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PubMed1986

Fundamental aspects in tumor photochemotherapy: interactions of porphyrins with membrane model systems and cells.

Some molecular aspects underlying photochemotherapy and photodiagnosis of tumors with porphyrins are reviewed. The nature of the clinically used photosensitizer HpD is first presented along with structures of molecules found to be efficient in vitro. The possible role of pH in the preferential retention of dicarboxylic porphyrins by tumors is discussed in light of results obtained with membrane models. The uptake of dicarboxylic porphyrins by cells most likely involves passive mechanisms. Cell photoinactivation using a purified porphyrin does not depend upon the incubation time but only on the intracellular concentration of the dye. This likely reflects a poor specificity of the photoinactivation processes with regard to the cellular localization of the dye. The properties which should be presented by more efficient photosensitizers are discussed.

Blood Proteins↗

PubMed1997

Effect of central metal substitution on linear dichroism of porphyrins: evidence of out-of-plane transition moments.

Absorption anisotropy and emission anisotropy measurements in poly(vinyl) alcohol (PVA) films of different porphyrin derivatives are reported. Wavelength dependent absorption anisotropy in oriented PVA films, and wavelength dependent excitation spectrum of emission anisotropy of fluorescent porphyrin derivatives in isotropic PVA films indicate the presence of multiple transition moments with different well-defined orientation. Comparison of linear dichroism and orientation behavior in stretched PVA films of deuteroporphyrin III (C2V symmetry) and its iron derivative reveals significant out-of-plane transition moment components. A considerable participation of out-of-plane polarized absorption components is also observed for metal derivatives of non-symmetrical protoporphyrin IX. It appears that central metal substitutions in porphyrin rings do not produce 'circular' degeneration of electronic transition moments. Instead, the presence of metal induces absorption components orthogonal to the porphyrin plane.

Anisotropy↗

PubMed2000

Complexes produced by associated forms of porphyrin bound with hydrophobic-hydrophilic copolymer and transition metal ions.

Properties of protonated dimeric forms of meso-tetraphenylporphine (TPP) and meso-tetra(p-aminophenyl)porphine (TAPP) bound with copolymer and also complexes produced by associated TAPP bound with copolymer, Mn2+, and Fe3+ are investigated by absorption, luminescence, and Raman spectroscopy. According to absorption spectra of protonated dimers of TPP, three dimeric forms of the porphyrin are observed in the ground state. However, selective excitation of these forms according to the fluorescence spectra reveals only two dimeric forms in the excited state. In contrast, similar selective excitation of TAPP bound with copolymer in aqueous-dioxane solution results in weak changes in the fluorescence spectra, nevertheless, there is strong interaction between porphyrin and macromolecular carboxyl groups in the ground state. In the case of the formation of the complexes between associated TAPP bound with copolymer, Mn2+ and Fe3+, a new band in the near IR region with a maximum at 840 nm is built up in the fluorescence spectrum. However, this near IR emission is completely quenched when new strong vibrational bands at approximately 1800 and 1900 cm-1 are revealed in the resonance Raman spectra of the complexes. The observed effects are explained in terms of direct participation of water molecules involved in the water-porphyrin dimeric complex in the processes of transformation of excitation energy. The involvement of water in this dimeric complex can lead to redistribution of flows of the energy degradation when transition metal ions play a role of the agent which enhances the trapping properties of the porphyrin-metal-ions complexes.

Dimerization↗

PubMed1998

Cell cycle dependency of porphyrin uptake in a glioma cell line.

We used a two-color analysis system to assess the porphyrin uptake and DNA content in four established cell lines of glioma employing flow cytometry (FCM). The FCM study revealed porphyrin uptake in all cells, regardless of the phase of the cell cycle they were in. However, those in the G0/G1 phase showed moderate uptake of porphyrin and those in the G2/M phase showed a higher uptake. These results indicated the advantage of using porphyrin as the carrier of tumor targeting agents as a therapeutic strategy for malignant tumors.

