-
International Journal of Molecular... Jul 2021Porphyrins and their analogues feature remarkably in nature, being prosthetic groups in a wide variety of primary metabolites playing a pivotal role in many biological...
Porphyrins and their analogues feature remarkably in nature, being prosthetic groups in a wide variety of primary metabolites playing a pivotal role in many biological processes [...].
Topics: Catalysis; Macrocyclic Compounds; Porphyrins
PubMed: 34299107
DOI: 10.3390/ijms22147487 -
BMC Cancer May 2021Photodynamic therapy (PDT) is an anticancer treatment that utilizes the interaction of light and a photosensitiser (PS), promoting tumour cell death mediated by...
BACKGROUND
Photodynamic therapy (PDT) is an anticancer treatment that utilizes the interaction of light and a photosensitiser (PS), promoting tumour cell death mediated by generation of reactive oxygen species. In this study, we evaluated the in vitro photoactivity of four meso-substituted porphyrins and a porphyrin coupled to a fullerene.
METHODS
The cell line employed was the LM3 mammary adenocarcinoma, and the PS with the best photokilling activity was administered to mice bearing the LM3 subcutaneously implanted adenocarcinoma. The TEMCP porphyrin and its analogue TEMCC chlorine contain four identical carbazoyl substituents at the meso positions of the tetrapyrrolic macrocycle and have A symmetry. The TAPP derivative also has A symmetry, and it is substituted at the meso positions by aminopropoxy groups. The DAPP molecule has ABAB symmetry with aminopropoxy and the trifluoromethyl substituents in trans positions. The TCP-C dyad is formed by a porphyrin unit covalently attached to the fullerene C.
RESULTS
The PSs are taken up by the cells with the following efficiency: TAPP> TEMCP = TEMCC > DAPP >TCP-C, and the amount of intracellular PS correlates fairly with the photodamage degree, but also the quantum yields of singlet oxygen influence the PDT outcome. TAPP, DAPP, TEMCC and TEMCP exhibit high photoactivity against LM3 mammary carcinoma cells, being TAPP the most active. After topical application of TAPP on the skin of mice bearing LM3 tumours, the molecule is localized mainly in the stratum corneum, and at a lower extent in hair follicles and sebaceous glands. Systemic administration of TAPP produces a tumour: normal skin ratio of 31.4, and high accumulation in intestine and lung.
CONCLUSION
The results suggest a potential use of topical TAPP for the treatment of actinic keratosis and skin adnexal neoplasms. In addition, selectivity for tumour tissue after systemic administration highlights the selectivity of and potentiality of TAPP as a new PS.
Topics: Animals; Male; Mice; Mice, Inbred BALB C; Microscopy, Fluorescence; Photochemotherapy; Photosensitizing Agents; Porphyrins; Skin Neoplasms; Tissue Distribution
PubMed: 33985453
DOI: 10.1186/s12885-021-08286-6 -
Marine Drugs Jan 2023Two novel free porphyrins, isabellins A and B, as well as the known compounds corallistin D and deuteroporphyrin IX were isolated from a marine sponge sp. LC-MS...
Two novel free porphyrins, isabellins A and B, as well as the known compounds corallistin D and deuteroporphyrin IX were isolated from a marine sponge sp. LC-MS analysis of the crude extract revealed that the natural products were present both as free porphyrins and iron(III) coordinated hemins, designated isabellihemin A, isabellihemin B, corallistihemin D and deuterohemin IX, respectively. Structures were determined via high-resolution mass spectrometry, UV-Vis spectroscopy and extensive NOESY NMR spectroscopic experiments. The type-I alkyl substitution pattern of isabellin A and isabellihemin A was assigned unambiguously by single crystal X-ray diffraction. Biological evaluation of the metabolites revealed potent cytotoxicity for isabellin A against the NS-1 murine myeloma cell line.
Topics: Animals; Mice; Hemin; Porphyrins; Porifera; Ferric Compounds; Cell Line, Tumor; Multiple Myeloma; Australia; Magnetic Resonance Spectroscopy
PubMed: 36662214
DOI: 10.3390/md21010041 -
International Journal of Molecular... Mar 2023Chlorophyll and heme are essential molecules for photosynthesis and respiration, which are competing branches of the porphyrin metabolism pathway. Chlorophyll and heme...
