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Journal of Inorganic Biochemistry Oct 2023Heme enzymes are involved in the binding and metabolism of hydroxylamine (RNHOH) and aldoxime (RCH=NOH) compounds (R = H, alkyl, aryl). We report the synthesis and...
Heme enzymes are involved in the binding and metabolism of hydroxylamine (RNHOH) and aldoxime (RCH=NOH) compounds (R = H, alkyl, aryl). We report the synthesis and X-ray crystal structure of a metalloporphyrin in complex with an arylhydroxylamine, namely that of (TPP)Rh(PhNHOH)(CHCl) (TPP = tetraphenylpophryinato dianion). The crystal structure reveals, in addition to N-binding of PhNHOH to Rh, the presence of an intramolecular H-bond between the hydroxylamine -OH proton and a porphyrin N-atom. Results from density functional theory (DFT) calculations support the presence of this intramolecular H-bond in this global minimum structure, and a natural bond order (NBO) analysis reveals that this H-bond comprises a donor π N=C (porphyrin) to acceptor σ* O-H (hydroxylamine) interaction of 2.32 kcal/mol. While DFT calculations predict the presence of similar intramolecular H-bond interactions in the related aldoxime complexes (TPP)Rh(RCH=NOH)(CHCl) in their global minima structures, the X-ray crystal structure obtained for the (TPP)Rh(CH(CH)CH=NOH)(CHCl) complex is consistent with the local (non-global) minima conformation that does not have this intramolecular H-bond interaction.
Topics: Porphyrins; Rhodium; Metalloporphyrins; Hydroxylamines; Oximes
PubMed: 37517330
DOI: 10.1016/j.jinorgbio.2023.112337 -
Journal of Materials Chemistry. B Nov 2023Covalent organic frameworks (COFs) have promising applications in enhanced phototherapy. However, COFs that can sustainably play a role in phototherapy without...
Covalent organic frameworks (COFs) have promising applications in enhanced phototherapy. However, COFs that can sustainably play a role in phototherapy without continuous irradiation are extremely scarce. Herein, we report the fabrication of porphyrin-anthracene multifunctional COFs (Por-DPA) for sustainable photosterilization and bacterial-infected wound healing. A porphyrin photosensitizer, as one of the monomers, was used to provide photothermal and photodynamic activities under irradiation. An anthracene derivative, a good chemical source of singlet oxygen (O), was selected as another monomer to capture O and release it continuously cycloreversion in the dark. The prepared Por-DPA COF prevents the self-aggregation quenching of the photosensitizer and thermal damage caused by continuous exposure to external light sources. Besides, Por-DPA exhibits good photothermal conversion performance and efficient O production capacity through dual pathways of photosensitization and cycloreversion. The developed sustainable photosterilization platform not only has good bactericidal effects on and , but also promotes wound healing without obvious side effects, and is expected to be a novel efficient bactericide.
Topics: Photosensitizing Agents; Metal-Organic Frameworks; Porphyrins; Phototherapy; Singlet Oxygen
PubMed: 37987617
DOI: 10.1039/d3tb02017g -
Chemical Reviews May 2022The replacement of one or more pyrrolic building block(s) of a porphyrin by a nonpyrrolic heterocycle leads to the formation of so-called pyrrole-modified porphyrins... (Review)
Review
The replacement of one or more pyrrolic building block(s) of a porphyrin by a nonpyrrolic heterocycle leads to the formation of so-called pyrrole-modified porphyrins (PMPs), porphyrinoids of broad structural variability. The wide range of coordination environments (type, number, charge, and architecture of the donor atoms) that the pyrrole-modified frameworks provide to the central metal ions, the frequent presence of donor atoms at their periphery, and their often observed nonplanarity or conformational flexibility distinguish the complexes of the PMPs clearly from those of the traditional square-planar, dianionic, N-coordinating (hydro)porphyrins. Their different coordination properties suggest their utilization in areas beyond which regular metalloporphyrins are suitable. Following a general introduction to the synthetic methodologies available to generate pyrrole-modified porphyrins, their general structure, history, coordination chemistry, and optical properties, this Review highlights the chemical, electronic (optical), and structural differences of specific classes of metalloporphyrinoids containing nonpyrrolic heterocycles. The focus is on macrocycles with similar "tetrapyrrolic" architectures as porphyrins, thusly excluding the majority of expanded porphyrins. We highlight the relevance and application of these metal complexes in biological and technical fields as chemosensors, catalysts, photochemotherapeutics, or imaging agents. This Review provides an introduction to the field of metallo-PMPs as well as a comprehensive snapshot of the current state of the art of their synthesis, structures, and properties. It also aims to provide encouragement for the further study of these intriguing and structurally versatile metalloporphyrinoids.
