- Thermochemistry of solution of some quaternized derivatives of tetra(4-pyridyl)porphine in water
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Quaternized tetra(4-pyridyl)porphine derivatives: tetra(N-carboxymethyl-4- pyridyl)porphine tetrachloride, tetra(N-carboxymethyl-4-pyridyl)porphine tetrabromide, tetra(N-methyl-4-pyridyl)porphine tetraiodide, and tetra(N-ethoxycarbonylmethyl-4-pyridyl)porphine tetrachloride, were synthesized, isolated, and purified. The enthalpies of solution of these compounds in water at 298.15 K were determined calorimetrically. The effect of functional substituents in porphyrin ligands on the enthalpies of solution is discussed.
- Berezin,Berezina,Semeikin,V'Yugin
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- Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds
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A series of chiral synthetic compounds is reported that shows intricate but specific hierarchical assembly because of varying positions of coordination and hydrogen bonds. The evolution of the aggregates (followed by absorption spectroscopy and temperature-dependent circular dichroism studies in solution) reveal the influence of the proportion of stereogenic centers in the side groups connected to the chromophore ring in their optical activity and the important role of pyridyl groups in the self-assembly of these chiral macrocycles. The optical activity spans 2 orders of magnitude depending on composition and constitution. Two of the aggregates show very high optical activity even though the isolated chromophores barely give a circular dichroism signal. Molecular modeling of the aggregates, starting from the pyridine-zinc(II) porphyrin interaction and working up, and calculation of the circular dichroism signal confirm the origin of this optical activity as the chiral supramolecular organization of the molecules. The aggregates show a broad absorption range, between approximately 390 and 475 nm for the transitions associated with the Soret region alone, that spans wavelengths far more than the isolated chromophore. The supramolecular assemblies of the metalloporphyrins in solution were deposited onto highly oriented pyrolitic graphite in order to study their hierarchy in assembly by atomic force microscopy. Zero and one-dimensional aggregates were observed, and a clear dependence on deposition temperature was shown, indicating that the hierarchical assembly took place largely in solution. Moreover, scanning electron microscopy images of porphyrins and metalloporphyrins precipitated under out-of-equilibrium conditions showed the dependence of the number and position of chiral amide groups in the formation of a fibrillar nanomaterial. The combination of coordination and hydrogen bonding in the complicated assembly of these molecules-where there is a clear hierarchy for zinc(II)-pyridyl interaction followed by hydrogen-bonding between amide groups, and then van der Waals interactions-paves the way for the preparation of molecular materials with multiple chromophore environments.
- Oliveras-González, Cristina,Di Meo, Florent,González-Campo, Arántzazu,Beljonne, David,Norman, Patrick,Simón-Sorbed, Maite,Linares, Mathieu,Amabilino, David B.
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- Novel Amphiphilic G-Quadruplex Binding Synthetic Derivative of TMPyP4 and Its Effect on Cancer Cell Proliferation and Apoptosis Induction
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Porphyrins are well-known anticancer agents because of their high binding affinity for G-quadruplex DNA and excellent photophysical properties. Several studies carried out using TMPyP4 established it as an efficient chemotherapeutic and a photodynamic therapeutic (PDT) agent, but its use as a lead molecule has been restricted because of its high level of binding to double-stranded DNA (dsDNA), which may have side effects on normal cells and tissues. To minimize its interaction with dsDNA and to enhance internalization into cells, an analogue of TMPyP4 (5Me) was synthesized. Its selectivity for G-quadruplex DNA over dsDNA was evaluated by spectroscopic methods, and its role in stabilizing G-quadruplex DNA was assessed by fluorescence lifetime and thermal melting experiments. Biophysical studies indicated that 5Me interacts well with G-quadruplex DNA. In vitro cytotoxicity experiments with tumor cell lines (PANC-1, B16F10, and MDA MB 231) have revealed that 5Me can inhibit the growth of cancer cells comparable to TMPyP4. MTT and apoptotic assays demonstrated the ability of 5Me to specifically affect cancer cells over normal cells. Cell cycle analysis showed that 5Me, like TMPyP4, induces G2/M phase cell cycle arrest. In addition, 5Me is more effectively taken up by both cancer and normal cells than TMPyP4. In addition, we have noticed that 5Me is more efficient than TMPyP4 in inhibiting the growth of the cancer cells after irradiation with light (600-720 nm, 20 J/cm2, 50 mW/cm2). By and large, these experimental results indicate that 5Me can be an efficient chemotherapeutic as well as a PDT agent.
- Chilakamarthi, Ushasri,Koteshwar, Devulapally,Jinka, Sudhakar,Vamsi Krishna, Narra,Sridharan, Kathyayani,Nagesh, Narayana,Giribabu, Lingamallu
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- Oxygen sensing materials based on mesoporous silica MCM-41 and Pt(II)-porphyrin complexes
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The preparation and properties of luminescent oxygen sensing materials based on two Pt(II)-porphyrin complexes: platinum meso-tetrakis(4-N-methylpyridyl)porphyrin (PtTMPyP4+) and platinum meso-tetrakis(4-N-pyridyl)porphyrin (PtTPyP) assembled in mesoporous silica (MCM-41) are described. The luminescence of Pt(II)-porphyrin/MCM-41 assembly materials can be extremely quenched by molecular oxygen with good sensitivity (I0/I100 > 7) and rapid response times (4+/MCM-41 (20 mg g-1) exhibits very high sensitivity (I0/I00 > 50). Even when the concentration of oxygen is 1%, the luminescence intensity of PtTMPyP 4+/MCM-41 (20 mg g-1) can be quenched by 83.33%. The Royal Society of Chemistry 2005.
- Zhang, Huidong,Sun, Yinghui,Ye, Kaiqi,Zhang, Ping,Wang, Yue
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- Synthesis, RNA binding and nuclease activity of porphyrin-hydroxamic acid derivatives
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The interaction modes and nuclease activity against RNA of methylpyridiniumyl/phenyl-hydroxamic acid porphyrin adducts have been investigated. These compounds are derived from the tetracationic meso-tetrakis(N-methyl-4-pyridiniumyl)porphyrin (H2TMPyP-4) by replacing one or two pyridinium rings with a phenyl group. This group is bearing an aliphatic chain of three carbon atoms in the para position to a hydroxamic acid. A different interaction mode is observed depending on the number of charges and hydroxamic acid function. The nuclease activity of the porphyrin adducts against RNA has been demonstrated. Also the effect of the presence of various lanthanide ions on the porphyrin nuclease activity has been tested.
- Marketaki, Maria,Touloupakis, Eleftherios,Charalambidis, Georgios,Chalbot, Marie-Cécile,Ghanotakis, Demetrios F.,Coutsolelos, Athanassios G.
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- A platinum functional porphyrin conjugate: An excellent cancer killer for photodynamic therapy
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A novel tetracationic porphyrin-platinum(II) conjugate was synthesized and characterized. This complex, 4Pt(dach)ClTPyP, showed reasonable water solubility, lack of aggregation, and high singlet oxygen quantum yield. It also exhibited low dark cytotoxicity and excellent photocytotoxicity (Colon26: 0.17 μM; Sarcoma180: 0.25 M). The mechanisms of cell death have been investigated and are attributed to high singlet oxygen generation, internalization into nucleus, and a caspase-3 induced apoptosis pathway. In the in vivo photodynamic therapy (PDT) assay, 4Pt(dach)ClTPyP completely killed tumor tissue, not simply displaying inhibition of tumor growth, and no recurrence was seen 18 days later after a single administration. All these findings of 4Pt(dach)ClTPyP shed light on a potential clinical use for cancer PDT in the future.