Brain Neoplasms↗

PubMed1998

Porphyrin metabolism in rats intaking chemical carcinogens.

This study was performed on rats receiving nitrosamine precursors as potent liver carcinogens in order to investigate and follow up the porphyrin metabolism during the intake of hepatocarcinogens. As clarified from our results, progressive increases in free erythrocyte porphyrins, erythrocyte protoporphyrins, haem content and hepatic total porphyrins were observed after 2 months of intaking these carcinogens and further increases were gradually observed in parallel with the continued intake of these chemicals, which was extended to 7 months. At the same time, such elevations were also observed in the activity of hepatic delta-aminolevulinic acid (ALA)-synthetase and uroporphyrinogen-1-synthetase either in hepatic tissues or erythrocytes of these carcinogen-subjected rats. However, significant inhibition was found in the activity of erythrocyte ALA-dehydratase, which reached 40.5% of the control values after 7 months. Therefore, these observations demonstrated that the intake of hepatocarcinogens may influence the rate of hepatic porphyrin and haem biosynthesis.

5-Aminolevulinate Synthetase↗

PubMed1999

Augmentation of 12-O-tetradecanoyl 13-phorbol acetate-mediated tumor promoting response by the porphyrin photosensitization of 7,12-dimethyl benz[a]anthracene-initiated murine skin: role of in situ generated reactive oxygen species.

Recently, we have shown that sustained ROS generation by prolonged porphyrin-mediated photosensitization in murine skin acts as a stage I and weak complete tumor promoter. Further to this, in the present study, we show that porphyrin photosensitization of DMBA-initiated murine skin results in the augmentation of TPA-mediated tumor promoting response. The photosensitization increased tumor yield to 15 tumors per mouse as compared to 7.5 tumors per mouse in the group treated with TPA alone. Further, 100% tumor incidence in the TPA-treated photosensitized group occurred at week 11 whereas it occurred at week 19 in the TPA alone treated group. Porphyrin photosensitization slightly decreased the latency period of TPA-mediated tumor formation by 1 week. The TPA-mediated ODC induction (1300% of saline-treated control) has been augmented in the photosensitized group (1950%). However, the amount of [3H]thymidine incorporation was not significantly different in the photosensitized TPA-treated and TPA alone-treated groups. Similarly, TPA treatment in photosensitized animals augmented the depletion of cutaneous glutathione and enhancement of lipid peroxidation. These changes were attenuated in butylated hydroxytoluene-pretreated animals. Our results suggest that cutaneous porphyrin photosensitization augments TPA-mediated tumor promotion in murine skin.

9,10-Dimethyl-1,2-benzanthracene↗

PubMed1988

High-performance liquid chromatography of porphyrins.

Techniques for the analysis of porphyrins in the biomedical fields are reviewed. The emphasis is on high-performance liquid chromatography and its aspplications in: (1) the quantitative analysis of porphyrins in blood, urine and faeces; (2) qualitative porphyrin profiles in normal subjects and in the porphyrias; (3) assay of haem biosynthetic enzyme activities and (4) resolution of type isomers of porphyrins and porphyrinogens. Detection systems, quantitation methods, peak identification and sample preparation procedures are discussed.

Animals↗

PubMed2001

Detection of porphyrin using a short peptide immobilized on a surface plasmon resonance sensor chip.

In this paper the development and feasibility of a novel detection system for a low molecular weight chemical, in which a peptide was utilized as a binding molecule, are described. Surface plasmon resonance (SPR) apparatus was used as a transducer. The porphyrin binding peptide, PSP2, was used as a model peptide ligand, while a porphyrin derivative, H(2)TMpyP, was used as a model low-molecular-weight chemical. PSP2 was covalently immobilized onto the SPR sensor chip and SPR measurement using the PSP2-immobilized chip for various concentrations of porphyrin was carried out. H(2)TMpyP was detectable in the range from 100 ng ml(-1) to 10 microg ml(-1) with a linear correlation and good precision and the PSP2-immobilized chip could be regenerated within 1 min after measurement in this system. From comparison of the detection manners of three porphyrin derivatives, the ability of a short peptide to discriminate between differences in molecular structure was demonstrated. Moreover, the self-assembled monolayer (SAM) of PSP2 was successfully prepared on the gold substrate and H(2)TMpyP could be detected using the PSP2-SAM chip.