Topics: Coordination Complexes; Metalloporphyrins; Molecular Conformation; Porphyrins; Pyrroles
PubMed: 35302354
DOI: 10.1021/acs.chemrev.1c00694 -
Chemical Reviews Jan 2022Direct photocatalyzed hydrogen atom transfer (-HAT) can be considered a method of choice for the elaboration of aliphatic C-H bonds. In this manifold, a photocatalyst... (Review)
Review
Direct photocatalyzed hydrogen atom transfer (-HAT) can be considered a method of choice for the elaboration of aliphatic C-H bonds. In this manifold, a photocatalyst (PC) exploits the energy of a photon to trigger the homolytic cleavage of such bonds in organic compounds. Selective C-H bond elaboration may be achieved by a judicious choice of the hydrogen abstractor (key parameters are the electronic character and the molecular structure), as well as reaction additives. Different are the classes of PCs available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, a metal-oxo porphyrin and a tris(amino)cyclopropenium radical dication. The processes (mainly C-C bond formation) are in most cases carried out under mild conditions with the help of visible light. The aim of this review is to offer a comprehensive survey of the synthetic applications of photocatalyzed -HAT.
Topics: Hydrogen; Ketones; Molecular Structure; Porphyrins
PubMed: 34355884
DOI: 10.1021/acs.chemrev.1c00263 -
Molecules (Basel, Switzerland) Oct 2022The syntheses of two triads are reported. Each triad is composed of two perylene-monoimides linked to a porphyrin via an ethyne unit, which bridges the perylene...
The syntheses of two triads are reported. Each triad is composed of two perylene-monoimides linked to a porphyrin via an ethyne unit, which bridges the perylene 9-position and a porphyrin 5- or 15-position. Each triad also contains a single tether composed of an alkynoic acid or an isophthalate unit. Each triad provides panchromatic absorption (350-700 nm) with fluorescence emission in the near-infrared region (733 or 743 nm; fluorescence quantum yield ~0.2). The syntheses rely on the preparation of -AB-porphyrins bearing one site for tether attachment (A), an aryl group (B), and two open meso-positions. The AB-porphyrins were prepared by the condensation of a 1,9-diformyldipyrromethane and a dipyrromethane. The installation of the two perylene-monoimide groups was achieved upon the 5,15-dibromination of the porphyrin and the subsequent copper-free Sonogashira coupling, which was accomplished before or after the attachment of the tether. The syntheses provide relatively straightforward access to a panchromatic absorber for use in bioconjugation or surface-attachment processes.
Topics: Perylene; Porphyrins
PubMed: 36235037
DOI: 10.3390/molecules27196501 -
Small (Weinheim An Der Bergstrasse,... Feb 2022To better exploit all-liquid 3D architectures, it is essential to understand dynamic processes that occur during printing one liquid in a second immiscible liquid. Here,...
To better exploit all-liquid 3D architectures, it is essential to understand dynamic processes that occur during printing one liquid in a second immiscible liquid. Here, the interfacial assembly and transition of 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (H TPPS) over time provides an opportunity to monitor the interfacial behavior of nanoparticle surfactants (NPSs) during all-liquid printing. The formation of J-aggregates of H TPPS at the interface and the interfacial conversion of the J-aggregates of H TPPS to H-aggregates of H TPPS is demonstrated by interfacial rheology and in situ atomic force microscopy. Equally important are the chromogenic changes that are characteristic of the state of aggregation, where J-aggregates are green in color and H-aggregates are red in color. In all-liquid 3D printed structures, the conversion in the aggregate state with time is reflected in a spatially varying change in the color, providing a simple, direct means of assessing the aggregation state of the molecules and the mechanical properties of the assemblies, linking a macroscopic observable (color) to mechanical properties.
Topics: Porphyrins; Rheology; Surface-Active Agents
PubMed: 35142068
DOI: 10.1002/smll.202105017 -
ChemMedChem Oct 2020Porphyrin photosensitizers are widely used in photodynamic therapy (PDT) because of their unique diagnostic and therapeutic functions. However, many factors such as poor... (Review)
Review
Porphyrin photosensitizers are widely used in photodynamic therapy (PDT) because of their unique diagnostic and therapeutic functions. However, many factors such as poor water solubility and instability of porphyrin compounds have limited their clinical application. Metal-organic frameworks (MOFs) have the beneficial characteristics of versatility, high porosity, and excellent biocompatibility. Porphyrin-MOF nanomaterials have attracted the attention of researchers because MOFs can effectively suppress the quenching caused by the self-aggregation of porphyrin compounds and promote drug delivery. This article reviews the latest applications of porphyrin-MOF nanomedicine in type II photodynamic therapy by increasing tumour cell oxygen concentration, depleting tumour cell functional molecules and releasing signal molecules. Current potential limitations and future applications are also emphasized and discussed herein.
