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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 -
Molecules (Basel, Switzerland) Mar 2021Porphyrinic compounds are widespread in nature and play key roles in biological processes such as oxygen transport in blood, enzymatic redox reactions or photosynthesis.... (Review)
Review
Porphyrinic compounds are widespread in nature and play key roles in biological processes such as oxygen transport in blood, enzymatic redox reactions or photosynthesis. In addition, both naturally derived as well as synthetic porphyrinic compounds are extensively explored for biomedical and technical applications such as photodynamic therapy (PDT) or photovoltaic systems, respectively. Their unique electronic structures and photophysical properties make this class of compounds so interesting for the multiple functions encountered. It is therefore not surprising that optical methods are typically the prevalent analytical tool applied in characterization and processes involving porphyrinic compounds. However, a wealth of complementary information can be obtained from NMR spectroscopic techniques. Based on the advantage of providing structural and dynamic information with atomic resolution simultaneously, NMR spectroscopy is a powerful method for studying molecular interactions between porphyrinic compounds and macromolecules. Such interactions are of special interest in medical applications of porphyrinic photosensitizers that are mostly combined with macromolecular carrier systems. The macromolecular surrounding typically stabilizes the encapsulated drug and may also modify its physical properties. Moreover, the interaction with macromolecular physiological components needs to be explored to understand and control mechanisms of action and therapeutic efficacy. This review focuses on such non-covalent interactions of porphyrinic drugs with synthetic polymers as well as with biomolecules such as phospholipids or proteins. A brief introduction into various NMR spectroscopic techniques is given including chemical shift perturbation methods, NOE enhancement spectroscopy, relaxation time measurements and diffusion-ordered spectroscopy. How these NMR tools are used to address porphyrin-macromolecule interactions with respect to their function in biomedical applications is the central point of the current review.
Topics: Humans; Magnetic Resonance Spectroscopy; Micelles; Nucleic Acids; Phospholipids; Photosensitizing Agents; Polymers; Porphyrins; Proteins
PubMed: 33808335
DOI: 10.3390/molecules26071942 -
Biomacromolecules Dec 2022Porphyrins and their derivatives, representing the second-generation photosensitizers, can generate reactive oxygen species (ROS) and kill tumors upon light irradiation....
Porphyrins and their derivatives, representing the second-generation photosensitizers, can generate reactive oxygen species (ROS) and kill tumors upon light irradiation. To compensate for the fluorescence quenching and reduced ROS production caused by aggregation and rigid inherent hydrophobicity of porphyrins, a series of comparable random and block glycopolymers bearing betulin and porphyrin were prepared via RAFT polymerization. Betulin was introduced into the copolymers to decrease aggregation-induced quenching of porphyrins and to improve the photodynamic therapy (PDT) efficiency of copolymers. The characteristics, self-assembly, and photophysical chemistry properties of these copolymers were systemically studied. The effect of polymer structure on photophysical chemistry properties and cellular interaction was investigated as well to demonstrate their potential targeting for PDT applications.
Topics: Porphyrins; Photochemotherapy; Photosensitizing Agents; Triterpenes; Polymers
PubMed: 36350056
DOI: 10.1021/acs.biomac.2c00922 -
Molecules (Basel, Switzerland) Nov 2019The interest in assembling porphyrin derivatives is widespread and is accounted by the impressive impact of these suprastructures of controlled size and shapes in many... (Review)
Review
The interest in assembling porphyrin derivatives is widespread and is accounted by the impressive impact of these suprastructures of controlled size and shapes in many applications from nanomedicine and sensors to photocatalysis and optoelectronics. The massive use of porphyrin dyes as molecular building blocks of functional materials at different length scales relies on the interdependent pair properties, consisting of their chemical stability/synthetic versatility and their quite unique physicochemical properties. Remarkably, the driven spatial arrangement of these platforms in well-defined suprastructures can synergically amplify the already excellent properties of the individual monomers, improving conjugation and enlarging the intensity of the absorption range of visible light, or forming an internal electric field exploitable in light-harvesting and charge-and energy-transport processes. The countless potentialities offered by these systems means that self-assembly concepts and tools are constantly explored, as confirmed by the significant number of published articles related to porphyrin assemblies in the 2015-2019 period, which is the focus of this review.
Topics: Drug Delivery Systems; Light; Nanomedicine; Nanostructures; Porphyrins
PubMed: 31779097
DOI: 10.3390/molecules24234307 -
Angewandte Chemie (International Ed. in... Sep 2021Electrochemical sensors are indispensable in clinical diagnosis, biochemical detection and environmental monitoring, thanks to their ability to detect analytes in...