Amino Acid Sequence↗

PubMed2000

Photophysical properties of carborane-containing derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin.

Absorption, fluorescence emission, fluorescence excitation spectra and fluorescence decay kinetics of carborane derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin have been investigated. Carborane derivatives are prepared by acylation of the amino groups of 5,10,15,20-tetra(p-aminophenyl)porphyrin by 9-carboranyl acetyl chloride. From the analysis of the absorption and fluorescence spectra, it is concluded that covalent linking of carborane molecules to the tetraphenylporphyrin molecule significantly changes the self-conjugated pi-system of the porphyrin macrocycle: positions of maxima of absorption and fluorescence spectra shift to the red region by 3-8 nm; the halfwidths of these bands are broadened by 2.5-5.0 nm; the relative intensity of the bands I-IV also changes. The fluorescence decay kinetics of the carborane derivatives are biexponential. According to the experimental data and model simulation, it is concluded that the intramolecular electron transfer proceeds from the porphyrin excited part of the molecule to carboranyls with a rate constant of 415 ps(-1) and efficiency of 0.16-0.8. Recombination of separated charges occurs within 1.4 ns.

Boranes↗

PubMed2000

Long-range assemblies on poly(dG-dC)2 and poly(dA-dT)2: phosphonium cationic porphyrins and the importance of the charge.

The present paper describes synthesis and spectroscopic properties of novel cationic meso-tetraphenylporphyrins bearing two (trans) (P2) or three (P3) triphenylphosphonium substituents. The porphyrin aggregation in aqueous solutions is discussed in detail. Porphyrin binding to and self-organization onto long-range assemblies on poly(dA-dT)2 or poly(dG-dC)2 were probed by combination of absorption, fluorescence, circular dichroism (CD), transient and resonance light-scattering (RLS) techniques. The higher hydrophobicity of P2 is manifested by more extensive self-organization. Induced CD and intensive RLS indicate binding to the chiral environment on the nucleic acids exterior and exciton coupling between adjacent porphyrin moieties. The CD spectra of P2 on poly(dG-dC), and poly(dA-dT)2 suggest that the binding geometry is essentially independent of the base sequence. The fluorescence lifetime of about 4 ns was attributed to the long-range assembly. In the case of P3 the distinctly different CD spectra induced by GC or AT base-pair regions reveal that the number of the substituents determines how closely the porphyrin can approach the specific electronic environment on the nucleic acid exterior. The fluorescence lifetime of the P3 assembly is about 2 ns.

Circular Dichroism↗

PubMed2001

Selective distribution of porphyrins in skin thick basal cell carcinoma after topical application of methyl 5-aminolevulinate.

Topical photodynamic therapy (PDT) of superficial basal cell carcinoma (BCC) with 5-aminolevulinic acid (ALA) has achieved promising clinical results. However, the efficacy of this therapy for thick BCC is dramatically decreased by a limited diffusion of hydrophilic ALA into the tumor. Lipophilic esters of ALA may enhance their penetration into the lesion. In this randomized, open clinical study, microscopic fluorescence photometry incorporating a light-sensitive thermo-electrically cooled charge-coupled device (CCD) camera was employed to investigate the penetration of methyl 5-aminolevulinate-induced porphyrin fluorescence in thick BCC lesions. Both the distribution pattern and the amount of porphyrins in 32 lesions of 16 patients were studied after topical application of 16, 80 or 160 mg/g of methyl 5-aminolevulinate for 3 or 18 h. A highly selective and homogeneous distribution of methyl 5-aminolevulinate-induced porphyrin fluorescence was seen in all lesions studied, with much less fluorescence in the adjacent normal skin tissues. In lesions of up to 2 mm thickness the application of 160 mg/g methyl 5-aminolevulinate for 3 h showed the highest ratio of porphyrin fluorescence depth to tumor depth (0.98+/-0.04), thus providing a biologic rationale for a clinical PDT trial with this regimen.

