16834-13-2Relevant articles and documents
Thermochemistry of solution of some quaternized derivatives of tetra(4-pyridyl)porphine in water
Berezin,Berezina,Semeikin,V'Yugin
, p. 1955 - 1958 (2007)
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.
Novel Amphiphilic G-Quadruplex Binding Synthetic Derivative of TMPyP4 and Its Effect on Cancer Cell Proliferation and Apoptosis Induction
Chilakamarthi, Ushasri,Koteshwar, Devulapally,Jinka, Sudhakar,Vamsi Krishna, Narra,Sridharan, Kathyayani,Nagesh, Narayana,Giribabu, Lingamallu
, p. 6514 - 6527 (2018)
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.
Synthesis, RNA binding and nuclease activity of porphyrin-hydroxamic acid derivatives
Marketaki, Maria,Touloupakis, Eleftherios,Charalambidis, Georgios,Chalbot, Marie-Cécile,Ghanotakis, Demetrios F.,Coutsolelos, Athanassios G.
, p. 997 - 1005 (2012)
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.
A supramolecular bifunctional artificial enzyme with superoxide dismutase and glutathione peroxidase activities
Yu, Shuangjiang,Huang, Xin,Miao, Lu,Zhu, Junyan,Yin, Yanzhen,Luo, Quan,Xu, Jiayu,Shen, Jiacong,Liu, Junqiu
, p. 159 - 164 (2010)
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.
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
Stallivieri, Aurélie,Le Guern, Florent,Vanderesse, Régis,Meledje, Esme,Jori, Giulio,Frochot, Céline,Acherar, Samir
, p. 1290 - 1295 (2015)
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.
In vitro photodynamic inactivation of conidia of the phytopathogenic fungus Colletotrichum graminicola with cationic porphyrins
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
, p. 673 - 681 (2016)
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.
Preparation, characterization, and electrical properties of a self-assembled meso-pyridyl porphyrin monolayer on gold surfaces
Sathyapalan, Amarchand,Lohani, Anup,Santra, Sangita,Goyal, Saurabh,Ravikanth,Mukherji, Soumyo,Rao, V. Ramgopal
, p. 810 - 816 (2005)
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.
A Noble-Metal-Free Heterogeneous Photosensitizer-Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light
Ulusoy Ghobadi, T. Gamze,Akhuseyin Yildiz, Elif,Buyuktemiz, Muhammed,Sadigh Akbari, Sina,Topkaya, Derya,?sci, ümit,Dede, Yavuz,Yaglioglu, H. Gul,Karadas, Ferdi
, p. 17173 - 17177 (2018)
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.
Synthesis of coordination polymers of cobalt meso-pyridylporphyrins and its oxygen reduction properties
Saran, Neha,Thomas, Tincy Lis,Bhavana, Purushothaman
, (2021)
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.
Self-assembled molecular rafts at liquid|liquid interfaces for four-electron oxygen reduction
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.
, p. 498 - 506 (2012)
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.
Unsymmetrical porphyrins: the role of meso-substituents on their physical properties
Henriques, César A.,Gon?alves, Nuno P.F.,Abreu, Artur R.,Calvete, Mário J.F.,Pereira, Mariette M.
, p. 290 - 296 (2012)
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.
Distant protonated pyridine groups in water-soluble iron porphyrin electrocatalysts promote selective oxygen reduction to water
Matson, Benjamin D.,Carver, Colin T.,Von Ruden, Amber,Yang, Jenny Y.,Raugei, Simone,Mayer, James M.
, p. 11100 - 11102 (2012)
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
Synthesis, characterisation and magnetic behaviour of ionic metalloporphyrins: Metal-tetrakis(N-octyl-4-pyridinium)-porphyrins with tetrabromoferrate(III) anions
Zhou, Na,Sun, Zhicheng,Zhou, Qing,Lu, Xingmei,Shao, Huawu
, p. 445 - 450 (2013)
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.
Electrocatalytic water oxidation by a water-soluble nickel porphyrin complex at neutral ph with low overpotential
Han, Yongzhen,Wu, Yizhen,Lai, Wenzhen,Cao, Rui
, p. 5604 - 5613 (2015)
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.
Synthesis and in vitro photodynamic activities of water-soluble fluorinated tetrapyridylporphyrins as tumor photosensitizers
Ko, Yoon-Joo,Yun, Kyung-Jin,Kang, Min-Seok,Park, Jongmin,Lee, Kyung-Tae,Park, Seung Bum,Shin, Jung-Hyu
, p. 2789 - 2794 (2007)
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.
Graphene oxide and graphene quantum dots as delivery systems of cationic porphyrins: Photo-antiproliferative activity evaluation towards t24 human bladder cancer 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
, (2021/09/28)
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.