- Hu, Xiaojun,Ogawa, Kazuma,Li, Siqiaozhi,Kiwada, Tatsuto,Odani, Akira
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- A supramolecular bifunctional artificial enzyme with superoxide dismutase and glutathione peroxidase activities
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For constructing a bifunctional antioxidative enzyme with both superoxide dismutase (SOD) and glutathione peroxidase (GPx) activities, a supramolecular artificial enzyme was successfully constructed by the self-assembly of the Mn(III)meso-tetra[1-(1-adamantyl methyl ketone)-4-pyridyl] porphyrin (MnTPyP-M-Ad) and cyclodextrin-based telluronic acid (2-CD-TeO3H) through host-guest interaction in aqueous solution. The self-assembly of the adamantyl moieties of Mn(III) porphyrin and the β-CD cavities of 2-CD-TeO3H was demonstrated by the NMR spectra. In this supramolecular enzyme model, the Mn(III) porphyrin center acted as an efficient active site of SOD and tellurol moiety endowed GPx activity. The SOD-like activity (IC50) of the new catalyst was found to be 0.116 μM and equals to 2.56% of the activity of the native SOD. Besides this, supramolecular enzyme model also showed a high GPx activity, and a remarkable rate enhancement of 27-fold compared to the well-known GPx mimic ebselen was observed. More importantly, the supramolecular artificial enzyme showed good thermal stability.
- Yu, Shuangjiang,Huang, Xin,Miao, Lu,Zhu, Junyan,Yin, Yanzhen,Luo, Quan,Xu, Jiayu,Shen, Jiacong,Liu, Junqiu
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- Synthesis and characterization of a new magnetic nanocomposite with metalloporphyrin (Co-TPyP) and sulfated tin dioxide (Fe3O4@SnO2/SO42-), and investigation of its photocatalytic effects in the degradation of Rhodamine B
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To achieve the synthesis of (Fe3O4@SnO2/SO42-), after the preparation of magnetic nanoparticles of Fe3O4 (MNP), tin dioxide was supported on the MNP, and it was sulfated using ammonium sulfate. To improve the photocatalytic activity of this magnetic nanocatalyst, after the synthesis of 5,10,15,20-tetra(4-pyridyl) porphyrin and its cobalt metalloporphyrin, (Co-TPyP) was stabilized on Fe3O4@SnO2/SO42-. The structure and morphology were characterized by XRD, EDX, FT-IR, SEM and FE-SEM. The X-ray diffraction studies showed tetragonal SnO2 and the orthorhombic structure of Fe3O4. The Fe3O4@SnO2/SO42- is an acidic heterogeneous nanocatalyst with excellent magnetic properties and can be easily separated from the reaction mixture by an external magnetic field. The photocatalytic activity was investigated by studying the photodegradation of Rhodamine B (RhB) in aqueous solution under visible light irradiation. The simplicity of the workup processes, the low cost of the catalyst and its high efficiency in the degradation of RhB are outstanding advantages of this procedure.
- Ghafuri, Hossein,Mohammadi, Fatemeh,Rahimi, Rahmatallah,Mohammadiyan, Esmaeel
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- Synthesis and photophysical properties of the photoactivatable cationic porphyrin 5-(4-N-dodecylpyridyl)-10,15,20-tri(4-N-methylpyridyl)-21H,23H-porphyrin tetraiodide for anti-malaria PDT
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This article describes a new synthetic method for obtaining three water soluble porphyrins. The more sophisticated porphyrin [5-(4-N-dodecylpyridyl)-10,15,20-tri(4-N-methylpyridyl)-21H,23H-porphyrin tetraiodide], also named C12 porphyrin, was obtained through a three step methodology. The improvements, compared to syntheses described in the literature, mostly concern the purification procedures. The photophysical properties of the three porphyrins are described and the C12 porphyrin presents a very good 1O2 yield compared to its chemical intermediates. This porphyrin seems to be a very promising candidate for PDT applications.
- Stallivieri, Aurélie,Le Guern, Florent,Vanderesse, Régis,Meledje, Esme,Jori, Giulio,Frochot, Céline,Acherar, Samir
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- Synthesis and Antimicrobial Activity of a Pyridine Complex of (Acetato)[5,10,15,20-tetrakis(N-methylpyridin- 4-yl)porphinato]manganese(III) Tetratosylate
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Aiming at preparation of new biologically active donor?acceptor complexes, a water-soluble manganese(III) complex with 5,10,15,20-tetrakis(N-methylpyridin-4-yl)porphine tetratosylate was synthesized and its reaction with pyridine was studied by spectrophotometry using the molar ratio method. In water a 1: 1 donor?acceptor complex with pyridine is formed. The chemical structure of the compounds was established by spectral methods. (Acetato)[5,10,15,20-tetrakis(N-methylpyridin-4-yl)porphinato]manganese(III) tetratosylate and especially its donor?acceptor complex with pyridine showed an antifungal activity against Candida albicans.
- Ovchenkova,Bichan,Lyubimtsev,Garasko,Lomova
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- In vitro photodynamic inactivation of conidia of the phytopathogenic fungus Colletotrichum graminicola with cationic porphyrins
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Photodynamic inactivation (PDI) is an efficient approach for the elimination of a series of microorganisms; however, PDI involving phytopathogenic filamentous fungi is scarce in the literature. In the present study, we have demonstrated the photoinactivating properties of five cationic meso-(1-methyl-4-pyridinio)porphyrins on conidia of the phytopathogen Colletotrichum graminicola. For this purpose, photophysical properties (photostability and 1O2 singlet production) of the porphyrins under study were first evaluated. PDI assays were then performed with a fluence of 30, 60, 90 and 120 J cm-2 and varying the porphyrin concentration from 1 to 25 μmol L-1. Considering the lowest concentration that enabled the best photoinactivation, with the respective lowest effective irradiation time, the meso-(1-methyl-4-pyridinio)porphyrins herein studied could be ranked as follows: triple-charged 4 (1 μmol L-1 with a fluence of 30 J cm-2) > double-charged-trans2 (1 μmol L-1 with 60 J cm-2) > tetra-charged 5 (15 μmol L-1 with 90 J cm-2) > mono-charged 1 (25 μmol L-1 with 120 J cm-2). Double-charged-cis-porphyrin 3 inactivated C. graminicola conidia in the absence of light. Evaluation of the porphyrin binding to the conidia and fluorescence microscopic analysis were also performed, which were in agreement with the PDI results. In conclusion, the cationic porphyrins herein studied were considered efficient photosensitizers to inactivate C. graminicola conidia. The amount and position of positive charges are related to the compounds' amphiphilicity and therefore to their photodynamic activity.
- Vandresen, Camila Chevonica,Gon?alves, Alan Guilherme,Ducatti, Diogo Ricardo Bazan,Murakami, Fabio Seigi,Noseda, Miguel Daniel,Duarte, Maria Eugenia Rabello,Barreira, Sandra Mara Woranovicz
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- Effect of structural variation on tumor targeting efficacy of cationically charged porphyrin derivatives: Comparative in-vitro and in-vivo evaluation for possible potential in PET and PDT
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Tetracationic (TMPyP) and tricationic porphyrin (TriMPyCOOHP) derivatives were synthesized, characterized and investigated for binding with DNA by Isothermal Titration Calorimetry as well as by UV–Vis spectroscopy in order to study the effect of structural variation on tumor targeting efficacy of cationically charged porphyrin derivatives. Fluorescence cell imaging studies performed in cancer cell lines corroborated the findings of aforementioned studies. Photocytotoxicity experiments in A549 cell lines revealed relatively higher light dependent cytotoxic effects exerted by TMPyP compared to TriMPyCOOHP. In-vivo experiments in tumor bearing animal model revealed relatively longer retention of 68Ga-TMPyP in tumorous lesion compared to that of 68Ga-TriMPyCOOHP. The study reveals that removal of one of the positive charges of the tetracationic porphyrin derivatives significantly reduces their DNA binding ability and cytotoxicity as well as brings changes in the pharmacokinetic pattern and tumor retention in small animal model.
