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At least 973 records · Page 54Linked to original sources
PubMed2006

Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna.

Starting from a 1,3-phenylene-linked diporphyrin zinc(II) complex 2ZA, repeated stepwise Ag(I)-promoted coupling reactions provided linear oligomers 4ZA, 6ZA, 8ZA, and 12ZA. The intramolecular cyclization reaction of 12ZA under dilute conditions (1x10(-6) M) gave porphyrin ring C12ZA with a diameter of approximately 35 A in 60% yield. This synthetic strategy has been applied to a 1,3-phenylene-linked tetraporphyrin 4ZB to provide 8ZB, 12ZB, 16ZB, 24ZB, and 32ZB. The intramolecular coupling reaction of 24ZB gave a larger 24-mer porphyrin ring C24ZB with a diameter of approximately 70 A in 34% yield. These two large porphyrin rings were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy, UV-visible spectroscopy, gel permeation chromatography (GPC) analysis, and scanning tunneling microscopy (STM) techniques. The STM images of C12ZA reveal largely circular structures, whereas those of C24ZB exhibit mostly ellipsoidal shapes, indicating more conformational flexibility of C24ZB. Similar to the case of C12ZA, the efficient excitation energy transfer along the ring has been confirmed for C24ZB by using the time-correlated single-photon counting (TCSPC) and picosecond transient absorption anisotropy (TAA) measurements, and occurs with a rate of (35 ps)(-1) for energy hops between neighboring tetraporphyrin subunits. Collectively, the present work provides an important step for the construction of large cyclic-arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna.

Light-Harvesting Protein Complexes↗
PubMed2006

Efficient charge injection from the S2 photoexcited state of special-pair mimic porphyrin assemblies anchored on a titanium-modified ITO anode.

A novel surface fabrication methodology has been accomplished, aimed at efficient anodic photocurrent generation by a photoexcited porphyrin on an ITO (indium-tin oxide) electrode. The ITO electrode was submitted to a surface sol-gel process with titanium n-butoxide in order to deposit a titanium monolayer. Subsequently, porphyrins were assembled as monolayers on the titanium-treated ITO surface via phosphonate, isophthalate, and thiolate groups. Slipped-cofacial porphyrin dimers, the so-called artificial special pair at the photoreaction center, were organized through imidazolyl-to-zinc complementary coordination of imidazolylporphyrinatozinc(II) units, which were covalently immobilized by ring-closing olefin metathesis of allyl side chains. The modified surfaces were analyzed by means of X-ray photoelectron spectroscopy. Photoirradiation of the porphyrin dimer generated a large anodic photocurrent in aqueous electrolyte solution containing hydroquinone as an electron sacrificer, due to the small reorganization energy of the dimer. The use of different linker groups led to significant differences in the efficiencies of anodic photocurrent generation. The apparent flat-band potentials evaluated from the photocurrent properties at various pH values and under biased conditions imply that the band structure of the ITO electrode is modified by the anchoring species. The quantum yield for the anodic photocurrent generation by photoexcitation at the Soret band is increased to 15 %, a surprisingly high value without a redox cascade structure on the ITO electrode surface, while excitation at the Q band is not so significant. Extensive exploration of the photocurrent properties has revealed that hot injection of the photoexcited electron from the S2 level into the conduction band of the ITO electrode takes place before internal conversion to the S1* state, through the strong electronic communication of the phosphonyl anchor with the sol-gel-modified ITO surface.

Dimerization↗
PubMed2003

Circular dichroism and the interactions of water soluble porphyrins with DNA.

The size, sign, and profile of induced circular dichroism (CD) features in the Soret region are reliable indicators of the binding modes of porphyrins and metalloporphyrins to DNA. Porphyrins shown (using such CD criteria) to be intercalators in monodispersed DNA duplexes prove extremely useful for the detection and characterization of organized, condensed forms of nucleic acids (psi-condensates). In addition, certain select porphyrin derivatives can form extended assemblies on nonaggregated DNA templates. A combination of CD and resonance light scattering (RLS) measurements allows for sensitive detection and characterization of these porphyrin arrays.

Animals↗
PubMed2001

Synthesis and solution characterization of a porphyrin-CCK8 conjugate.