Chlorophyll and heme are essential molecules for photosynthesis and respiration, which are competing branches of the porphyrin metabolism pathway. Chlorophyll and heme balance regulation is very important for the growth and development of plants. The chimeric leaves of var. were composed of central photosynthetic tissue (PT) and marginal albino tissue (AT), which were ideal materials for the study of porphyrin metabolism mechanisms. In this study, the regulatory function of ALA content on porphyrin metabolism (chlorophyll and heme balance) was revealed by comparing PT and AT, 5-Aminolevulinic Acid (ALA) exogenous supply, and interference of expression. The AT remained similar in porphyrin metabolism flow level to the PT by keeping an equal ALA content in both tissues, which was very important for the normal growth of the chimeric leaves. As the chlorophyll biosynthesis in AT was significantly inhibited, the porphyrin metabolism flow was directed more toward the heme branch. Both tissues had similar Mg contents; however, Fe content was significantly increased in the AT. The chlorophyll biosynthesis inhibition in the white tissue was not due to a lack of Mg and ALA. A 1.5-fold increase in ALA content inhibited chlorophyll biosynthesis while promoting heme biosynthesis and hemA expression. The doubling of ALA content boosted chlorophyll biosynthesis while decreasing expression and heme content. expression interference resulted in a higher ALA content and a lower chlorophyll content, while the heme content remained at a relatively low and stable level. Conclusively, a certain amount of ALA was important for the stability of porphyrin metabolism and the normal growth of plants. The ALA content appears to be able to regulate chlorophyll and heme content by bidirectionally regulating porphyrin metabolism branch direction.
Topics: Porphyrins; Aminolevulinic Acid; Ananas; Chlorophyll; Heme
PubMed: 36982348
DOI: 10.3390/ijms24065274 -
International Journal of Molecular... Dec 2022In this study, organo-inorganic nanohybrids with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin...
In this study, organo-inorganic nanohybrids with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin and its complexes with Zn(II) and Pd(II) (, M = 2H, Zn(II) and Pd(II)) into gadolinium layered hydroxide (). The combination of powder XRD, CHNS analysis, FT-IR, EDX, and TG confirmed the layered structure of the reaction products. The basal interplanar distances in samples were 22.3-22.6 Å, corresponding to the size of an intercalated tetrapyrrole molecule. According to SEM data, hybrids consisted of individual lamellar nanoparticles 20-50 nm in thickness. The enzyme-like activity of individual constituents, and sulfoporphyrins , and , and hybrid materials, was studied by chemiluminescence analysis using the ABAP/luminol system in phosphate buffer solution. All the individual porphyrins exhibited dose-dependent antioxidant properties with respect to alkylperoxyl radicals at pH 7.4. The intercalation of free base porphyrin into the preserved the radical scavenging properties of the product. Conversely, in samples containing Zn(II) and Pd(II) complexes, the antioxidant properties of the porphyrins changed to dose-dependent prooxidant activity. Thus, an efficient approach to the design and synthesis of advanced materials with switchable enzyme-like activity was developed.
Topics: Porphyrins; Gadolinium; Spectroscopy, Fourier Transform Infrared; Hydroxides
PubMed: 36499698
DOI: 10.3390/ijms232315373 -
Molecular Medicine Reports Jul 2019Nanomaterials play crucial roles in the diagnosis and treatment of diseases. Photothermal and photodynamic therapy, as two minimally invasive therapeutic methods, have... (Review)
Review
Nanomaterials play crucial roles in the diagnosis and treatment of diseases. Photothermal and photodynamic therapy, as two minimally invasive therapeutic methods, have promising potential in the diagnosis and prevention of cancer. Recently, many photothermal materials (such as noble metal material, transition metal sulfur oxides, carbon material and upconversion nanomaterial) and photodynamic materials (such as phthalein cyanogen, porphyrins and other dye molecules) have been applied in photothermal therapy (PTT) and photodynamic therapy (PDT). Moreover, as nanomaterials have suitable biocompatibility, these materials have been applied in cancer therapy. In the present review, we summarized the effects of different material types, synthesis methods, material morphologies and surface modifications on the outcomes of cancer therapy. The application of nanomaterials in PTT and PDT was introduced and the advantages and disadvantages of PTT and PDT in the prevention of cancer were discussed. Finally, we discussed the application of nanomaterials in the combination of PTT and PDT in cancer treatment.