- Guleria, Mohini,Suman, Shishu K.,Mitra, Jyotsna B.,Shelar, Sandeep B.,Amirdhanayagam, Jeyachitra,Sarma, Haladhar D.,Dash, Ashutosh,Das, Tapas
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- Preparation, characterization, and electrical properties of a self-assembled meso-pyridyl porphyrin monolayer on gold surfaces
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A meso-pyridyl porphyrin, 5-(4-(2-(4-(S-acetylthiomethyl)phenyl)ethynyl)phenyl)-10,15,20-tris(4-pyridyl) porphyrin was synthesized by coupling of 5-{4-ethynyl}phenyl-10,15,20-tris(4-pyridyl) porphyrin with 4-(S-acetylthiomethyl)-4-iodobenzene under mild palladium coupling conditions. The meso-pyridyl porphyrin was used for the preparation of self assembled monolayers on gold substrates. The gold substrates were made by the thermal evaporation of gold on oxidized Si(100) surfaces. The self-assembled monolayers (SAMs) were characterized using ground state UV absorption and X-ray photoelectron spectroscopic (XPS) techniques and also by scanning probe microscopy (SPM) techniques. The UV-absorption spectra of the porphyrin monolayer exhibited a 10 nm red shift in the Soret band compared to the porphyrin in CHCl3 solution. This indicates that the porphyrin molecules are aligned on the gold substrate in a side-by-side orientation. The typical shifts in the binding energy by XPS revealed that the chemisorption of the thiolate species of the porphyrin to the surface occurs through a strong sulfur-gold bonding mechanism. Basic hexagonal (√3×√3) R 30° well ordered self-assembled monolayers of meso-pyridyl porphyrin was observed by molecular-resolution atomic force microscopy (AFM). Room temperature current-voltage (I-V) spectra by scanning tunneling spectroscopy (STS) at varying set point current were collected to study the electronic transport properties of the monolayers on the gold surface. CSIRO 2005.
- Sathyapalan, Amarchand,Lohani, Anup,Santra, Sangita,Goyal, Saurabh,Ravikanth,Mukherji, Soumyo,Rao, V. Ramgopal
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- Synthesis and antibacterial activity of new poly-S-lysine-porphyrin conjugates
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Studies on the synthesis, structural elucidation, and biological evaluation of new conjugates of poly-S-lysine with meso-substituted porphyrins are described. The new conjugates were used in the photoinactivation of antibiotic-resistant Gram-positive bacteria (Staphylococcus aureus strains ATCC 25923 and MRSA 110) and Gram-negative bacteria (Escherichia coli strain O4). The results show that the cationic conjugates are able to photosensitize the efficient inactivation of both types of bacteria.
- Tomé, Jo?o P. C.,Neves, Maria G. P. M. S.,Tomé, Augusto C.,Cavaleiro, José A. S.,Soncin, Marina,Magaraggia, Michela,Ferro, Stefania,Jori, Giulio
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- A Noble-Metal-Free Heterogeneous Photosensitizer-Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light
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An entirely earth-abundant chromophore-relay water oxidation catalyst triad system, which is robust and efficient at neutral pH, is presented. The synthesis involves the coordination of a porphyrin derivative to a bridging Fe(CN)5 group, which is then reacted with Co ions to prepare a covalently linked chromophore–Prussian blue analogue assembly. Light-driven water oxidation studies in the presence of an electron scavenger indicate that the triad is active and it maintains a steady activity for at least three hours. Transient absorption experiments and computational studies reveal that the Fe(CN)5 group is more than a linker as it takes part in electron-transfer and co-operates with porphyrin in the charge separation process.
- Ulusoy Ghobadi, T. Gamze,Akhuseyin Yildiz, Elif,Buyuktemiz, Muhammed,Sadigh Akbari, Sina,Topkaya, Derya,?sci, ümit,Dede, Yavuz,Yaglioglu, H. Gul,Karadas, Ferdi
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- Porphyrinic coordination lattices with fluoropillars
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The combined use of porphyrins and fluorides to fabricate pillared coordination sheets is presented. Multiple features, such as coordinatively unsaturated metal sites, an optimal pore space, and a fluoride-decorated internal surface, make the new materials ideal adsorbents with high capacity and affinity for carbon dioxide. In addition, the new materials are shown to be suitable single-source precursors to afford fluorine-doped graphene analogues for application in oxygen reduction reaction electrodes.
- Lin, Qipu,Mao, Chengyu,Kong, Aiguo,Bu, Xianhui,Zhao, Xiang,Feng, Pingyun
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- Synthesis of coordination polymers of cobalt meso-pyridylporphyrins and its oxygen reduction properties
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The present work sheds light on the role of coordinating side groups on the porphine ring in deciding the extent of the metalation reaction as well as the formation of coordination polymers of porphyrin. Electrocatalytic activity of coordination polymers of isomers of pyridylporphyrins has been investigated after pyrolysing them at different temperatures. The pyrolysed materials were characterized by XRD, XPS, SEM, TEM and BET techniques. The electrocatalytic behaviour of the sample were investigated by modifying the glassy carbon electrode with the sample (in both normal and pyrolysed form). The electrode modified using the pyrolysed sample of polymerized pyridylporphyrin at 800 °C acted as a good electrocatalyst for the reduction of dioxygen. The studies on kinetics of oxygen reduction using rotating disk electrode shows the reduction through 2-electron pathway forming H2O2 in alkaline medium.
- Saran, Neha,Thomas, Tincy Lis,Bhavana, Purushothaman
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- Cationic porphyrin@SPION nanospheres as multifunctional anticancer therapeutics: Magnetic targeting, photodynamic potential and bio-safety research
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The synthesis and characterization of carboxyl-functionalized superparamagnetic iron oxide nanoparticles (SPION)-attached cationic porphyrins with different positive charges (porphyrin@SPION) are described as pH-sensitive, multifunctional photosensitization. These nanospheres exhibit excellent targeted cell accumulation under external magnetic field and outstanding cell photocytotoxicity in weak acidic solution, which is the pH for most tumors. The dicationic porphyrin@SPION has the smartest pH-responding release and lowest half-maximal inhibitory concentration (IC50) values after visible light irradiation against HeLa cells. Moreover, the delivery safety of these porphyrin@SPION nanospheres was considered by investigating their behaviors in human plasma during the delivery process. The results elucidate that these nanospheres have no significant deleterious influence on the frame conformation of protein in their delivery process and thus are relatively safe in the drug delivery process. Our study demonstrates that the combination of targeted magnetic-loading drug design methodology with the PDT potential of cationic porphyrins may be a very useful strategy to develop novel tumor-oriented multifunctional anticancer therapeutics.
- Zhao, Ping,Liu, Min-Chao,Madanayake, Thushara W.,Reena, Chawla,Zheng, Min,Cheng, Zhen-Feng,Huang, Yu-Min,Wang, Xia-Hong
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p. 103137 - 103148
(2016)
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- Self-assembled molecular rafts at liquid|liquid interfaces for four-electron oxygen reduction
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The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP4+) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS4-), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning Electron Microscopy. Density functional theory calculations confirm the possibility of formation of the catalytic CoTMPyP4+/ CoTPPS4- complex and its capability to bind oxygen.
