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Chemical Reviews May 2022Confusion is a novel concept of isomerism in porphyrin chemistry, delivering a steady stream of new chemistry since the discovery of N-confused porphyrin, a porphyrin... (Review)
Review
Confusion is a novel concept of isomerism in porphyrin chemistry, delivering a steady stream of new chemistry since the discovery of N-confused porphyrin, a porphyrin mutant, in 1994. These days, the number of confused porphyrinoids is increasing, and confusion and associated fusion are found in various fields such as supramolecular chemistry, materials chemistry, biological chemistry, and catalysts. In this review, the birth and growth of confused porphyrinoids in the last three decades are described.
Topics: Isomerism; Porphyrins
PubMed: 35230807
DOI: 10.1021/acs.chemrev.1c00065 -
Biosensors & Bioelectronics Jun 2018It remains a significant challenge to study the interactions between metal ions and porphyrin molecules at single ion level. Here, we constructed a nanopore-based...
It remains a significant challenge to study the interactions between metal ions and porphyrin molecules at single ion level. Here, we constructed a nanopore-based sensing for label-free and real-time analysis of the interaction between Cu and 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin (TPPS). The results demonstrate that emerging electronic signatures of the Cu-TPPS complex that is completely different form the original free TPPS were observed in the α-hemolysin (α-HL) nanopore. Based on the distinctive electronic signal patterns between TPPS and Cu-TPPS complex, the unique nanopore sensor can achieve a highly sensitive detection of Cu in aqueous media. The frequency of signature events showed a linear response toward the concentration of Cu in the range of 0.03 µM - 1.0 μM, with a detection limit of 16 nM (S/N = 3). The sensing system also exhibited high selectivity against other metal ions, and the feasibility of this approach for practical applications was demonstrated with the determination of Cu in running water.
Topics: Biosensing Techniques; Copper; Hemolysin Proteins; Ions; Metals; Nanopores; Porphyrins; Single Molecule Imaging; Water
PubMed: 29571164
DOI: 10.1016/j.bios.2018.03.002 -
Astrobiology Jul 2022Metal complexes of porphyrins and porphyrin-type compounds are ubiquitous in all three domains of life, with hemes and chlorophylls being the best-known examples. Their...
Metal complexes of porphyrins and porphyrin-type compounds are ubiquitous in all three domains of life, with hemes and chlorophylls being the best-known examples. Their diagenetic transformation products are found as geoporphyrins, in which the characteristic porphyrin core structure is retained and which can be up to 1.1 billion years old. Because of this, and their relative ease of detection, metalloporphyrins appear attractive as chemical biosignatures in the search for extraterrestrial life. In this study, we investigated the stability of solid chlorido(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III) [FeCl(oep)], which served as a model for heme-like molecules and iron geoporphyrins. [FeCl(oep)] was exposed to a variety of astrobiologically relevant extreme conditions, namely: aqueous acids and bases, oxidants, heat, and radiation. Key results are: (1) the [Fe(oep)] core is stable over the pH range 0.0-13.5 even at 80°C; (2) the oxidizing power follows the order ClO > HO > ClO > HNO > ClO; (3) in an inert atmosphere, the iron porphyrin is thermally stable to near 250°C; (4) at high temperatures, carbon dioxide gas is not inert but acts as an oxidant, forming carbon monoxide; (5) a decomposition layer is formed on ultraviolet irradiation and protects the [FeCl(oep)] underneath; (6) an NaCl/NaHCO salt mixture has a protective effect against X-rays; and (7) no such effect is observed when [FeCl(oep)] is exposed to iron ion particle radiation. The relevance to potential iron porphyrin biosignatures on Mars, Europa, and Enceladus is discussed.
Topics: Heme; Hydrogen Peroxide; Iron; Metalloporphyrins; Oxidants; Porphyrins
PubMed: 35647896
DOI: 10.1089/ast.2021.0144 -
Nanomedicine (London, England) May 2019Nanoscale metal-organic frameworks (MOFs) have been widely used as controlled drug delivery vehicles and cancer therapy agents due to their intrinsic superior... (Review)
Review
Nanoscale metal-organic frameworks (MOFs) have been widely used as controlled drug delivery vehicles and cancer therapy agents due to their intrinsic superior properties. Scientists have made remarkable achievements in the field of nanomedicine by using the MOFs and MOF-based multifunctional nanomaterials due to the easy synthesis into nanoscale and functionalization. In this review, we highlight the recent progress of nanoscale MOFs as drug delivery vehicles for cancer theranostics. We divide the discussion into three parts. The first and second parts focus on the drug delivery of unmodified MOF and modified MOFs, respectively, while the third part focuses on porphyrin MOFs as photosensitizers for photodynamic therapy. Finally, we conclude by identifying areas of research that we believe will propel the translation and application of MOFs.