In this paper we report the synthesis and a detailed NMR solution characterization of a new CCK8 analogue and its indium(III) complex, PK-CCK8 and In-PK-CCK8. The new compounds contain a porphyrin moiety covalently bound through an amide bond to the side chain of a Lys residue introduced at the N-terminus of CCK8. A molecular dynamics simulation, based on the NMR structure of the complex between CCK8 and the N-terminal extracellular arm of the CCK(A) receptor, is also reported. Both the NMR study and the molecular dynamics simulation indicate that the porphyrin-peptide conjugate might be able to bind to the CCK(A) receptor model. The results of the molecular dynamics calculations show that the conformational features of the CCK8/CCK(A) receptor model complex and of the PK-CCK8/CCK(A) receptor-model complex are similar. This evidence supports the view that the introduction of the porphyrin-Lys moiety does not influence the mode of ligand binding to the CCK(A) receptor model. The NMR structure of PK-CCK8 in DMSO consists of a well defined pseudo-helical N-terminal region, while the C-terminal region is flexible. Moreover, the absence of NOE contacts between the porphyrin and the peptide indicates that the macrocyclic ring is directed away from the peptide region involved in the binding with the receptor.

Computer Simulation↗
PubMed2005

Circular dichroism spectroscopic study of non-covalent interactions of poly-L-glutamic acid with a porphyrin derivative in aqueous solutions.

The interactions of poly-L-glutamic acid and a cationic porphyrin derivative in aqueous solutions were studied by the combination of vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectroscopies. It was found that non-covalent interactions between both agents influence the structure of the polymeric matrix and the guest porphyrins and vice versa, but the physico-chemical properties of the solutions, especially the pH and the relative permittivity of the solvent, play a key role in the structure of the polypeptide part of the formed complexes. It was shown that the interaction with porphyrins prevents the precipitation of poly-L-glutamic acid in aqueous solution at acidic pH. In special conditions, the porphyrins attached to the polypeptide probably possess face-to-face interaction as demonstrated by the enhancement of the characteristic ECD signal and the appearance of sidebands on its short and long wavelength sides.

Circular Dichroism↗
PubMed1996

Surface active peptide-mediated porphyrin aggregation.

Surface active pentapeptide [2(HCOO-). Lys-Ala-Ala-Lys(Z)-Tyr-OCH3] has been synthesized and its micelle formation investigated using conductometric, pH metric, and UV spectroscopic techniques. The double head double tail peptide molecules are shown to interact with water soluble meso-tetrakis (4-sulfonatophenyl)-porphyrin [TPPS]H2 to form characteristic H-type aggregate at low concentrations, as evidenced by UV-Vis and fluorescence spectroscopic techniques. Spectroscopic analysis reveals that the aggregate contains 1:2 porphyrin-peptide combination. The equilibrium constant for the formation of peptide-porphyrin complex has been obtained by using absorption spectral data. The present studies provide new insight into the peptide-porphyrin interaction.

Amino Acid Sequence↗
PubMed1984

Influence of pH on porphyrin production in Propionibacterium acnes.

Propionibacterium acnes was grown on Eagle's medium for 4-15 days at pH 5.3-7.2 The porphyrin production was measured both by direct fluorometry and by high pressure liquid chromatography (HPLC). The greatest concentration of porphyrins was produced at pH 6.1. Protoporphyrin was the dominant porphyrin species present in the bacteria in all samples. The relative amount of coproporphyrin was greatest at pH 6.7 after 4 days of incubation. In human skin there are local variations in the pH; therefore our findings may be of importance for porphyrin production in acne.

Chromatography, High Pressure Liquid↗
PubMed1978

Porphyrin-like compounds genesis under simulated abiotic conditions.

Experiments with gas mixtures intended to simulate the primaeval atmosphere of the Earth yielded many biologically important chemicals. Investigations into the synthesis of porphyrin-like compounds from methane, ammonia and water vapour were carried out by using high frequency discharges. Microanalyses of porphyrins showed that porphyrin-like pigments were formed in this way. The presence of divalent cations in the reaction system increased the yield of porphyrin-like pigments also involving the direct synthesis of their metal complexes. The ready formation of these compounds in abiotic conditions is significant, suggesting the possibility of their appearance during the early stage of chemical evolution.

Ammonia↗
PubMed1986

Porphyrin synthesis in primary nervous tissue cultures from 10(-3) M delta-aminolaevulinic acid in the presence of melatonin and neuropeptides.

Of the primary neuronal tissue cultures (glia cell, neuronal cells, mixed and retina cultures), the neuronal cells of (cells + medium) display the highest total porphyrin production from 10(-3) M delta-aminolaevulinic acid (ALA). In the presence of 10(-3)-10(-6) M melatonin, the quantity of total porphyrins produced by the neuronal cultures decreases in inverse proportion to the concentration. Oxytocin, lysine-vasopressin, CCK-8 sulphate ester and des-Tyr-gamma-endorphin in concentrations of 10(-5) and 10(-6) M block the porphyrin synthesis of the glia cells and display different effects on that of the neuronal cells. They enhance the total porphyrin synthesis of the cell cultures, with the exception of 10(-5) M des-Tyr-gamma-endorphin, which exerts an inhibitory effect on the glia cells.