- Olaya, Astrid J.,Schaming, Delphine,Brevet, Pierre-Francois,Nagatani, Hirohisa,Zimmermann, Tomas,Vanicek, Jiri,Xu, Hai-Jun,Gros, Claude P.,Barbe, Jean-Michel,Girault, Hubert H.
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- Cucurbit[8]uril-based supramolecular nanocapsules with a multienzyme-cascade antioxidative effect
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A supramolecular nanocapsule was constructed by the ternary host-guest complexation of azobenzene (Azo) and methylviologen (MV) to cucurbit[8]uril (CB[8]) and the subsequent self-assembly. The supramolecular nanocapsule with both glutathione peroxidase (GPx) and superoxide dismutase (SOD) activities can mimic the intracellular enzymatic reactive oxygen species (ROS) defense system.
- Liu, Shengda,Tian, Ruizhen,Xu, Jiayun,Wang, Liang,Sun, Jianxin,Jiang, Xiaojia,Wang, Tingting,Li, Xiumei,Luo, Quan,Liu, Junqiu
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- Unsymmetrical porphyrins: the role of meso-substituents on their physical properties
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The synthesis of one-step meso-porphyrins type AxBy containing alkyl and pyridyl groups is described. An initial assess of the amphiphilic proprieties were determined by its log Kow using fluorescence detection techniques and values from 1.42 to 2.15 were observed. The melting points of this set of porphyrins was determined and a strong effect of the number and size of the meso-alkyl chain is ascribed.
- Henriques, César A.,Gon?alves, Nuno P.F.,Abreu, Artur R.,Calvete, Mário J.F.,Pereira, Mariette M.
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- Syntheses, electrochemistry and photophysical properties of a series of meso-pyridylpentafluorophenylporphyrins
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This work presents the synthesis and characterization of a series of substituted pyridylpentafluroporphyrins, including the separation of the cis- and trans-isomers, the latter being characterized by X-ray crystallography. The spectroscopic and electrochemical properties of the series are dependent on the number of electron withdrawing pentafluorophenyl substituent, but they do not depend on the symmetry of the molecule. Ongoing from the monosubstituted to the more substituted pentafluorophenyl porphyrin H2(MPyTFPP) derivative, the Soret bands are slightly red-shifted and their quantum fluorescence yields range from 0.035 to 0.046, consistent with the value of 0.045 for the fully substituted 5,10,15,20-tetrapentafluorophenylporphyrin (dichloromethane solutions). The redox potentials of the reductive processes of monoanion and dianion formation are also sensitive to the number of pentafluoro substituents, shifting 180 mV to more positive values for the P0/P-1 process ongoing from the monopentafluoro to the tris-pentafluorophenyl substituted derivative.
- Moreira, Emmanuel Z.,Ferreira, Alba D.Q.,Neri, Cláudio Roberto,Mukhopadhyay, Sumitra,Dovidauskas, Sérgio,Nikolaou, Sofia,Iamamoto, Yassuko
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- Distant protonated pyridine groups in water-soluble iron porphyrin electrocatalysts promote selective oxygen reduction to water
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Fe(iii)-meso-tetra(pyridyl)porphyrins are electrocatalysts for the reduction of dioxygen in aqueous acidic solution. The 2-pyridyl derivatives, both the triflate and chloride salts, are more selective for the desired 4e - reduction than the iso
- Matson, Benjamin D.,Carver, Colin T.,Von Ruden, Amber,Yang, Jenny Y.,Raugei, Simone,Mayer, James M.
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- Kinetic and mechanism of the aqueous selective oxidation of sulfides to sulfoxides:
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The selective oxidation of sulfides with hydrogen peroxide to give sulfoxides was carried out in aqueous solution by water-soluble manganese porphyrin as mimics of cytochrome P450-like catalyst. Different factors that influencing the selective oxidation of sulfides, for example, catalyst, amount of catalyst, solvent and reaction temperature were investigated. MnTE4PyP (meso-tetrakis(N-ethylpyridinium-4-yl) manganese porphyrin) was efficient and selective catalyst for oxidation of various sulfides. The reaction showed first-order dependence in both [sulfide] and [H2O2], and a fractional order respect to catalyst. Oxygen atom transfer mechanism involves high-valence intermediate was proposed, which was supported by kinetic orders and spectrophotometric evidences. Copyright
- Zhou, Xian-Tai,Ren, Gang-Qing,Ji, Hong-Bing
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- Synthesis, characterisation and magnetic behaviour of ionic metalloporphyrins: Metal-tetrakis(N-octyl-4-pyridinium)-porphyrins with tetrabromoferrate(III) anions
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A series of magnetic, ionic-substituted tetrapyridyl metalloporphyrins, [tetrakis(N-octyl-4-pyridinium)-metal-porphyrin][ tetrabromoferrate(III)]4 (metal=iron, cobalt, manganese, copper or zinc), have been synthesised. All compounds show weak ferromagnetic behaviour at room temperature and respond to an external neodymium magnet.
- Zhou, Na,Sun, Zhicheng,Zhou, Qing,Lu, Xingmei,Shao, Huawu
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- Electrocatalytic water oxidation by a water-soluble nickel porphyrin complex at neutral ph with low overpotential
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The water-soluble cationic nickel(II) complex of meso-tetrakis(4-N-methylpyridyl)porphyrin (1) can electrocatalyze water oxidation to O2 in neutral aqueous solution (pH 7.0) with the onset of the catalytic wave appearing at 14;1.0 V (vs NHE). The homogeneous catalysis with 1 was verified. Catalyst 1 exhibited water oxidation activity in a pH range 2.0-8.0 and had a strict linear dependence of catalytic current on its concentration. After 10 h of constant potential electrolysis at 1.32 V (vs NHE), a negligible difference of the solution was observed by UV-vis. In addition, inspection of the working electrode by electrochemistry, scanning electron microscope (SEM), and energy dispersive X-ray spectroscopy (EDX) showed no sign of deposition of NiOx films. These results strongly argued that 1 is a real molecular electrocatalyst for water oxidation. The turnover frequency (TOF) for this process was 0.67 s-1 at 20 °C. On the basis of results from the kinetic isotope effect (KIE) and inhibition experiments, electrochemical studies in various buffer solutions with different anions and pHs, and DFT calculations, a catalytic cycle of 1 for water oxidation via a formally Ni(IV) species was proposed.
- Han, Yongzhen,Wu, Yizhen,Lai, Wenzhen,Cao, Rui
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- Coordination of pyridine and piperidine by cobalt complexes of water-soluble porphyrin and phthalocyanines
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The extracoordination reactions of nitrogen-containing bases pyridine and piperidine with cobalt complexes of water-soluble porphyrin and phthalocyanines were studied. The stability constants of the axial complexes of cobalt porphyrins and cobalt phthalocyanines with pyridine and piperidine were determined.
- Guseva,Pukhovskaya,Golubchikov
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- Synthesis and in vitro photodynamic activities of water-soluble fluorinated tetrapyridylporphyrins as tumor photosensitizers
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A series of water-soluble fluorinated cationic porphyrins were designed, synthesized, and characterized. In vitro photocytotoxicity of these compounds was evaluated by MTT assay on HeLa cells. Their photocytotoxicity was dependent on the positions of the cations and the fluorines in the pyridine ring, and 5,10,15,20-tetrakis-(N-methyl-2-fluoro-pyridin-3-yl)-porphyrin (8) showed the most potent photo-induced cytotoxicity without photobleaching. PDT-induced ROS inside HeLa cells was measured with flow cytometry using ROS-sensitive fluorometric probe, 2,7-dichlorofluororescin (DCF), which revealed high correlations of ROS with cellular cytotoxicity. FACS analysis shows that PDT with porphyrin 8 induced apoptosis in HeLa cells. In summary, efficient generation of ROS, biological effectiveness, and good photostability of porphyrin 8 indicate its potential application in photodynamic therapy (PDT) in the near future.
