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Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021

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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 (31 December 2021) | Viewed by 46233

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Prof. Dr. Maria G. P. M. S. Neves

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Department of Chemistry and LAQV-REQUIMTE, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: organic synthesis; tetrapyrrolic macrocycles; photodynamic therapy; sensing; G-quadruplex ligands; solar cells; catalysis
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Dr. M. Amparo F. Faustino

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LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: porphyrin derivatives and analogues; cyclo-addition reactions; photodynamic applications; DSSC cells; antimicrobials; antitumoral
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Dr. Nuno M. M. Moura

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Department of Chemistry and LAQV-REQUIMTE, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: organic chemistry; heterocycles; porphyrinoids; chemosensing; photodynamic processes; energy conversion systems; remediation
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Special Issue Information

Dear Colleagues,

Natural and synthetic macrocycles, like porphyrins, corroles, and phthalocyanines, among others, are considered strong and extremely versatile candidates to be used in different fields, such as catalysis, molecular recognition and sensing, medicine (e.g., photodynamic therapy, medical imaging, theranostic) and in the development of advanced biomimetic models and functional materials.

All these applications are strongly dependent on the availability of compounds with adequate and specific structural features and can consequently justify the high investment of different researcher groups to synthesize and modify natural and synthetic porphyrin derivatives or analogues and also to assess their photochemical/photophysical and biological properties, among others. This Special Issue, following the success of the previous ones in 2016 and 2018, aims to provide a forum for the dissemination of the latest information on the synthesis and functionalization of tetrapyrrolic macrocycles and their potential applications in different fields.

You may choose our Joint Special Issue in Chemistry.

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

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Keywords

tetrapyrrolic macrocycles
porphyrins and analogues
synthesis
functionalization
application

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Related Special Issues

Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications in Molecules (12 articles)
Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018 in Molecules (14 articles)
Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications IV in Chemistry (1 article)
Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications, Volume IV in Molecules (1 article)

Published Papers (9 papers)

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Research

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16 pages, 2549 KiB

Open AccessArticle

Self-Assembled Nanomaterials Based on Complementary Sn(IV) and Zn(II)-Porphyrins, and Their Photocatalytic Degradation for Rhodamine B Dye

by Nirmal K. Shee and Hee-Joon Kim

Molecules 2021, 26(12), 3598; https://doi.org/10.3390/molecules26123598 - 11 Jun 2021

Cited by 23 | Viewed by 3008

Abstract

A series of porphyrin triads (1–6), based on the reaction of trans-dihydroxo-[5,15-bis(3-pyridyl)-10,20-bis(phenyl)porphyrinato]tin(IV) (SnP) with six different phenoxy Zn(II)-porphyrins (ZnLⁿ), was synthesized. The cooperative metal–ligand coordination of 3-pyridyl nitrogens in the SnP with the phenoxy Zn(II)-porphyrins, followed by the self-assembly process, leads to the formation of nanostructures. The red-shifts and remarkable broadening of the absorption bands in the UV–vis spectra for the triads in CHCl₃ indicate that nanoaggregates may be produced in the self-assembly process of these triads. The emission intensities of the triads were also significantly reduced due to the aggregation. Microscopic analyses of the nanostructures of the triads reveal differences due to the different substituents on the axial Zn(II)-porphyrin moieties. All these nanomaterials exhibited efficient photocatalytic performances in the degradation of rhodamine B (RhB) dye under visible light irradiation, and the degradation efficiencies of RhB in aqueous solution were observed to be 72~95% within 4 h. In addition, the efficiency of the catalyst was not impaired, showing excellent recyclability even after being applied for the degradation of RhB in up to five cycles. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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17 pages, 2469 KiB

Open AccessArticle

Cationic Pyrrolidine/Pyrroline-Substituted Porphyrins as Efficient Photosensitizers against E. coli

by Bruno M. F. Ladeira, Cristina J. Dias, Ana T. P. C. Gomes, Augusto C. Tomé, Maria G. P. M. S. Neves, Nuno M. M. Moura, Adelaide Almeida and M. Amparo F. Faustino

Molecules 2021, 26(2), 464; https://doi.org/10.3390/molecules26020464 - 17 Jan 2021

