The Role of the Counterions in Self-Assembly of J-Aggregates from meso-Aryl Substituted Porphyrin Diacids in Aqueous Solutions

Gradova, Margaret A.; Kuryakov, Vladimir N.; Лобанов, А. В.

doi:10.6060/mhc150871g

Cited by 7 publications

(4 citation statements)

References 25 publications

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“…Other efforts focused on nonplanar porphyrin diacids in supramolecular assemblies. [97] In one report, Honda and co- Figure 15. Ad odecasubstituted porphyrin like 56 is "pre-distorted" due to repulsive peri-interactions of the meso-a nd b-substituents.…”

Section: Porphyrin (Di)cationsmentioning

confidence: 98%

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Kielmann

Senge

2018

Angew Chem Int Ed

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The core N-H units of planar porphyrins are often inaccessible to forming hydrogen-bonding complexes with acceptor molecules. This is due to the fact that the amine moieties are "shielded" by the macrocyclic system, impeding the formation of intermolecular H-bonds. However, methods exist to modulate the tetrapyrrole conformations and to reshape the vector of N-H orientation outwards, thus increasing their availability and reactivity. Strategies include the use of porpho(di)methenes and phlorins (calixphyrins), as well as saddle-distorted porphyrins. The former form cavities due to interruption of the aromatic system. The latter are highly basic systems and capable of binding anions and neutral molecules via N-H⋅⋅⋅X-type H-bonds. This Review discusses the role of porphyrin(oid) ligands in various coordination-type complexes, means to access the core for hydrogen bonding, the concept of conformational control, and emerging applications, such as organocatalysis and sensors.

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Section: Porphyrin (Di)cationsmentioning

confidence: 98%

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Kielmann

Senge

2018

Angew Chem Int Ed

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“…> 300 °C. 1 H NMR (CDCl 3 , 300 MHz): δ 8.85 (s, 8H, H-β), 8.22 (dt, 8H, J = 7.8, 1.7 Hz, H o -Ph), 7.76 (m, 12H, H m -Ph and H p -Ph), −2.77 (s, 2H, N-H) ppm. 13 C NMR (CDCl 3 , 75.5 MHz) δ: 142.3 (C ipso -Ph), 134.7 (C o -Ph), 131.2 (C-β), 127.8 (C m -Ph), 126.8 (C p -Ph), 120.3 (C-meso) ppm.…”

Section: Methodsmentioning

confidence: 99%

“…Combining protonated porphyrins with anionic species can lead to self-assembled supramolecular structures. [1][2][3] Since one of the effects of protonation is lowering the reduction potentials, 4,5 protonated porphyrins are attractive for the construction of donor-acceptor assemblies, where the porphyrin moiety acts as an electron-acceptor.…”

mentioning

confidence: 99%

Elucidating the Electroreduction Mechanism of the Monoprotonated Octaethylporphyrin. A Comparative Study with the Diprotonated Octaethyl- and meso-Tetraphenyl-porphyrins

Castro-Cruz

Arias-Aranda

Farfán

et al. 2020

J. Electrochem. Soc.

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The electrochemical reduction mechanisms of diprotonated tetraphenylporphyrin (H2TPP) and mono- and diprotonated octaethylporphyrin (H2OEP) were studied in tetrabutylammonium perchlorate/benzonitrile. The diprotonated forms of both porphyrins undergo two one-electron reversible reduction processes forming isophlorin. Contrastingly, monoprotonated H2OEP is reduced in a single process involving a two-electron one-proton transfer that yields two types of short-lived intermediates, isophlorin and neutral phlorin. The existence of intermolecular proton transfer reactions, from the parent protonated porphyrin to the isophlorin or neutral phlorin, to form phlorin cation species (isophlorin protonated at the meso-position) was demonstrated. In-situ UV–vis spectroelectrochemical experiments allowed us to identify the absorption of the isophlorin species of H2TPP but not of H2OEP. These results show that the lack of phenyl substituents increases the rate of protonation at the meso-position. Finally, it was demonstrated that the protonation of the porphyrin macrocycle not only lowers the reduction potentials but also increases the reactivity of the electrogenerated species.

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“…The other concentrations are not proper for this inactivation, Figure 8. This fact could be interpreted knowing different aggregated and ionized forms of TSPP [93] and geometrical configurations of these forms with their reduced photochemical activity, as H-aggregates [94]. The action of this PS is highly dependent on the temperature, Figure 9.…”

Section: Influence Of Dicationic (J-aggregates) Tspp Form On Apdtmentioning

confidence: 97%

Revisiting Tetra-p-Sulphonated Porphyrin as Antimicrobial Photodynamic Therapy Agent

Ion

2021

Coatings

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Photodynamic inactivation is known as a new antimicrobial photodynamic therapy (aPDT). It is based on the administration of a photosensitizer located in the bacterial/viral cell followed by exposure to light radiations (with a proper wavelength corresponding with the maximum value of absorption of the photosensitizer) that generate singlet oxygen or reactive oxygen species, which lead to the death of different microorganisms. This review will present an overview beyond the state-of-the-art of the photosensitizer types (based on tetra-p-sulphonated-phenyl porphyrin—TSPP, which is able to form cationic and J-aggregates forms at different pH values ((1–4) and concentrations around 10−5 M) and their applications of PDT for viruses, especially. The mechanism of dicationic and J-aggregates formation is presented in this paper, and the photophysical parameters have been collected and harmonized to support their behaviours. Studies on Herpes Simplex virus type 1 (HSV-1) are useful, because without the help of HSV-1, the COVID-19 virus may not be able to cause serious illness or death in humans. This method could be a new direction for COVID treatment and immunization, either to prevent infections or to develop photoactive fabrics (e.g., masks, suits, gloves) to disinfect surfaces, under artificial light and/or natural sunlight. The use of photodynamic therapy (PDT) can be an alternative approach against SARS-CoV-2 that deserves to be explored.

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The Role of the Counterions in Self-Assembly of J-Aggregates from meso-Aryl Substituted Porphyrin Diacids in Aqueous Solutions

Cited by 7 publications

References 25 publications

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Elucidating the Electroreduction Mechanism of the Monoprotonated Octaethylporphyrin. A Comparative Study with the Diprotonated Octaethyl- and meso-Tetraphenyl-porphyrins

Revisiting Tetra-p-Sulphonated Porphyrin as Antimicrobial Photodynamic Therapy Agent

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