- Ko, Yoon-Joo,Yun, Kyung-Jin,Kang, Min-Seok,Park, Jongmin,Lee, Kyung-Tae,Park, Seung Bum,Shin, Jung-Hyu
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Read Online
- The construction of C(sp3)–O bond via copper porphyrin catalyzed cross-dehydrogenative coupling reaction: Substituent and electronic effect of the catalysts
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The push-pull electronic and steric effect of copper porphyrin catalysts on the cross-dehydrogenative coupling (CDC) reaction between the hydroxyl group of phenol substrates and C(sp3)-H bond have been investigated. Results showed that copper porphyrin bearing electron-withdrawing, bulky steric hindrance or heteroatom of pyridyl groups could increase the catalytic activity in the reaction. 5,10,15,20-(tetrakis(4-pyridyl)porphyrin)copper (CuTPyP) was found the best among all tested catalysts. Phenol substrates bearing various functional groups afforded moderate to excellent yields (99%). Significantly, as compared to other tested copper porphyrins, CuTPyP not only exhibited remarkable higher activity but also could shorten the reaction time from 12 to 6 h.
- Wang, Feng-Hua,Liu, Zheng-Yan,Yang, Shuang,Shi, Lei,Lin, Dong-Zi,Liu, Hai-Yang,Yuan, Gao-Qing
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supporting information
p. 2053 - 2062
(2021/05/26)
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- Graphene oxide and graphene quantum dots as delivery systems of cationic porphyrins: Photo-antiproliferative activity evaluation towards t24 human bladder cancer cells
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The development of new photodynamic therapy (PDT) agents designed for bladder cancer (BC) treatments is of utmost importance to prevent its recurrence and progression towards more invasive forms. Here, three different porphyrinic photosensitizers (PS) (TMPyP, Zn-TMPyP, and P1-C5 ) were non-covalently loaded onto graphene oxide (GO) or graphene quantum dots (GQDs) in a one-step process. The cytotoxic effects of the free PS and of the corresponding hybrids were compared upon blue (BL) and red-light (RL) exposure on T24 human BC cells. In addition, intracellular reactive oxygen species (ROS) and singlet oxygen generation were measured. TMPyP and Zn-TMPyP showed higher efficiency under BL (IC50: 0.42 and 0.22 μm, respectively), while P1-C5 was more active under RL (IC50: 0.14 μm). In general, these PS could induce apoptotic cell death through lysosomes damage. The in vitro photosensitizing activity of the PS was not compromised after their immobilization onto graphene-based nanomaterials, with Zn-TMPyP@GQDs being the most promising hybrid system under RL (IC50: 0.37 μg/mL). Overall, our data confirm that GO and GQDs may represent valid platforms for PS delivery, without altering their performance for PDT on BC cells.
- Fateixa, Sara,Faustino, Maria A. F.,Gomes, Ana T. P. C.,Lazzarotto, Silvia,Menilli, Luca,Miolo, Giorgia,Monteiro, Ana R.,Morais, Filipe M. P.,Moura, Nuno M. M.,Neves, Maria G. P. M. S.,Trindade, Tito
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- Photophysical and bactericidal properties of pyridinium and imidazolium porphyrins for photodynamic antimicrobial chemotherapy
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Despite advances achieved over the last decade, infections caused by multi-drug-resistant bacterial strains are increasingly becoming important societal issues that need to be addressed. New approaches have already been developed in order to overcome this problem. Photodynamic antimicrobial chemotherapy (PACT) could provide an alternative to fight infectious bacteria. Many studies have highlighted the value of cationic photosensitizers in order to improve this approach. This study reports the synthesis and the characterization of cationic porphyrins derived from methylimidazolium and phenylimidazolium porphyrins, along with a comparison of their photophysical properties with the well-known N-methylpyridyl (pyridinium) porphyrin family. PACT tests conducted with the tetracationic porphyrins of these three families showed that these new photosensitizers may offer a good alternative to the classical pyridinium porphyrins, especially against S.aureus and E.coli. In addition, they pave the way to new cationic photosensitizers by the means of derivatization through amide bond formation.
- Arnoux, Philippe,Frochot, Céline,Guern, Florent Le,Leroy-Lhez, Stéphanie,Nurlykyz, Yesmurzayeva,Ouk, Tan-Sothéa,Sol, Vincent,Yerzhan, Issabayev
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- PHOTODYNAMIC CATIONIC PORPHYRIN COMPOSITES
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A photodynamic composite including a porphyrin having four quaternized nitrogens, wherein the porphyrin is covalently bonded to a polymer containing reactive amines covalently bonded to a solid-state support is claimed. A method for sanitizing contaminated water is claimed including exposing the contaminated water to the photodynamic composite, in the presence of light and oxygen, wherein, a sufficient quantity of singlet oxygen and super oxide anions is provided by the chemical reaction of the light and the photosensitizer to destroy the pollutants or pathogens present in the contaminated water and to oxidize organic contaminants into carbon dioxide and water; thereby rendering the water potable.
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Paragraph 0038
(2021/02/19)
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- Comparative in vitro Studies of the Topoisomerase I Inhibition and Anticancer Activities of Metallated N-Confused Porphyrins and Metallated Porphyrins
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Using the original approach, a series of metallated N-confused porphyrins and metallated porphyrins have been synthesized and characterized. For all the synthesized porphyrins, in vitro studies of cytotoxic activity against K562, U937, HL-60, Jurkat, A549 and HeLa cancer cell lines, the ability to induce apoptosis and effects on the cell cycle as well as the kinetics of proliferative activity of porphyrins and their respective metallated complexes in real time have been developed. The inhibitory activity of metallated porphyrins against human topoisomerase I and the possible mechanism of inhibition have been carried out by modelling using molecular docking.
- D'yakonov, Vladimir A.,Dzhemilev, Usein M.,Dzhemileva, Lilya U.,Halder, Nyancy,Ramazanov, Ilfir R.,Rath, Harapriya
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- Acid catalysis in confined channels of metal-organic frameworks: Boosting orthoformate hydrolysis in basic solutions
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Enzymes use a confined docking cavity and residual groups in the cavity to regulate substrate selectivity and catalytic activity. By mimicking enzymes, we herein report that metal-organic framework (MOF) KLASCC-1, with channels and inside-channel pyridyl groups, can promote orthoformate hydrolysis in basic solutions. By studying pH-dependent hydrolysis and using an analogue MOF that lacks inside-channel pyridyl groups, we proved protonated pyridyl groups as acid catalytic sites for orthoformate hydrolysis. By using MOFs with only open pyridyl groups, we demonstrated the necessity of the confined channels. X-ray diffraction structures of KLASCC-1 with encapsulated substrates confirmed that these channels can regulate activity and size selectivity. Recycling tests and crystallographic studies confirmed that KLASCC-1 kept its framework structure in catalysis. This work shows the potentials of using MOFs for host-guest catalysis that cannot be otherwise completed and underlines the advantages of using crystal engineering to identify active sites.