Cited by 10 | Viewed by 3038

Abstract

New porphyrin–pyrrolidine/pyrroline conjugates were prepared by revisiting 1,3-dipolar cycloaddition reactions between a porphyrinic azomethine ylide and a series of dipolarophiles. Cationic conjugates obtained by alkylation of the pyrrolidine/pyrroline cycloadducts showed ability to generate singlet oxygen and to produce iodine in presence of KI when irradiated with visible light. Some of the cationic derivatives showed photobactericidal properties towards a Gram-negative bioluminescent E. coli. In all cases, these features were significantly improved using KI as coadjutant, allowing, under the tested conditions, the photoinactivation of the bacterium until the detection limit of the method with a drastic reduction of the required photosensitizer concentration and irradiation time. The obtained results showed a high correlation between the ability of the cationic porphyrin derivative to produce singlet oxygen and iodine and its E. coli photoinactivation profile. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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11 pages, 3025 KiB

Open AccessArticle

Photodynamic Inactivation of Methicillin-Resistant Staphylococcus aureus by a Natural Food Colorant (E-141ii)

by Cynthia S. A. Caires, Cicera M. Silva, Alessandra R. Lima, Lurian M. Alves, Thalita H. N. Lima, Ana C. S. Rodrigues, Marilene R. Chang, Samuel L. Oliveira, Corinne Whitby, Valter A. Nascimento and Anderson R. L. Caires

Molecules 2020, 25(19), 4464; https://doi.org/10.3390/molecules25194464 - 29 Sep 2020

Cited by 15 | Viewed by 3302

Abstract

This study evaluates the photosensitizing effectiveness of sodium copper chlorophyllin, a natural green colorant commonly used as a food additive (E-141ii), to inactivate methicillin-sensitive and methicillin-resistant Staphylococcus aureus under red-light illumination. Antimicrobial photodynamic inactivation (aPDI) was tested on a methicillin-sensitive reference strain (ATCC 25923) and a methicillin-resistant Staphylococcus aureus strain (GenBank accession number Mh087437) isolated from a clinical sample. The photoinactivation efficacy was investigated by exposing the bacterial strains to different E-141ii concentrations (0.0, 1.0, 2.5, 5.0, 10.0, and 20.0 µM) and to red light (625 nm) at 30 J cm⁻². The results showed that E-141ii itself did not prevent bacterial growth for all tested concentrations when cultures were placed in the dark. By contrast, E-141ii photoinactivated both methicillin-sensitive Staphylococcus aureus (MSSA) and methicillin-resistant Staphylococcus aureus (MRSA) under red-light illumination. However, different dose responses were observed for MSSA and MRSA. Whilst the MSSA growth was inhibited to the detection limit of the method with E-141ii at 2.5 µM, >10 µM concentrations were required to inhibit the growth of MRSA. The data also suggest that E-141ii can produce reactive oxygen species (ROS) via Type I reaction by electron transfer from its first excited singlet state to oxygen molecules. Our findings demonstrate that the tested food colorant has great potential to be used in aPDI of MRSA. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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13 pages, 979 KiB

Open AccessArticle

Oxazolochlorins 21. Most Efficient Access to meso-Tetraphenyl- and meso-Tetrakis(pentafluorophenyl)porpholactones, and Their Zinc(II) and Platinum(II) Complexes

by Damaris Thuita, Dinusha Damunupola and Christian Brückner

Molecules 2020, 25(18), 4351; https://doi.org/10.3390/molecules25184351 - 22 Sep 2020

Cited by 5 | Viewed by 3839

Abstract

meso-Phenyl- and meso-pentafluorophenyl-porpholactones, their metal complexes, as well as porphyrinoids directly derived from them are useful in a number of technical and biomedical applications, and more uses are expected to be discovered. About a dozen competing and complementary pathways toward their synthesis were reported. The suitability of the methods changes with the meso-aryl group and whether the free base or metal derivatives are sought. These circumstances make it hard for anyone outside of the field of synthetic porphyrin chemistry to ascertain which pathway is the best to produce which specific derivative. We report here on what we experimentally evaluated to be the most efficient pathways to generate the six key compounds from the commercially available porphyrins, meso-tetraphenylporphyrin (TPP) and meso-tetrakis(pentafluorophenyl)porphyrin (T^FPP): free base meso-tetraphenylporpholactone (TPL) and meso-tetrakis(pentafluorophenyl)porpholactone (T^FPL), and their platinum(II) and zinc(II) complexes TPLPt, T^FPLPt, TPLZn, and T^FPLZn, respectively. Detailed procedures are provided to make these intriguing molecules more readily available for their further study. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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23 pages, 3809 KiB

