant and a hybrid manganese(III)-porphyrin magnetic reusable nanocomposite as the catalyst. High activity, selectivity, and stability were obtained, with up to four recycling cycles without the loss of activity and selectivity for epoxide. The anticancer effect of the newly synthesized isopulegol epoxide diastereomers was evaluated on a human osteosarcoma cell line (MG-63); both diastereomers showed similar in vitro potency. The measured IC50 values were significantly lower than those reported for other monoterpene analogues, rendering these epoxide isomers as promising anti-tumor agents against low prognosis osteosarcoma. Full article
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Open AccessArticle
A H2O2-Responsive Boron Dipyrromethene-Based Photosensitizer for Imaging-Guided Photodynamic Therapy
Molecules 2019, 24(1), 32; https://doi.org/10.3390/molecules24010032 - 21 Dec 2018
Cited by 4
Abstract
In this study, we demonstrate a novel H2O2 activatable photosensitizer (compound 7) which contains a diiodo distyryl boron dipyrromethene (BODIPY) core and an arylboronate group that quenches the excited state of the BODIPY dye by photoinduced electron transfer (PET). [...] Read more.
In this study, we demonstrate a novel H2O2 activatable photosensitizer (compound 7) which contains a diiodo distyryl boron dipyrromethene (BODIPY) core and an arylboronate group that quenches the excited state of the BODIPY dye by photoinduced electron transfer (PET). The BODIPY-based photosensitizer is highly soluble and remains nonaggregated in dimethyl sulfoxide (DMSO) as shown by the intense and sharp Q-band absorption (707 nm). As expected, compound 7 exhibits negligible fluorescence emission and singlet oxygen generation efficiency. However, upon interaction with H2O2, both the fluorescence emission and singlet oxygen production of the photosensitizer can be restored in phosphate buffered saline (PBS) solution and PBS buffer solution containing 20% DMSO as a result of the cleavage of the arylboronate group. Due to the higher concentration of H2O2 in cancer cells, compound 7 even with low concentration is particularly sensitive to human cervical carcinoma (HeLa) cells (IC50 = 0.95 μM) but hardly damage human embryonic lung fibroblast (HELF) cells. The results above suggest that this novel BODIPY derivative is a promising candidate for fluorescence imaging-guided photodynamic cancer therapy. Full article
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Open AccessArticle
5-Phenyl-10,15,20-Tris(4-sulfonatophenyl)porphyrin: Synthesis, Catalysis, and Structural Studies
Molecules 2018, 23(12), 3363; https://doi.org/10.3390/molecules23123363 - 19 Dec 2018
Cited by 1
Abstract
A convenient protocol for the preparation of 5-phenyl-10,15,20-tris(4-sulfonatophenyl)porphyrin, a water-soluble porphyrin with unique aggregation properties, is described. The procedure relies on the one-pot reductive deamination of 5-(4-aminophenyl)-10,15,20-tris(4-sulfonatophenyl)porphyrin, that can be in turn easily obtained from 5,10,15,20-tetraphenylporphyrin by a known three-step sequence involving mononitration, [...] Read more.
A convenient protocol for the preparation of 5-phenyl-10,15,20-tris(4-sulfonatophenyl)porphyrin, a water-soluble porphyrin with unique aggregation properties, is described. The procedure relies on the one-pot reductive deamination of 5-(4-aminophenyl)-10,15,20-tris(4-sulfonatophenyl)porphyrin, that can be in turn easily obtained from 5,10,15,20-tetraphenylporphyrin by a known three-step sequence involving mononitration, nitro to amine reduction and sulfonation of the phenyl groups. This method provides the title porphyrin in gram scale, and compares very favorably with the up to now only described procedure based on the partial sulfonation of TPP, that involves a long and tedious chromatographic enrichment of the final compound. This has allowed us to study for the first time both the use of its zwitterionic aggregate as a supramolecular catalyst of the aqueous Diels–Alder reaction, and the morphology of the aggregates obtained under optimized experimental conditions by atomic force microscopy and also by transmission electron cryomicroscopy. Full article
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Open AccessArticle
Photophysical Properties of Nitrated and Halogenated Phosphorus Tritolylcorrole Complexes: Insights from Theory
Molecules 2018, 23(11), 2779; https://doi.org/10.3390/molecules23112779 - 26 Oct 2018
Cited by 3
Abstract
The photophysical properties of a series of nitrated and halogenated phosphorus tritolylcorrole complexes were studied in dichloromethane solvent by using the density functional theory. Particular emphasis was given to the absorption spectra, the energy gap between the excited singlet and triplet states, and [...] Read more.