- Zhou, Guojun,Wang, Bo,Cao, Rui
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supporting information
p. 14848 - 14853
(2020/10/13)
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- Conformational-Switch Based Strategy Triggered by [18] π Heteroannulenes toward Reduction of Alpha Synuclein Oligomer Toxicity
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A water-soluble meso-carboxy aryl substituted [18] heteroannulene (porphyrin) and its Zn-complex have been found to be viable in targeting α-Syn aggregation at all its key microevents, namely, primary nucleation, fibril elongation, and secondary nucleation, by converting the highly heterogeneous and cytotoxic aggresome into a homogeneous population of minimally toxic off-pathway oligomers, that remained unexplored until recently. With the EC50 and dissociation constants in the low micromolar range, these heteroannulenes induce a switch in the secondary structure of toxic prefibrillar on-pathway oligomers of α-Syn, converting them into minimally toxic nonseeding off-pathway oligomers. The inhibition of the aggregation and the reduction of toxicity have been studied in vitro as well as inside neuroblastoma cells.
- Chakraborty, Ritobrita,Sahoo, Sumit,Halder, Nyancy,Rath, Harapriya,Chattopadhyay, Krishnananda
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p. 573 - 587
(2018/10/31)
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- Regioselective reduction of 5-aryl-10,15,20-tris(pyridyl) porphyrin to 5-aryl-10,15,20-tris(pyridyl)dihydroporphyrin (chlorin)
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Dihydroporphyrins or chlorins differ from porphyrins only by saturation of a peripheral double bond of the macrocycle. However, this small structural difference leads to a significant increase of the absorption band at approximately 650 nm, which makes them very interesting candidates for photodynamic therapy applications. The reduction of porphyrins bearing two, three or four pyridyl substituents with tin(II) chloride has been developed for the synthesis of dihydroporphyrins in yields of 15-73%. The reduction of 5-(aryl)-10,15,20-tris(2 or 4-pyridyl)porphyrin with tin(II) chloride dihydrate demonstrated good regioselectivity. Porphyrins with one meso-aryl bearing one electron-donating group (EDG) gave 5-aryl-10,15,20-tris(2-or 4-pyridyl)-17,18-dihydroporphyrins in 17-72% yield. Porphyrins with one meso-aryl bearing one or more electron-withdrawing groups (EWG) gave 5-aryl-10,15,20-tris(4-pyridyl)-17,18-dihydroporphyrins or 5-aryl-10,15,20-tris(4-pyridyl)-7,8-dihydroporphyrins in 15-21% yield and isobacteriochlorin. We have also proven the possibility of functionalizing these compounds to design new regioisomerically pure photosensitizers.
- Brégier, Frédérique,Godard, Jérémy,Thiais, Jordan,Bouramtane, Soukaina,Moulin, Alexia,Champavier, Yves,Mailleau, Alexis,Chaleix, Vincent,Sol, Vincent
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p. 1380 - 1397
(2019/11/13)
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- Neutral Porphyrin Derivative Exerts Anticancer Activity by Targeting Cellular Topoisomerase i (Top1) and Promotes Apoptotic Cell Death without Stabilizing Top1-DNA Cleavage Complexes
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Camptothecin (CPT) selectively traps topoisomerase 1-DNA cleavable complexes (Top1cc) to promote anticancer activity. Here, we report the design and synthesis of a new class of neutral porphyrin derivative 5,10-bis(4-carboxyphenyl)-15, 20-bis(4-dimethylaminophenyl)porphyrin (compound 8) as a potent catalytic inhibitor of human Top1. In contrast to CPT, compound 8 reversibly binds with the free enzyme and inhibits the formation of Top1cc and promotes reversal of the preformed Top1cc with CPT. Compound 8 induced inhibition of Top1cc formation in live cells was substantiated by fluorescence recovery after photobleaching (FRAP) assays. We established that MCF7 cells treated with compound 8 trigger proteasome-mediated Top1 degradation, accumulate higher levels of reactive oxygen species (ROS), PARP1 cleavage, oxidative DNA fragmentation, and stimulate apoptotic cell death without stabilizing apoptotic Top1-DNA cleavage complexes. Finally, compound 8 shows anticancer activity by targeting cellular Top1 and preventing the enzyme from directly participating in the apoptotic process.
- Das, Subhendu K.,Ghosh, Arijit,Paul Chowdhuri, Srijita,Halder, Nyancy,Rehman, Ishita,Sengupta, Souvik,Sahoo, Krushna Chandra,Rath, Harapriya,Das, Benu Brata
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p. 804 - 817
(2018/02/17)
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- "ship in a bottle" Porph@MOMs as highly efficient catalysts for selective controllable oxidation and insights into different mechanisms in heterogeneous and homogeneous environments
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In the present work, three "ship in a bottle" Porph@MOMs are reported as biomimetic oxidation catalysts for different reactions. These frameworks are constructed from trimesic acid and metal ions (M = Fe, Co and Mn) in which tetra(N-methyl-4-pyridyl)porphyrin (MTMPyP) is encapsulated within the cavities. Additionally, the catalytic activities of the corresponding homogeneous compounds, FeTMPyP, CoTMPyP and MnTMPyP, and the frameworks without porphyrins within the cavities were investigated in the foregoing oxidation reactions. The prepared 3D porous structures have the ability to control selectivity toward the desired product. Furthermore, they are capable of acting as effective peroxidase mimics, which successfully catalyze the oxidation of diverse olefins as well as hydrocarbons using TBHP as an oxidant. The heterogeneous catalysts significantly enhance conversion in contrast to their corresponding homogeneous systems. Remarkably, an insight into the catalyst behavior was gained from the proposed mechanism based on the reversal of selectivity. Investigation of the stability and reusability of the catalysts revealed the heterogeneity character of the catalyst with no desorption during the course of oxidation reactions. The high yields, clean reactions, high thermal stability and reusability of the catalysts make them good candidates for heterogeneous catalysts in various oxidation reactions.
- Saghian,Dehghanpour,Sharbatdaran
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supporting information
p. 12872 - 12881
(2018/08/01)
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- Photodynamic effect of meso-(aryl)porphyrins and meso-(1-methyl-4-pyridinium)porphyrins on HaCaT keratinocytes
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Sixteen porphyrins, including neutral, anionic and cationic meso-(aryl)porphyrins and meso-(1-methyl-4-pyridinium)porphyrins were herein evaluated in terms of their photosensitizing properties against HaCaT keratinocytes. After an initial screening, the cationic porphyrins were studied in more details, by both determining their log POWand performing PDT assays in lower porphyrin concentrations. Porphyrins presenting two or more adjacent positively charged groups, directly linked to the macrocycle meso positions, appeared to be the most effective photosensitizers. The present study also included the dicationic 5,10-diphenyl-15,20-di(1-methylpyridinium-4-yl)porphyrin (14b), which has previously shown promising results on a psoriasis-like in vivo model. Overall results indicated that the beneficial effect related to porphyrins on psoriasis can be related to the decreasing of keratinocyte viability. Furthermore, some of the cationic porphyrins studied appeared as candidates to be utilized as photosensitizers for psoriasis treatment.
- Slomp, Amanda M.,Barreira, Sandra M.W.,Carrenho, Luise Z.B.,Vandresen, Camila C.,Zattoni, Ingrid F.,Ló, Stephanie M.S.,Dallagnol, Juliana C.C.,Ducatti, Diogo R.B.,Orsato, Alexandre,Duarte, M. Eugênia R.,Noseda, Miguel D.,Otuki, Michel F.,Gon?alves, Alan G.