Open AccessFeature PaperArticle

Weak Interactions and Conformational Changes in Core-Protonated A₂- and A_x-Type Porphyrin Dications

by Christopher J. Kingsbury, Keith J. Flanagan, Hans-Georg Eckhardt, Marc Kielmann and Mathias O. Senge

Molecules 2020, 25(14), 3195; https://doi.org/10.3390/molecules25143195 - 13 Jul 2020

Cited by 14 | Viewed by 3826

Abstract

Individual chemical motifs are known to introduce structural distortions to the porphyrin macrocycle, be it in the core or at the periphery of the macrocycle. The interplay when introducing two or more of these known structural motifs has been scarcely explored and is not necessarily simply additive; these structural distortions have a chance to compound or negate to introduce new structural types. To this end, a series of compounds with complementary peripheral (5,15-disubstitution) and core (acidification) substitution patterns were investigated. The single-crystal X-ray structures of 18 5,15-diphenylporphyrin, 5,15-diphenylporphyrindi-ium diacid, and related compounds are reported, including the first example of a 5,15-dialkylporphyrindi-ium. Normal-coordinate structural decomposition (NSD) analysis is used for a detailed analysis of the conformation of the porphyrin subunit within the crystal structures. An elongation of porphyrin macrocycles along the C₅,C₁₅- axis (B_2g symmetry) is observed in all of the free base porphyrins and porphyrin dications; distance across the core is around 0.3 Å in the free base and diacid compounds, and more than doubled in 5,15-dipentylporphyrin and 5,15-dipentylporphyrindi-ium diacid. While the free base porphyrins are largely planar, a large out-of-plane distortion can be observed in 5,15-diphenylporphyrin diacids, with the expected “projective saddle” shape characteristic for such systems. The combination of these two distortions (B_2u and B_2g) from regular porphyrin structure results in a macrocycle best characterized in the chiral point-group D₂. A rare structural type of a cis-hydrogen bond chelate is observed for 5,15-dipentylporphyrindi-ium diacid, which adopts an achiral C_2v symmetry. Crystallographic data indicate that the protonated porphyrin core forms hydrogen bonding chelates (N-H⋯X⋯H-N) to counter-anions. Weaker interactions, such as induced intramolecular C-H⋯O interactions from the porphyrin periphery are described, with distances characteristic of charge-assisted interactions. This paper offers a conceptual framework for accessing porphyrin macrocycles with designable distortion and symmetry, useful for the selective perturbation of electronic states and a design-for-application approach to solid state porphyrin materials. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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Review

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25 pages, 49662 KiB

Open AccessFeature PaperReview

Fluorescence Spectroscopy of Porphyrins and Phthalocyanines: Some Insights into Supramolecular Self-Assembly, Microencapsulation, and Imaging Microscopy

by Raquel Teixeira, Vanda Vaz Serra, David Botequim, Pedro M. R. Paulo, Suzana M. Andrade and Sílvia M. B. Costa

Molecules 2021, 26(14), 4264; https://doi.org/10.3390/molecules26144264 - 14 Jul 2021

Cited by 16 | Viewed by 4563

Abstract

The molecular interactions of anionic tetrasulfonate phenyl porphyrin (TPPS) with poly(amido amine) (PAMAM) dendrimers of generation 2.0 and 4.0 (G2 and G4, respectively) forming H- or J-aggregates, as well as with human and bovine serum albumin proteins (HSA and BSA), were reviewed in the context of self-assembly molecular complementarity. The spectroscopic studies were extended to the association of aluminum phthtalocyanine (AlPCS₄) detected with a PAMAM G4 dendrimer with fluorescence studies in both steady state and dynamic state, as well as due to the fluorescence quenching associated to electron-transfer with a distribution of lifetimes. The functionalization of TPPS with peripheral substituents enables the assignment of spontaneous pH-induced aggregates with different and well-defined morphologies. Other work reported in the literature, in particular with soft self-assembly materials, fall in the same area with particular interest for the environment. The microencapsulation of TPPS studies into polyelectrolyte capsules was developed quite recently and aroused much interest, which is well supported and complemented by the extensive data reported on the Imaging Microscopy section of the Luminescence of Porphyrins and Phthalocyanines included in the present review. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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23 pages, 3260 KiB

Open AccessFeature PaperReview

Peptide-Tetrapyrrole Supramolecular Self-Assemblies: State of the Art

by Paolo Dognini, Christopher R. Coxon, Wendel A. Alves and Francesca Giuntini

Molecules 2021, 26(3), 693; https://doi.org/10.3390/molecules26030693 - 28 Jan 2021