Topics: Animals; Antineoplastic Agents; Drug Carriers; Drug Liberation; Humans; Metal-Organic Frameworks; Nanomedicine; Nanoparticles; Photochemotherapy; Photosensitizing Agents; Porphyrins
PubMed: 31084393
DOI: 10.2217/nnm-2018-0347 -
Chemical Reviews Feb 2017Ever since the discovery of the porphyrin ring in "pigments of life", such as chlorophyll and hemoglobin, it has become a prime synthetic target for optoelectronic... (Review)
Review
Ever since the discovery of the porphyrin ring in "pigments of life", such as chlorophyll and hemoglobin, it has become a prime synthetic target for optoelectronic properties and in the design of metal complexes. During one such early expedition on the synthesis of porphyrin, Woodward proposed that condensing pyrrole with an aldehyde under acidic conditions yields the "precursor" porphyrinogen macrocycle. Its four-electron oxidation leads to the "transitory" 20π isophlorin, which undergoes subsequent two-electron oxidation to form the 18π "porphyrin". Due to its fleeting lifetime, it has been a synthetic challenge to stabilize the tetrapyrrolic isophlorin. This macrocycle symbolizes the antiaromatic character of a porphyrin-like macrocycle. In addition, the pyrrole NH also plays a key role in the proton-coupled, two-electron oxidation of isophlorin to the aromatic porphyrin. However, a major aspect of its unstable nature was attributed to its antiaromatic character, which is understood to destabilize the macrocycle upon conjugation. Antiaromaticity in general has not gained significant attention mainly due to the lack of stable 4nπ systems. In this regard, a stable isophlorin and its derivatives provide a glimmering hope to peek into the world of antiaromatic systems. This review will focus on the attempted synthesis of antiaromatic isophlorin ever since its conception. Based on recent synthetic advances, the chemistry of isophlorins can be expected to blossom into expanded derivatives of this antiaromatic macrocycle. Along with the synthetic details, the structural, electronic, and redox properties of isophlorin and its expanded derivatives will be elaborated.
Topics: Molecular Structure; Oxidation-Reduction; Porphyrins
PubMed: 27966924
DOI: 10.1021/acs.chemrev.6b00544 -
Journal of Cancer Research and Clinical... Sep 2022Esophageal cancer is the most common gastrointestinal tumor and is difficult to be eradicated with conventional treatment. Porphyrin-based photosensitizers (PSs)...
PURPOSE
Esophageal cancer is the most common gastrointestinal tumor and is difficult to be eradicated with conventional treatment. Porphyrin-based photosensitizers (PSs) mediated photodynamic therapy (PDT) could kill tumor cells with less damage to normal cells. As the most widely used porphyrin-based photosensitizer in clinics, Photofrin II has excellent anti-tumor effect. However, it has some disadvantages such as weak absorption at near infrared region, the complexity of components and prolonged skin photosensitivity. Here series novel 5,15-diaryl-10,20-dihalogeno porphyrin derivatives were afforded and evaluated to develop more effective and safer photosensitizers for tumor therapy.
METHODS
The photophysical properties and singlet oxygen generation rates of 5,15-diaryl-10,20-dihalogeno porphyrins (I, II) were tested. The cytotoxicity of I and II were measured by MTT assay. The pathway of cell death was studied by flow cytometry. In vivo photodynamic efficacy of I and II in Eca-109 tumor-bearing BABL/c nude mice were measured and histopathological analysis were examined.
RESULTS
5,15-Diaryl-10,20-dihalogeno porphyrins I and II were synthesized. The longest absorption wavelength of these halogenated porphyrins (λ = 660 nm) displayed a red shift around 30 nm compared to the unhalogenated porphyrins PS (λ = 630 nm). The singlet oxygen generation rates of I and II were significantly higher than PS and HMME. All PSs mediated PDT showed obvious cytotoxic effect against Eca-109 cells compared to HMME in vitro and in vivo. Among these PSs, II exhibited appropriate absorption in the phototherapeutic window, higher O generation rate (k = 0.0061 s), the strongest phototoxicity (IC = 0.4 μM), lower dark toxicity, high generation of intracellular ROS in Eca-109 cells and excellent photodynamic anti-tumor efficacy in vivo. Besides, cell necrosis was induced by compound II mediated PDT.
CONCLUSION
All new compounds have obvious photodynamic anti-esophageal cancer effects. Among them, the photosensitizer II showed excellent efficacy in vitro and in vivo, which has the potential to become a photodynamic anti-tumor drug.
Topics: Animals; Antineoplastic Agents; Cell Line, Tumor; Esophageal Neoplasms; Mice; Mice, Nude; Photochemotherapy; Photosensitizing Agents; Porphyrins; Singlet Oxygen
PubMed: 35522290
DOI: 10.1007/s00432-022-04037-7 -
Journal of Enzyme Inhibition and... Dec 2020With the development of photodynamic therapy (PDT), remarkable studies have been conducted to generate photosensitisers (PSs), especially porphyrin PSs. A variety of... (Review)
Review
With the development of photodynamic therapy (PDT), remarkable studies have been conducted to generate photosensitisers (PSs), especially porphyrin PSs. A variety of chemical modifications of the porphyrin skeleton have been introduced to improve cellular delivery, stability, and selectivity for cancerous tissues. This review aims to highlight the developments in porphyrin-based structural modifications, with a specific emphasis on the role of PDT in anticancer treatment and the design of PSs to achieve a synergistic effect on multiple targets.