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supporting information
p. 156 - 161
(2016/12/27)
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- Synthesis, G-quadruplexes DNA binding, and photocytotoxicity of novel cationic expanded porphyrins
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Intensive reports allowed the conclusion that molecules with extended aromatic surfaces always do good jobs in the DNA interactions. Inspired by the previous successful researches, herein, we designed a series of cationic porphyrins with expanded planar substituents, and evaluated their binding behaviors to G-quadruplex DNA using the combination of surface-enhanced raman, circular dichroism, absorption spectroscopy and fluorescence resonance energy transfer melting assays. Asymmetrical tetracationic porphyrin with one phenyl-4-N-methyl-4-pyridyl group and three N-methyl-4-pyridyl groups exhibit the best G4-DNA binding affinities among all the designed compounds, suggesting that the bulk of the substituents should be matched to the width of the grooves they putatively lie in. Theoretical calculations applying the density functional theory have been carried out and explain the binding properties of these porphyrins reasonably. Meanwhile, these porphyrins were proved to be potential photochemotherapeutic agents since they have photocytotoxic activities against both myeloma cell (Ag8.653) and gliomas cell (U251) lines.
- Jin, Shu-Fang,Zhao, Ping,Xu, Lian-Cai,Zheng, Min,Lu, Jia-Zheng,Zhao, Peng-Liang,Su, Qiu-Lan,Chen, Hui-Xian,Tang, Ding-Tong,Chen, Jiong,Lin, Jia-Qi
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p. 110 - 117
(2015/05/27)
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- ORGANIC COMPOUND, CHARGE-TRANSPORTING MATERIAL, AND ORGANIC ELECTROLUMINESCENT ELEMENT
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There are provided an organic having both excellent hole transporting property and satisfactory electron transporting and showing excellent durability against electric oxidation/reduction and a high triplet excitation level, and a charge transporting material and an organic electroluminescent device each using the organic compound. The organic compound is represented by following Formula (I): wherein Cz 1 and Cz 2 each represent a carbazolyl group; Z represents a direct bond or an arbitrary linkage group enabling the conjugation of nitrogen atoms in the carbazole rings of Cz 1 and Cz 2 with each other; and Q represents a direct bond connecting to "G" in following Formula (II): wherein Ring B 1 represents a six-membered aromatic heterocyclic ring having "n" nitrogen atom(s) as hetero atom(s); "n" represents an integer of from 1 to 3; G represents a direct bond or an arbitrary linkage group connecting to Q when G connects to Q; Gs connect to carbon atoms at the ortho-position and the para-position with respect to nitrogen atom(s) in Ring B 1 ; G represents an aromatic hydrocarbon group when G does not connect to Q; and "m" represents an integer of from 3 to 5.
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- SnIV porphyrin scaffolds for axially bonded multiporphyrin arrays: Synthesis and structure elucidation by NMR studies
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A simple, one-step, supramolecular strategy was adopted to synthesize SnIV-porphyrin-based axially bonded triads and higher oligomers by using meso-pyridyl SnIV porphyrin, meso-hydroxyphenyl-21,23- dithiaporphyrin, and RuII porphyrin as building blocks and employing complementary and non-interfering SnIV-O and RuII...N interactions. The multiporphyrin arrays are stable and robust and were purified by column chromatography. 1H, 1H-1H COSY and NOESY NMR spectroscopic studies were used to unequivocally deduce the molecular structures of SnIV-porphyrin-based triads and higher oligomers. Absorption and electrochemical studies indicated weak interaction among the different porphyrin units in triads and higher oligomers, in support of the supramolecular nature of the arrays. Steady-state fluorescence studies on triads indicated the possibility of energy transfer in the singlet state from the basal SnIV porphyrin to the axial 21,23-dithiaporphyrin. However, the higher oligomers were weakly fluorescent due to the presence of heavy Ru II porphyrin unit(s), which quench the fluorescence of the Sn IV porphyrin and 21,23-dithiaporphyrin units. Supramolecular arrays consisting of up to seven porphyrin units (see figure) were prepared on the basis of SnIV porphyrins by stepwise and one-pot synthetic strategies and their structures elucidated by detailed NMR spectroscopic studies.
- Dvivedi, Avanish,Pareek, Yogita,Ravikanth, Mangalampalli
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supporting information
p. 4481 - 4490
(2014/05/06)
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- A simple method for efficient synthesis of tetrapyridyl-porphyrin using Adler method in acidic ionic liquids
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We investigated the preparation of tetraphenylporphyrin (TPP) using the several acidic ionic liquids, [HC4im][X] (X- = CF 3SO3-, ClO4-, Cl -, CF3CO2-, and BF4 -), as acid catalytic media. For such ionic liquids, the anion (X-) of [HC4im][X] is related to the acidity of the ionic liquid, and affects porphyrin formation. This synthetic method using acidic ionic liquids can also be applied to other meso-substituted phenyl porphyrins and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP), which has 4-pyridyl moieties at four meso positions. In [HC4im][CF3CO 2], TPyP could be obtained in 11% yield, and the [HC 4im][CF3CO2] could be reused at least 3 times without any loss of its catalytic activity. The TPyP synthesis methodology using acidic ionic liquids can remove the ionic liquids from TPyP by easy filtration in contrast to the traditional Alder method, which needs vacuum distillation or liquid-liquid extraction for removing propionic acid. Our proposed porphyrin preparation method using the acidic ionic liquids potentially have wide applications to various useful porphyrin analogues. This journal is the Partner Organisations 2014.
- Kitaoka, Satoshi,Nobuoka, Kaoru,Ihara, Keita,Ishikawa, Yuichi
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p. 26777 - 26782
(2014/07/21)
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- Manganese porphyrin immobilized on montmorillonite: A highly efficient and reusable catalyst for the aerobic epoxidation of olefins under ambient conditions
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Highly efficient aerobic epoxidation of olefins catalyzed by cationic meso-tetrakis-(1-methyl-4-pyridyl) (TM4PyP) metalloporphyrins immobilized into montmorillonite (MT) interlayer was achieved. The heterogeneous catalysts were characterized by diffuse reflectance UV spectra, infrared, X-ray diffraction, nitrogen adsorption isotherm and scanning electron microscopy. Manganese porphyrin (MnTM4PyP-MT) showed excellent activity and selectivity for the aerobic epoxidation of olefins under ambient conditions, in which more 90% yields of epoxides were obtained. The clay basal spacing played significant role in the catalytic efficiency and selectivity for different olefins. The catalyst could be reused consecutively five times without significant loss of activity.
- Zhou, Xiantai,Ji, Hongbing
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p. 1032 - 1039
(2013/01/15)
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- Oxidative cleavage of isoeugenol to vanillin under molecular oxygen catalysed by cobalt porphyrin intercalated into lithium taeniolite clay
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Three types of Co-porphyrin complexes differing in their porphyrin-ring substituents and nonionic or cationic structure were intercalated into lithium taeniolite (LiTN) using a simple cation exchange method. All the intercalated catalysts displayed expanded clearance spaces (in the range of 0.30-0.51 nm) compared with that of the parent LiTN (0.24 nm). The catalysts were applied for the oxidative cleavage of isoeugenol to vanillin with molecular oxygen as the sole oxidant, and the reaction proceeded effectively under mild reaction conditions. The highest vanillin selectivity of 72% was obtained with CoTPyP/TN, which had the widest clearance space among the three Co-porphyrin catalysts. These intercalated catalysts showed high stability during oxidation, enabling their recycling for at least three runs.
- Adilina, Indri Badria,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
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experimental part
p. 72 - 79
(2012/08/08)
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- CATALYTIC CARBONYLATION CATALYSTS AND METHODS
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In one aspect, the present invention provides catalysts for the carbonylation of heterocycles. The inventive catalysts feature metal-ligand complexes having cationic functional groups tethered to the ligand, wherein the tethered cationic groups are associated with anionic metal carbonyl species. The invention also provides methods of using the inventive catalysts to affect the ring opening carbonylation of epoxides.