Aminolevulinic Acid↗
PubMed1986

The prevention of porphyrin loss from tissues during routine histological processing: quantitative studies on the Harderian gland.

The rodent Harderian gland is an important site of porphyrin biosynthesis and storage. Porphyrins are visible at the light and electron microscope level as large intraluminal accretions, as large interstitial accretions surrounded by foreign body giant cells, or as small interstitial deposits within free macrophages. Since porphyrins are soluble in a wide range of solvents, it is important to employ histological routines which minimize porphyrin loss during processing in addition to giving good tissue preservation. In this quantitative investigation, these requirements were optimally achieved with fixation in 3% buffered glutaraldehyde and the use of amyl acetate as a clearing agent.

Animals↗
PubMed1992

Inhibition of ferrochelatase and accumulation of porphyrins in mouse hepatocyte cultures exposed to porphyrinogenic chemicals.

The ability of 3,5-diethoxycarbonyl-1,4-dihydrocollidine (DDC), 3,5-diethoxycarbonyl-4-ethyl-1,4-dihydro-2,6-dimethylpyridine (EDDC) and griseofulvin to induce porphyria in primary cultures of mouse hepatocytes has been examined. Exposure of cultured mouse hepatocytes to DDC, EDDC or griseofulvin resulted in a marked inhibition of ferrochelatase which was sustained over the 4-day exposure period. Maximal concentrations of DDC (25 microM), EDDC (25 microM) and griseofulvin (25 microM) resulted in 14-fold, 30-fold and 9-fold increases, respectively, in total porphyrin in the culture medium. Analysis of the porphyrins accumulating indicated a predominance of protoporphyrin with all three xenobiotics. Addition of 5-aminolaevulinic acid (ALA) to mouse hepatocyte cultures (10-1000 microM) resulted in much larger increases (up to 164-fold) in porphyrin accumulation in the medium and the porphyrin accumulating was predominantly uroporphyrin. These studies have demonstrated that primary cultures of mouse hepatocytes provide a valid mechanism-based in vitro model of the hepatic porphyrias produced by the dihydropyridines and griseofulvin in mice.

Aminolevulinic Acid↗
PubMed2001

Oxidative chemistry of nickel porphyrins.

The oxidative chemistry of nickel(II) porphyrins is reviewed. Whether electron abstraction occurs from the metal to yield Ni(III) or from the porphyrin to yield Ni(II) pi cation radicals is discussed in terms of the relative energy levels of the metal and porphyrin orbitals. The effects of axial ligands in further modulating this ordering as well as the orbital occupancy of Ni(III) are also reviewed. Structural considerations, based on existing stereochemical data for Ni(I), high spin Ni(II) and related Ni(III) tetraaza complexes, are used to predict the metrics of Ni(III) porphyrins for which no structural data are available.

Nickel↗
PubMed2007

Lymph node metastasis detection of ovarian cancer by porphyrin fluorescence photodetection: case report.

The concept of intraoperative in vivo diagnosis and selective resection of infiltrated lymph nodes in ovarian cancer has not been evaluated despite the increased morbidity associated with pelvic and paraaortic lymph node dissection and its questionable therapeutic value. Fluorescence photodetection is based on the application of a photosensitizer relatively selective for malignant tissue, which after light activation of appropriate wavelength, shows fluorescence. Six hours after oral application of 10 mg/kg body weight 5-aminolevulinic acid, the abdominal cavity of a patient with suspicion of recurrent ovarian cancer was inspected using a laparoscope and blue light at 380-440 nm. Spectral measurements at a wavelength of 635 nm, multiple peritoneal biopsies, and lymph node excisions were performed. White light inspection and porphyrin fluorescence photodetection revealed no intraperitoneal metastases and multiple biopsies were negative. Fluorescence-positive lymph nodes were visible only in the left common iliac region and a specific porphyrin fluorescence peak could be detected. In contrary, no increased porphyrin fluorescence of intraperitoneal tissues or skin was seen. Fluorescence microscopy showed the characteristic red fluorescence in the infiltrated parts of the lymph node tissue by the papillary ovarian cancer. Histology of the other sites was negative. No systemic or cutaneous side effects were recorded. This data is a proof of the concept that porphyrin fluorescence-guided lymph node metastasis detection is possible in ovarian cancer and should stimulate further research in this field.

Female↗
PubMed2006

Self-organization of porphyrins and fullerenes for molecular photoelectrochemical devices.

