Editorial

4 pages, 190 KiB

Open AccessEditorial

Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018

by Nuno M. M. Moura, Maria Amparo F. Faustino and Maria Graça P. M. S. Neves

Molecules 2020, 25(3), 433; https://doi.org/10.3390/molecules25030433 - 21 Jan 2020

Cited by 2 | Viewed by 2209

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

Research

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17 pages, 3153 KiB

Open AccessArticle

A Convenient Synthesis of Pentaporphyrins and Supramolecular Complexes with a Fulleropyrrolidine

by Joana I. T. Costa, Andreia S. F. Farinha, Filipe A. Almeida Paz and Augusto C. Tomé

Molecules 2019, 24(17), 3177; https://doi.org/10.3390/molecules24173177 - 01 Sep 2019

Cited by 4 | Viewed by 2855

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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11 pages, 1726 KiB

Open AccessArticle

Isomers of β,β-Dinitro-5,10,15,20-tetraphenylporphyrin Derivatives: Valuable Starting Materials for Further Transformations

by Agnieszka Mikus, Mariusz Rosa and Stanisław Ostrowski

Molecules 2019, 24(5), 838; https://doi.org/10.3390/molecules24050838 - 27 Feb 2019

Cited by 11 | Viewed by 3223

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 (Cu^II, Ni^II, Co^II) 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 (Cu^II, Ni^II, Co^II) 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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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23 pages, 8281 KiB

Open AccessFeature PaperArticle

Multicharged Phthalocyanines as Selective Ligands for G-Quadruplex DNA Structures

by Catarina I. V. Ramos, Susana P. Almeida, Leandro M. O. Lourenço, Patrícia M. R. Pereira, Rosa Fernandes, M. Amparo F. Faustino, João P. C. Tomé, Josué Carvalho, Carla Cruz and M. Graça P. M. S. Neves

Molecules 2019, 24(4), 733; https://doi.org/10.3390/molecules24040733 - 18 Feb 2019

Cited by 40 | Viewed by 6616

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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21 pages, 8231 KiB

Open AccessFeature PaperArticle

Supramolecular Hybrid Material Based on Engineering Porphyrin Hosts for an Efficient Elimination of Lead(II) from Aquatic Medium

by Chahrazad El Abiad, Smaail Radi, Maria A. F. Faustino, M. Graça P. M. S. Neves and Nuno M. M. Moura

Molecules 2019, 24(4), 669; https://doi.org/10.3390/molecules24040669 - 14 Feb 2019

Cited by 13 | Viewed by 2942

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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10 pages, 2302 KiB

Open AccessCommunication

Synthesis of Meso-Diarylaminocorroles via S_NAr Reactions

by Kento Ueta, Takayuki Tanaka and Atsuhiro Osuka

Molecules 2019, 24(3), 642; https://doi.org/10.3390/molecules24030642 - 12 Feb 2019

Cited by 7 | Viewed by 3974

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 S_NAr-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 S_NAr-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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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13 pages, 1625 KiB

Open AccessArticle

Novel Hexadeca-Substituted Metal Free and Zinc(II) Phthalocyanines; Design, Synthesis and Photophysicochemical Properties

by Ayoub I. Awaji, Baybars Köksoy, Mahmut Durmuş, Ateyatallah Aljuhani and Shaya Y. Alraqa

Molecules 2019, 24(1), 77; https://doi.org/10.3390/molecules24010077 - 26 Dec 2018

Cited by 13 | Viewed by 4533

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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16 pages, 2300 KiB

Open AccessArticle

Bioinspired-Metalloporphyrin Magnetic Nanocomposite as a Reusable Catalyst for Synthesis of Diastereomeric (−)-Isopulegol Epoxide: Anticancer Activity Against Human Osteosarcoma Cells (MG-63)

by Lucas D. Dias, Ana L. M. Batista de Carvalho, Sara M. A. Pinto, Gilberto L. B. Aquino, Mário J. F. Calvete, Liane M. Rossi, M. P. M. Marques and Mariette M. Pereira

Molecules 2019, 24(1), 52; https://doi.org/10.3390/molecules24010052 - 24 Dec 2018

Cited by 14 | Viewed by 3701

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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15 pages, 4923 KiB

Open AccessArticle

A H₂O₂-Responsive Boron Dipyrromethene-Based Photosensitizer for Imaging-Guided Photodynamic Therapy

by Zhi-Wei Wang, Dan Su, Xiao-Qiang Li, Jing-Jing Cao, De-Chao Yang and Jian-Yong Liu

Molecules 2019, 24(1), 32; https://doi.org/10.3390/molecules24010032 - 21 Dec 2018

Cited by 17 | Viewed by 4819

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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13 pages, 6592 KiB

Open AccessArticle

5-Phenyl-10,15,20-Tris(4-sulfonatophenyl)porphyrin: Synthesis, Catalysis, and Structural Studies

by Aitor Arlegui, Zoubir El-Hachemi, Joaquim Crusats and Albert Moyano

Molecules 2018, 23(12), 3363; https://doi.org/10.3390/molecules23123363 - 19 Dec 2018

Cited by 10 | Viewed by 5664

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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10 pages, 1933 KiB

Open AccessArticle

Photophysical Properties of Nitrated and Halogenated Phosphorus Tritolylcorrole Complexes: Insights from Theory

by Marta Erminia Alberto, Bruna Clara De Simone, Gloria Mazzone, Nino Russo and Marirosa Toscano

Molecules 2018, 23(11), 2779; https://doi.org/10.3390/molecules23112779 - 26 Oct 2018

Cited by 6 | Viewed by 2417

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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12 pages, 4581 KiB

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

by Patrícia Foletto, Fabiula Correa, Luciano Dornelles, Bernardo A. Iglesias, Carolina H. da Silveira, Pablo A. Nogara, João B. T. da Rocha, Maria A. F. Faustino and Oscar E. D. Rodrigues

Molecules 2018, 23(10), 2588; https://doi.org/10.3390/molecules23102588 - 10 Oct 2018

Cited by 17 | Viewed by 3848

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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Review

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17 pages, 2323 KiB

Open AccessReview

Reactive Cobalt–Oxo Complexes of Tetrapyrrolic Macrocycles and N-based Ligand in Oxidative Transformation Reactions

by Atif Ali, Waseem Akram and Hai-Yang Liu

Molecules 2019, 24(1), 78; https://doi.org/10.3390/molecules24010078 - 26 Dec 2018

Cited by 31 | Viewed by 7545

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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20 pages, 9413 KiB

Open AccessReview

Recent Advances in Catalyzed Sequential Reactions and the Potential Use of Tetrapyrrolic Macrocycles as Catalysts

by Everton Henrique Santos, Charles Carvalho, Carolina Machado Terzi and Shirley Nakagaki

Molecules 2018, 23(11), 2796; https://doi.org/10.3390/molecules23112796 - 28 Oct 2018

Cited by 17 | Viewed by 4209

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

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018)

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