Electrochemical sensors are indispensable in clinical diagnosis, biochemical detection and environmental monitoring, thanks to their ability to detect analytes in real-time with direct electronic readout. However, electrochemical sensors are challenged by sensitivity-the need to detect low concentrations, and selectivity-to detect specific analytes in multicomponent systems. Herein, a porphyrinic metal-organic framework (PP-MOF), Mn-PCN-222 is deposited on a conductive indium tin oxide (ITO) surface. It affords Mn-PCN-222/ITO, a versatile voltammetric sensor able to detect redox-active analytes such as inorganic ions, organic hazardous substances and pollutants, including nitroaromatics, phenolic and quinone-hydroquinone toxins, heavy metal ions, biological species, as well as azo dyes. As a working electrode, the high surface area of Mn-PCN-222/ITO enables high currents, and therefore leverages highly sensitive analysis. The metalloporphyrin centre facilitates analyte-specific redox catalysis to simultaneously detect more than one analyte in binary and ternary systems allowing for detection of a wide array of trace pollutants under real-world conditions, most with high sensitivity.
Topics: Biosensing Techniques; Electrochemical Techniques; Environmental Pollutants; Manganese; Metal-Organic Frameworks; Particle Size; Porphyrins; Surface Properties; Trace Elements
PubMed: 34260128
DOI: 10.1002/anie.202107860 -
Chemical Communications (Cambridge,... Feb 2022Cooperative coacervation of a porphyrin and a polycation electrolyte gives birth to photoactive membraneless protocells liquid-liquid phase separation, where...
Cooperative coacervation of a porphyrin and a polycation electrolyte gives birth to photoactive membraneless protocells liquid-liquid phase separation, where J-aggregates are formed to offer energy transduction pathways, rendering an adaptive platform for confining photocatalytic reactions within protocell compartments.
Topics: Electrolytes; Molecular Structure; Particle Size; Photochemical Processes; Polyelectrolytes; Porphyrins
PubMed: 35098960
DOI: 10.1039/d1cc07113k -
Journal of Inorganic Biochemistry Oct 2021Electronic charge near the active site is an important factor for controlling the reactivity of metalloenzymes. Here, to investigate the effect of the cationic charge...
Electronic charge near the active site is an important factor for controlling the reactivity of metalloenzymes. Here, to investigate the effect of the cationic charge near the heme in heme proteins, we synthesized new iron porphyrin complexes (1 and 2) having cationic 3-methyl-N-methyl-2-pyrdinium group and N-methyl-2-pyridinium group at one of the four meso-positions, respectively. The N-methyl-2-pyridinium groups could be introduced by Stille coupling used palladium catalysts. Oxoiron(IV) porphyrin π-cation radical complexes (Compound I) of 1 (1-CompI) and 2 (2-CompI) are soluble in most organic solvents, allowing direct comparison of their electronic structure and reactivity with Compound I of tetramesitylporphyrin (3-CompI) and tetrakis-(2,6-dichlorophenyl)porphyrin (4-CompI) under the same conditions. Spectroscopic data for 1-CompI are close to those for 3-CompI, but the redox potential for 1-CompI is close to that of 4-CompI. Kinetic analysis of the epoxidation reactions shows that 1-CompI and 2-CompI are (~250-fold) more reactive than 3-CompI, and comparable to 4-CompI. DFT calculations allow to propose that the positive shift of the redox potential and the enhanced reactivity of 1-CompI and 2-CompI is induced by the intramolecular electric field effect of N-methyl-2-pyridinium cation, not by the electron-withdrawing effect.
Topics: Coordination Complexes; Density Functional Theory; Iron; Metalloporphyrins; Models, Chemical; Oxidation-Reduction; Porphyrins; Pyridinium Compounds; Static Electricity
PubMed: 34293682
DOI: 10.1016/j.jinorgbio.2021.111542 -
Chemosphere Nov 2022The diverse applications of porphyrin-based nano-sized metal-organic frameworks (NMOFs) lead to great exposure risks to human and environment. Understanding the cellular...
The diverse applications of porphyrin-based nano-sized metal-organic frameworks (NMOFs) lead to great exposure risks to human and environment. Understanding the cellular biological effects (such as toxicity, distribution, and localization) of porphyrinic NMOFs is a prerequisite to the assessment of their health risk. However, the characteristics of distribution, localization, and immune response induced by porphyrinic NMOFs have not been studied yet. Here, we report the size-dependent biological effects of porphyrinic NMOFs under sublethal dose. Various sizes of PCN-224 (30, 90, and 180 nm) were taken as model porphyrinic NMOFs. We found that 30 nm PCN-224 gave the highest uptake content, followed by 90 and 180 nm PCN-224. The mechanism for uptake was clathrin-mediated for 30 and 90 nm PCN-224, but clathrin- and glycosylphosphatidylinositol-mediated for 180 nm PCN-224. All PCN-224 were localized in lysosome with size-dependent velocity of colocalization transport. 30 nm PCN-224 induced the highest released cytokines than 90 and 180 nm PCN-224 accompanied with the activation of NF-κB pathway. This work reveals the mechanisms for the endocytosis of PCN-224 and the release of cytokine induced by PCN-224, which is helpful for the health risk assessment of NMOFs.
Topics: Humans; Clathrin; Cytokines; Glycosylphosphatidylinositols; Immunity; Metal-Organic Frameworks; NF-kappa B; Porphyrins
PubMed: 35850215
DOI: 10.1016/j.chemosphere.2022.135680