We have constructed a variety of molecular assemblies of porphyrin as a donor and fullerene as an acceptor on electrodes for molecular photoelectrochemical devices. Highly efficient energy- and electron-transfer processes have been realized at gold electrodes modified with self-assembled monolayers of porphyrin- or fullerene linked systems mimicking light-harvesting and charge separation in bacterial photosynthesis. Highly ordered organization of porphyrins and fullerenes has also been achieved using step-by-step self-assembly of porphyrin and fullerene units by association with gold nanoparticles or dendrimers on tin oxide electrodes, which exhibit high power-conversion efficiency of up to 1.5%. These results will provide valuable information on the design of donor-acceptor type molecular assemblies that can be tailored to construct highly efficient organic solar cells.

Electrodes↗
PubMed1988

The effect of iron overload on the mitochondrial porphyrin level in the hexachlorobenzene induced experimental porphyria.

Liver mitochondria isolated from rats treated with hexachlorobenzene plus iron, present a lower content of total porphyrin in respect to that of mitochondria from rats fed hexachlorobenzene alone. The in vitro mitochondrial porphyrin accumulation processes have been studied in mitochondria from iron loaded rats. It has been found that under these conditions the active porphyrin uptake process, which is driven by the K+ transmembrane gradient, is maximally inhibited in the presence of pentachlorophenol at a concentration similar to that found in vivo in the hexachlorobenzene experimental porphyria. By contrast the same degree of inhibition is presented by control mitochondria only in the presence of pentachlorophenol plus valinomycin, a condition which collapses the transmembrane K+ gradient. A strict correlation between porphyrin uptake and K+ concentration has been found in control as well as in iron treated mitochondria. A possible involvement of peroxidative reactions in the mitochondrial membranes has been proposed as a cause of the changes in the permeability properties of the mitochondrial membranes in the experimental chronic hepatic porphyria under conditions of iron overload.

Animals↗
PubMed1991

Inhibitory effect of porphyrins on the proliferation of mouse spleen lymphocytes in vitro.

The influence of various porphyrins (deuteroporphyrin IX, mesoporphyrin IX, protoporphyrin IX, hematoporphyrin) and two related compounds (hemin, biliverdin) on the spontaneous proliferation of mouse spleen lymphocytes has been estimated in vitro by the 3H-thymidine uptake assay. It has been found that porphyrins (endogenous ligands for the mitochondrial benzodiazepine receptor) produce a concentration-dependent inhibition of 3H-thymidine incorporation into the DNA of these cells. Metalloporphyrin-hemin has been observed to evoke a weak inhibitory effect, in a high concentration (10(-4)M), whereas biliverdin, a porphyrins degradation product, was inactive in the same experimental conditions. Those findings indicate that endogenous porphyrins, presumably acting through the mitochondrial benzodiazepine receptor, could regulate the proliferation of mouse spleen lymphocytes in vitro.

Animals↗
PubMed1995

Cationic porphyrin derivatives as inhibitors of polyamine catabolism.

The effects of six cationic porphyrins on several enzymes involved in polyamine biosynthesis and catabolism have been examined. Both spermidine and spermine synthase were unaffected by the porphyrins at up to 2 mM. By contrast, ornithine and S-adenosylmethionine decarboxylase were inhibited by the nickel and cobalt derivatives of meso-tetrakis(N-methyl-4-pyridiniumyl)porphyrin (T4MPyP) with IC50 values in the 10-100 microM region. Spermidine/spermine N1-acetyltransferase (SSAT) and polyamine oxidase (PAO) were highly sensitive to the six meso-substituted cationic porphyrins tested, with Ki values as low as 6 nM for SSAT and 85 nM for PAO. These inhibitors may prove useful in defining the structural features of the active site of these enzymes.

Acetyltransferases↗
PubMed1978

Quantitation of red cell porphyrins by fluorescence scanning after thin-layer chromatography.

This paper reports a new method for the quantitative determination of erythrocyte and plasma porphyrins by fluoroscanning of the methyl esters separated by thin-layer chromatography (TLC). After esterification overnight in the dark the polycarboxylated porphyrin methyl esters were extracted into chloroform and aliquots applied to the TLC plates within the range of quantities shown in a preliminary study to be directly proportional to fluorescence intensity. The accuracy and reliability of the technique was tested by comparison of RBC protoporphyrin values obtained by TLC with an established quantitative porphyrin solvent extraction method and with a rapid method presently in common use. Good correlation was demonstrated between the solvent extraction and the TLC techniques. The high sensitivity and adaptability of the TLC technique and its ability to clearly separate all the porphyrins present in the samples are discussed, along with the fluorescence mechanisms involved and the effects of instrumentation.

Chromatography, Thin Layer↗