The photophysical properties of a series of nitrated and halogenated phosphorus tritolylcorrole complexes were studied in dichloromethane solvent by using the density functional theory. Particular emphasis was given to the absorption spectra, the energy gap between the excited singlet and triplet states, and the magnitude of the spin-orbit couplings for a series of possible intersystem crossing channels between those excited states. The proposed study provides a better description of the photophysical properties of these systems while giving insights into their possible use as photosensitizers in photodynamic therapy. Full article
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Open AccessFeature PaperArticle
A New Protocol for the Synthesis of New Thioaryl-Porphyrins Derived from 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin: Photophysical Evaluation and DNA-Binding Interactive Studies
Molecules 2018, 23(10), 2588; https://doi.org/10.3390/molecules23102588 - 10 Oct 2018
Cited by 6
Abstract
A new protocol for the preparation of thioaryl-porphyrins is described. The compounds were prepared from different disulfides employing NaBH4 as a reducing agent. The methodology allowed the preparation of four different thioaryl-porphyrins in very-good to excellent yields under soft conditions, such as [...] Read more.
A new protocol for the preparation of thioaryl-porphyrins is described. The compounds were prepared from different disulfides employing NaBH4 as a reducing agent. The methodology allowed the preparation of four different thioaryl-porphyrins in very-good to excellent yields under soft conditions, such as short reaction times and smooth heating. Additionally, the photophysical properties of new compounds were determined and experimental and theoretical DNA interactions were assessed. Full article
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Review

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Open AccessReview
Reactive Cobalt–Oxo Complexes of Tetrapyrrolic Macrocycles and N-based Ligand in Oxidative Transformation Reactions
Molecules 2019, 24(1), 78; https://doi.org/10.3390/molecules24010078 - 26 Dec 2018
Cited by 2
Abstract
High-valent cobalt–oxo complexes are reactive transient intermediates in a number of oxidative transformation processes e.g., water oxidation and oxygen atom transfer reactions. Studies of cobalt–oxo complexes are very important for understanding the mechanism of the oxygen evolution center in natural photosynthesis, and helpful [...] Read more.
High-valent cobalt–oxo complexes are reactive transient intermediates in a number of oxidative transformation processes e.g., water oxidation and oxygen atom transfer reactions. Studies of cobalt–oxo complexes are very important for understanding the mechanism of the oxygen evolution center in natural photosynthesis, and helpful to replicate enzyme catalysis in artificial systems. This review summarizes the development of identification of high-valent cobalt–oxo species of tetrapyrrolic macrocycles and N-based ligands in oxidation of organic substrates, water oxidation reaction and in the preparation of cobalt–oxo complexes. Full article
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Open AccessReview
Recent Advances in Catalyzed Sequential Reactions and the Potential Use of Tetrapyrrolic Macrocycles as Catalysts
Molecules 2018, 23(11), 2796; https://doi.org/10.3390/molecules23112796 - 28 Oct 2018
Cited by 7
Abstract
Complexes of porphyrins and of other similar tetrapyrrolic macrocycles are extensively explored as catalysts for different chemical processes, and the development of solid catalysts for heterogeneous processes using molecules with the ability to act as multifunctional catalysts in one-pot reactions is increasing and [...] Read more.
Complexes of porphyrins and of other similar tetrapyrrolic macrocycles are extensively explored as catalysts for different chemical processes, and the development of solid catalysts for heterogeneous processes using molecules with the ability to act as multifunctional catalysts in one-pot reactions is increasing and can lead to the wider use of this class of molecules as catalysts. This mini review focuses on the application of this class of complexes as catalysts in a variety of sequential one-pot reactions. Full article
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