Topics: Animals; Antineoplastic Agents; Cell Proliferation; Drug Design; Drug Screening Assays, Antitumor; Humans; Molecular Structure; Neoplasms; Photochemotherapy; Photosensitizing Agents; Porphyrins
PubMed: 32329382
DOI: 10.1080/14756366.2020.1755669 -
International Journal of Molecular... Aug 2020Porphyrins have planar and conjugated structures, good optical properties, and other special functional properties. Owing to these excellent properties, in recent years,... (Review)
Review
Porphyrins have planar and conjugated structures, good optical properties, and other special functional properties. Owing to these excellent properties, in recent years, porphyrins and their analogues have emerged as a multifunctional platform for chemical sensors. The rich chemistry of these molecules offers many possibilities for metal ions detection. This review mainly discusses two types of molecular porphyrin and porphyrin composite sensors for metal ions detection, because porphyrins can be functionalized to improve their functional properties, which can introduce more chemical and functional sites. According to the different application materials, the section of porphyrin composite sensors is divided into five sub-categories: (1) porphyrin film, (2) porphyrin metal complex, (3) metal-organic frameworks, (4) graphene materials, and (5) other materials, respectively.
Topics: Fluorescent Dyes; Ions; Metal-Organic Frameworks; Metals; Molecular Probes; Porphyrins
PubMed: 32823943
DOI: 10.3390/ijms21165839 -
Expert Opinion on Drug Delivery 2023Porous coordination networks (PCNs) have been widely used in large number of applications such as light harvesting, catalysis, and biomedical applications. Inserting... (Review)
Review
INTRODUCTION
Porous coordination networks (PCNs) have been widely used in large number of applications such as light harvesting, catalysis, and biomedical applications. Inserting porphyrins into PCNs scaffolds can alleviate the solubility and chemical stability problems associated with porphyrin ligands and add functionality to PCNs. The discovery that some PCNs materials have photosensitizer and acoustic sensitizer properties has attracted significant attention in the field of biomedicine, particularly in cancer therapy. This article describes the latest applications of the porphyrin ligand-based family of PCNs in cancer chemodynamic therapy (CDT), photodynamic therapy (PDT), sonodynamic therapy (SDT), photothermal therapy (PTT), and combination therapies and offers some observations and reflections on them.
AREAS COVERED
This article discusses the use of the PCN family of MOFs in cancer treatment, specifically focusing on chemodynamic therapy, sonodynamic therapy, photodynamic therapy, photothermal therapy, and combination therapy.
EXPERT OPINION
Although a large number of PCNs have been developed for use in novel cancer therapeutic approaches, further improvements are needed to advance the use of PCNs in the clinic. For example, the main mechanism of action of PCNs against cancer and the metabolic processes in organisms, and how to construct PCNs that maintain good stability in the complex environment of organisms.
Topics: Humans; Porphyrins; Metal-Organic Frameworks; Photochemotherapy; Photosensitizing Agents; Neoplasms
PubMed: 37776531
DOI: 10.1080/17425247.2023.2260309 -
Basic & Clinical Pharmacology &... Mar 2023Pregnane X receptor (PXR) is known to stimulate haem synthesis, but detailed knowledge on the effects of PXR activation on porphyrin metabolism in humans is lacking. We... (Randomized Controlled Trial)
Randomized Controlled Trial
Pregnane X receptor (PXR) is known to stimulate haem synthesis, but detailed knowledge on the effects of PXR activation on porphyrin metabolism in humans is lacking. We utilized a randomized, crossover, open (blinded laboratory) and placebo-controlled trial with 600-mg rifampicin or placebo dosed for a week to investigate the effects of PXR activation on erythrocyte, plasma, faecal and urine porphyrins. Sixteen healthy volunteers participated on the trial, but the number of volunteers for blood and urine porphyrin analyses was 15 while the number of samples for faecal analyses was 14. Rifampicin increased urine pentaporphyrin concentration 3.7-fold (mean 1.80 ± 0.6 vs. 6.73 ± 4.4 nmol/L, p = 0.003) in comparison with placebo. Urine coproporphyrin I increased 23% (p = 0.036). Faecal protoporphyrin IX decreased (mean 31.6 ± 23.5 vs. 19.2 ± 27.8 nmol/g, p = 0.023). The number of blood erythrocytes was slightly elevated, and plasma bilirubin, catabolic metabolite of haem, was decreased. In conclusion, rifampicin dosing elevated the excretion of certain urinary porphyrin metabolites and decreased faecal protoporphyrin IX excretion. As urine pentaporphyrin and coproporphyrin I are not precursors in haem biosynthesis, increased excretion may serve as a hepatoprotective shunt when haem synthesis or porphyrin levels are increased.
Topics: Humans; Erythrocytes; Healthy Volunteers; Heme; Porphyrins; Rifampin; Pregnane X Receptor
PubMed: 36535687
DOI: 10.1111/bcpt.13826