Topics: Biocompatible Materials; Carbon; Humans; Nanostructures; Neoplasms; Photochemotherapy; Photosensitizing Agents; Porphyrins; Sulfur Oxides
PubMed: 31115497
DOI: 10.3892/mmr.2019.10218 -
Molecules (Basel, Switzerland) Jul 2022Dioxygen (O) is an environmentally benign and abundant oxidant whose utilization is of great interest in the design of bioinspired synthetic catalytic oxidation systems... (Review)
Review
Dioxygen (O) is an environmentally benign and abundant oxidant whose utilization is of great interest in the design of bioinspired synthetic catalytic oxidation systems to reduce energy consumption. However, it is unfortunate that utilization of O is a significant challenge because of the thermodynamic stability of O in its triplet ground state. Nevertheless, nature is able to overcome the spin state barrier using enzymes, which contain transition metals with unpaired -electrons facilitating the activation of O by metal coordination. This inspires bioinorganic chemists to synthesize biomimetic small-molecule iron porphyrin complexes to carry out the O activation, wherein Fe-O species have been implicated as the key reactive intermediates. In recent years, a number of Fe-O intermediates have been synthesized by activating O at iron centers supported on porphyrin ligands. In this review, we focus on a few examples of these advances with emphasis in each case on the particular design of iron porphyrin complexes and particular reaction environments to stabilize and isolate metal-O intermediates in dioxygen activation, which will provide clues to elucidate structures of reactive intermediates and mechanistic insights in biological processes.
Topics: Iron; Ligands; Metals; Oxygen; Porphyrins; Thermodynamics
PubMed: 35897870
DOI: 10.3390/molecules27154690 -
Molecules (Basel, Switzerland) Apr 2020Azides and porphyrinoids (such as porphyrin and corrole macrocycles) can give rise to new derivatives with significant biological properties and as new materials'... (Review)
Review
Azides and porphyrinoids (such as porphyrin and corrole macrocycles) can give rise to new derivatives with significant biological properties and as new materials' components. Significant synthetic approaches have been studied. A wide range of products (e.g., microporous organic networks, rotaxane and dendritic motifs, dendrimers as liquid crystals, as blood substitutes for transfusions and many others) can now be available and used for several medicinal and industrial purposes.
Topics: Azides; Molecular Structure; Porphyrins
PubMed: 32260294
DOI: 10.3390/molecules25071662 -
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 -
Scientific Reports May 2022Fe(III) 5,10,15,20-(tetraphenyl)porphyrin chloride (FeTPP) and Co(III) 5,10,15,20-(tetraphenyl)porphyrin chloride (CoTPP) were adsorbed on carbon Vulcan and studied as...
Fe(III) 5,10,15,20-(tetraphenyl)porphyrin chloride (FeTPP) and Co(III) 5,10,15,20-(tetraphenyl)porphyrin chloride (CoTPP) were adsorbed on carbon Vulcan and studied as electrocatalysts for the oxygen reduction reaction (ORR) before and after pyrolysis. The pyrolysis process was also simulated through ab initio molecular dynamic simulations and the minimum energy path for the O dissociation after the interaction with the metal center of the FeTPP and CoTPP were calculated. After the pyrolysis the FeTPP showed the best performances reducing O completely to HO with increased limiting current and lower overpotential. Tafel slops for the various catalysts did not change after the pyrolytic process suggesting that the mechanism for the ORR is not affected by the heat treatment. TEM images, X-ray diffraction, XPS spectroscopy, Fe Mössbauer, and DFT simulations, suggest that there is no breakdown of the macrocyclic complex at elevated temperatures, and that the macro cyclic geometry is preserved. Small variations in the Metal-O (M-O) binding energies and the M-N bond length were observed which is attributed to the dispersive interaction between the macrocycles and the irregular surface of the Vulcan substrate induced by the heat treatment and causing better interaction with the O molecule. The theoretical strategy herein applied well simulate and explain the nature of the M-N-C active sites and the performances towards the ORR.
Topics: Carbon; Chlorides; Ferric Compounds; Oxidation-Reduction; Oxygen; Porphyrins
PubMed: 35577862
DOI: 10.1038/s41598-022-11820-6