Topics: Antineoplastic Agents; Biocompatible Materials; Cell Proliferation; Humans; Metal-Organic Frameworks; Nanomedicine; Neoplasms; Photochemotherapy; Photosensitizing Agents; Porphyrins
PubMed: 32715651
DOI: 10.1002/cmdc.202000353 -
Journal of Materials Chemistry. B Jul 2023Porphyrins are naturally occurring organic molecules that have attracted widespread attention for their potential in the field of biomedical research. Porphyrin-based... (Review)
Review
Porphyrins are naturally occurring organic molecules that have attracted widespread attention for their potential in the field of biomedical research. Porphyrin-based metal-organic frameworks (MOFs) that utilize porphyrin molecules as organic ligands have gained attention from researchers due to their excellent results as photosensitizers in tumor photodynamic therapy (PDT). Additionally, MOFs hold significant promise and potential for other tumor therapeutic approaches due to their tunable size and pore size, excellent porosity, and ultra-high specific surface area. Active delivery of nanomaterials targeted molecules for tumor therapy has demonstrated greater accumulation, lower drug doses, higher therapeutic efficacy, and reduced side effects relative to passive targeting through the enhanced permeation and retention effect (EPR). This paper presents a comprehensive review of the targeting methods employed by porphyrin-based MOFs in tumor targeting therapy over the past few years. It further discusses the applications of porphyrin-based MOFs for targeted cancer therapy through various therapeutic methods. The objective of this paper is to provide a valuable reference and source of ideas for targeted therapy using porphyrin-based MOF materials and to inspire further exploration of their potential in the field of cancer therapy.
Topics: Humans; Metal-Organic Frameworks; Porphyrins; Neoplasms; Photosensitizing Agents; Drug Delivery Systems
PubMed: 37305964
DOI: 10.1039/d3tb00632h -
Molecules (Basel, Switzerland) Nov 2021Colorectal cancer (CRC) is a leading cause of cancer-related death. The demand for new therapeutic approaches has increased attention paid toward therapies with high... (Review)
Review
Colorectal cancer (CRC) is a leading cause of cancer-related death. The demand for new therapeutic approaches has increased attention paid toward therapies with high targeting efficiency, improved selectivity and few side effects. Porphyrins are powerful molecules with exceptional properties and multifunctional uses, and their special affinity to cancer cells makes them the ligands par excellence for anticancer drugs. Porphyrin derivatives are used as the most important photosensitizers (PSs) for photodynamic therapy (PDT), which is a promising approach for anticancer treatment. Nevertheless, the lack of solubility and selectivity of the large majority of these macrocycles led to the development of different photosensitizer complexes. In addition, targeting agents or nanoparticles were used to increase the efficiency of these macrocycles for PDT applications. On the other hand, gold tetrapyrrolic macrocycles alone showed very interesting chemotherapeutic activity without PDT. In this review, we discuss the most important porphyrin derivatives, alone or associated with other drugs, which have been found effective against CRC, as we describe their modifications and developments through substitutions and delivery systems.
Topics: Colorectal Neoplasms; Humans; Nanoparticles; Photochemotherapy; Photosensitizing Agents; Porphyrins
PubMed: 34885849
DOI: 10.3390/molecules26237268 -
International Journal of Molecular... May 2020The application of porphyrins and their derivatives have been investigated extensively over the past years for phototherapy cancer treatment. Phototherapeutic Porphyrins... (Review)
Review
The application of porphyrins and their derivatives have been investigated extensively over the past years for phototherapy cancer treatment. Phototherapeutic Porphyrins have the ability to generate high levels of reactive oxygen with a low dark toxicity and these properties have made them robust photosensitizing agents. In recent years, Porphyrins have been combined with various nanomaterials in order to improve their bio-distribution. These combinations allow for nanoparticles to enhance photodynamic therapy (PDT) cancer treatment and adding additional nanotheranostics (photothermal therapy-PTT) as well as enhance photodiagnosis (PDD) to the reaction. This review examines various porphyrin-based inorganic nanoparticles developed for phototherapy nanotheranostic cancer treatment over the last three years (2017 to 2020). Furthermore, current challenges in the development and future perspectives of porphyrin-based nanomedicines for cancer treatment are also highlighted.
Topics: Animals; Biocompatible Materials; Carbon; Humans; Magnetic Iron Oxide Nanoparticles; Mammary Neoplasms, Experimental; Metal Nanoparticles; Mice; Nanoparticles; Neoplasms; Photochemotherapy; Porphyrins; Quantum Dots; Silicon Dioxide; Theranostic Nanomedicine
PubMed: 32397477
DOI: 10.3390/ijms21093358