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Page/Page column 99
(2012/12/13)
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- Synthesis, structure, and photophysical properties of some gadolinium(III) porphyrinate complexes
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A series of gadolinium(III) porphyrinate complexes was synthesized in moderate yield from the interaction of meso-substituted porphyrin free bases with Ln[N(SiMe3)2]3·x[LiCl(THF) 3], followed by the addition of a tripodal anion LOMe - - an effective encapsulating agent for lanthanide ions. These new complexes were fully characterized by X-ray crystallography, elemental analysis, mass spectrometry, and infrared spectroscopy. The electronic spectra show a near-infrared phosphorescence from the triplet state of the porphyrin rings and exhibit a very characteristic vibronic-structured emission. A series of gadolinium(III) porphyrinate complexes was synthesized and fully characterized by spectroscopic and X-ray crystallographic methods. The electronic spectra show near-infrared phosphorescence from the triplet state of the porphyrin rings and exhibit a very characteristic vibronic-structured emission. Copyright
- Zhu, Xun-Jin,Zhang, Tao,Zhao, Shunsheng,Wong, Wai-Kwok,Wong, Wai-Yeung
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body text
p. 3314 - 3320
(2011/09/20)
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- The synthesis and photodynamic properties of meso-substituted, cationic porphyrin derivatives in HeLa cells
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A series of asymmetric porphyrins with varying substituents, such as 4-hydrophenyl and N-methyl-4-pyridyl, were synthesized and characterized and their cell uptake, intracellular localization, cytotoxicities and phototoxicities were evaluated in vitro. The most phototoxic of the porphyrins synthesized, 5,10-di-(N-methyl-4-pyridyl)-15,20-(4-hydroxyphenyl)-21,23H-porphyrin, which was mainly localized in the mitochondria and displayed low levels of dark toxicity toward human cancer HeLa cells, offers potential application in photodynamic therapy.
- Peng, Cheng-Liang,Lai, Ping-Shan,Chang, Cheng-Chung,Lou, Pei-Jen,Shieh, Ming-Jium
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experimental part
p. 140 - 147
(2010/10/03)
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- Solvent-free synthesis of meso-tetraarylporphyrins in air: Product diversity and yield optimization
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The scope and optimization of a solvent-free method for the rapid preparation and facile purification of technologically important meso-substituted aryl porphyrins, such as 5,10,15,20-tetraphenylporphyrin is presented. This one-step method involves heating the aromatic aldehyde to ~200°C in a vial fitted with a septum-lined cap, followed by addition of the pyrrole and maintaining the temperature for about 20 minutes. The dioxygen in air serves as the oxidant. Present results show that the addition of benzoic acid as a catalyst improves the yield of 5,10,15,20-tetraphenylporphyrin from 22% to 32% and of para halogenated phenylporphyrins from 10% to ~25%. Herein is also presented an examination of the many factors that influence the yield, the ease of purification, and the ability to scale up the reaction. Since the tarry by-products from this method are much less soluble than in most other synthetic strategies, much less solvent is required for purification; simple extraction is often sufficient. This method can be scaled in the lab to > 300 mg, and provides an attractive route to many meso-substituted porphyrins because of its minimal waste generation in terms of both solvent and chromatography support.
- Nia, Shabnam,Gong, Xianchang,Drain, Charles Michael,Jurow, Matthew,Rizvi, Waqar,Qureshy, Meroz
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experimental part
p. 621 - 629
(2011/10/11)
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- Phase-transfer of porphyrins by polypeptide-containing hyperbranched polymers and a novel iron(iii) porphyrin biomimetic catalyst
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Water-soluble porphyrins can be phase transferred by the hyperbranched multiarm copolymer PEI-PZLys; good catalytic activities and recyclabilities were observed for oxidation catalyzed by the encapsulated porphyrins. The Royal Society of Chemistry 2009.
- Ren, Qi-Zhi,Yao, Yuan,Ding, Xiao-Jian,Hou, Zong-Sheng,Yan, De-Yue
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supporting information; experimental part
p. 4732 - 4734
(2010/01/16)
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- Rational or statistical routes from 1-acyldipyrromethanes to meso-substituted porphyrins. Distinct patterns, multiple pyridyl substituents, and amphipathic architectures
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(Figure Presented) New methodology is described for the synthesis of porphyrins bearing four (A4, cis-A2B2, cis-ABC2, trans-A2B2) or fewer (A, cis-AB, cis-A2, trans-A)2 meso substituents. The method entails condensation of two 1-acyldipyrromethanes in the presence of a metal salt (MgBr2, 3 mol equiv) and a noncoordinating base (DBU, 10 mol equiv) in a noncoordinating solvent (toluene) with heating (conventional or microwave irradiation) and exposure to air. The rational synthesis of trans-A 2B2- or trans-A2-porphyrins was achieved via condensation of two identical 1-acyldipyrromethanes. The statistical synthesis of various meso-substituted porphyrins was achieved via condensation of two nonidentical 1-acyldipyrromethanes. Both routes possess attractive features including (1) no scrambling, (2) good yield (up to 60%) at high concentration (100 mM) for the macrocycle-forming step, (3) reasonable scope (aryl, heteroaryl, alkyl, or no substituent), (4) short reaction time (~2 h) via microwave irradiation, (5) magnesium porphyrins as the products, which easily undergo demetalation, and (6) facile chromatographic purification. A key advantage of the statistical route is to obtain a cis-substituted porphyrin without the corresponding trans isomer. For example, reaction of an A/B-substituted 1-acyldipyrromethane and the fully unsubstituted 1-formyldipyrromethane gave the magnesium chelates of three porphyrins: the trans-A2B2-porphyrin, the "hybrid" cis-AB-porphyrin, and porphine (no trans-AB-porphyrin can form), which were readily demetalated and separated as the free base species. Altogether 26 1-acyldipyrromethanes and 26 target porphyrins have been prepared, including many with two different pyridyl substituents. One set of amphipathic porphyrins includes cis-A2B2- or cis-A2BC-porphyrins wherein A = pentyl and B/C = pyridyl (o-, m-, p-). Taken together, the rational and statistical routes enable facile conversion of readily available 1-acyldipyrromethanes to diverse porphyrins bearing 1-4 meso substituents for which access is limited via other methods.
- Dogutan, Dilek Kiper,Ptaszek, Marcin,Lindsey, Jonathan S.
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p. 6187 - 6201
(2008/12/22)
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- Mild oxidation of styrene and its derivatives with ionic manganese porphyrin immobilized in the similarly structured ionic liquid
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Without the auxiliary involvement of axial ligands and organic solvents, the ionic manganese porphyrin 1c immobilized in [BPy][BF4] efficiently catalyzed the oxidation of styrene and its derivatives under mild conditions, affording high activity/oxide selectivity and good stability even after 5 recycling uses. Copyright
- Liu, Ye,Zhang, Hong-Jiao,Cai, Yue-Qin,Wu, Hai-Hong,Liu, Xiu-Li,Lu, Yong
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p. 848 - 849
(2008/02/12)
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- DNA binding and catalytic properties of positively charged corroles
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DNA likes corroles and peroxynitrite doesn't: The water-soluble manganese corrole (crystal structure shown) is a much better catalyst than the analogous porphyrin for decomposition of peroxynitrite (HOONO). The interactions of the two complexes with DNA are also significantly different. These findings suggest that positively charged corroles may be useful for therapeutic approaches. (Figure Presented)
- Gershman, Zoya,Goldberg, Israel,Gross, Zeev
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p. 4320 - 4324
(2008/03/11)
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