Cited by 14 | Viewed by 4784

Abstract

The covalent and noncovalent association of self-assembling peptides and tetrapyrroles was explored as a way to generate systems that mimic Nature’s functional supramolecular structures. Different types of peptides spontaneously assemble with porphyrins, phthalocyanines, or corroles to give long-range ordered architectures, whose structure is determined by the features of both components. The regular morphology and ordered molecular arrangement of these systems enhance the photochemical properties of embedded chromophores, allowing applications as photo-catalysts, antennas for dye-sensitized solar cells, biosensors, and agents for light-triggered therapies. Chemical modifications of peptide and tetrapyrrole structures and control over the assembly process can steer the organization and influence the properties of the resulting system. Here we provide a review of the field, focusing on the assemblies obtained from different classes of self-assembling peptides with tetrapyrroles, their morphologies and their applications as innovative functional materials. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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23 pages, 4100 KiB

Open AccessReview

Research Progress in Conversion of CO₂ to Valuable Fuels

by Luyi Xu, Yang Xiu, Fangyuan Liu, Yuwei Liang and Shengjie Wang

Molecules 2020, 25(16), 3653; https://doi.org/10.3390/molecules25163653 - 11 Aug 2020

Cited by 78 | Viewed by 7948

Abstract

Rapid growth in the world’s economy depends on a significant increase in energy consumption. As is known, most of the present energy supply comes from coal, oil, and natural gas. The overreliance on fossil energy brings serious environmental problems in addition to the scarcity of energy. One of the most concerning environmental problems is the large contribution to global warming because of the massive discharge of CO₂ in the burning of fossil fuels. Therefore, many efforts have been made to resolve such issues. Among them, the preparation of valuable fuels or chemicals from greenhouse gas (CO₂) has attracted great attention because it has made a promising step toward simultaneously resolving the environment and energy problems. This article reviews the current progress in CO₂ conversion via different strategies, including thermal catalysis, electrocatalysis, photocatalysis, and photoelectrocatalysis. Inspired by natural photosynthesis, light-capturing agents including macrocycles with conjugated structures similar to chlorophyll have attracted increasing attention. Using such macrocycles as photosensitizers, photocatalysis, photoelectrocatalysis, or coupling with enzymatic reactions were conducted to fulfill the conversion of CO₂ with high efficiency and specificity. Recent progress in enzyme coupled to photocatalysis and enzyme coupled to photoelectrocatalysis were specially reviewed in this review. Additionally, the characteristics, advantages, and disadvantages of different conversion methods were also presented. We wish to provide certain constructive ideas for new investigators and deep insights into the research of CO₂ conversion. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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34 pages, 20640 KiB

Open AccessFeature PaperReview

Riley Oxidation of Heterocyclic Intermediates on Paths to Hydroporphyrins—A Review

by Pengzhi Wang and Jonathan S. Lindsey

Molecules 2020, 25(8), 1858; https://doi.org/10.3390/molecules25081858 - 17 Apr 2020

Cited by 15 | Viewed by 10504

Abstract

Riley oxidation of advanced heterocyclic intermediates (dihydrodipyrrins and tetrahydrodipyrrins) is pivotal in routes to synthetic hydroporphyrins including chlorins, bacteriochlorins, and model (bacterio)chlorophylls. Such macrocycles find wide use in studies ranging from energy sciences to photomedicine. The key transformation (–CH₃ → –CHO) is often inefficient, however, thereby crimping the synthesis of hydroporphyrins. The first part of the review summarizes 12 representative conditions for Riley oxidation across diverse (non-hydrodipyrrin) substrates. An interlude summarizes the proposed mechanisms and provides context concerning the nature of various selenium species other than SeO₂. The second part of the review comprehensively reports the conditions and results upon Riley oxidation of 45 1-methyltetrahydrodipyrrins and 1-methyldihydrodipyrrins. A comparison of the results provides insights into the tolerable structural features for Riley oxidation of hydrodipyrrins. In general, Riley oxidation of dihydrodipyrrins has a broad scope toward substituents, but proceeds in only modest yield. Too few tetrahydrodipyrrins have been examined to draw conclusions concerning scope. New reaction conditions or approaches will be required to achieve high yields for this critical transformation in the synthesis of hydroporphyrins. Full article

(This article belongs to the Special Issue Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2020–2021)

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