Administration, Topical↗

PubMed1997

Photodynamic efficacy of naturally occurring porphyrins in endothelial cells in vitro and microvasculature in vivo.

Photodynamic therapy (PDT) has been described in terms of cellular and vascular effects. The precise mechanisms of cellular and vascular damage are still unknown. In this study, the photodynamic inactivation of endothelial cells in vitro and damage to the microvasculature in vivo by naturally occurring porphyrins (uroporphyrin III (UP), coproporphyrin III (CP) and protoporphyrin IX (PP)) were investigated. The chick chorioallantoic membrane model (CAM model) was used, which is convenient for the study of damage to the microcirculation induced by PDT. The hydrophilic porphyrins UP and CP exhibited low cytotoxicity towards endothelial cells. Only small amounts of UP and CP were taken up, resulting in weak inactivation after irradiation. In contrast, the more lipophilic PP showed a marked cytotoxicity. Considerable amounts of PP were accumulated in the cells, leading to pronounced inactivation after light exposure. For the three porphyrins, damage to the microvasculature was observed. The damage caused by the hydrophilic porphyrins UP and CP was strongly dependent on the drug and light dose. For vascular injury, the efficacy was graded as UP < CP < PP.

Animals↗

PubMed1998

Photophysical studies of excited-state characteristics of meso-tetrakis (4-N-methyl-pyridiniumyl) porphyrin bound to DNA.

The interaction of meso-tetrakis (4-N-methyl-pyridiniumyl) porphyrin (TMPyP) with DNA has been investigated at ionic strength (IS) values of 0.01 and 0.20 M (pH 6.8) using the flash-photolysis technique along with optical absorption and fluorescence data. It is found that the aggregation of TMPyP observed at the porphyrin excess reduces its total fluorescence intensity (JT) and the T-T absorption. At low IS the JT and the T-T absorption for the TMPyP monomers bound to the GC DNA sites are lower than those for the free ones, whereas binding to the AT sites (high IS) increases JT. At low IS the triplet decay of TMPyP is mono-exponential, the lifetime increasing with the [DNA] increase, while at high IS the addition of DNA transforms this profile to a bi-exponential form with lifetimes of the components independent of [DNA]. Binding to DNA reduces the quenching constants of the porphyrin triplet states by molecular oxygen (kq), the effect depending on the site and mode of binding. So, at low IS the kq value for the TMPyP externally bound to the GC sites (3.0 x 10(8) M-1 s-1) is five times lower than that for the free porphyrin and twice as high as that for the intercalated one. At high IS the TMPyP binding reduces the kq three-fold for the AT sites in the minor groove and 16-fold in the major groove as compared with the free one (approximately or equal to 1.6 x 10(9) M-1 s-1).

DNA↗

PubMed2001

Study on the supramolecular system of meso-tetrakis (4-sulfonatophenyl) porphyrin and cyclodextrins by spectroscopy.

The ability of beta-cyclodextrin (beta-CD), sulfurbutylether-beta-CD (SBE-beta-CD) and hydroxypropyl-beta-CD (HP-beta-CD) to break the aggregate of the meso-Tetrakis (4-sulfonatophenyl) porphyrin (TPPS4) and to form 2:1 inclusion complexes has been studied by adsorption and fluorescence spectroscopy. The formation constants are calculated, respectively by fluoremetry, from which the inclusion capacity of different CDs is compared and the inclusion mechanism of charged-beta-CD (SBE-beta-CD) is quite different from that of parent beta-CD. At lower pH, the complexation between HP-beta-CD and H2TPPS(2+)4 (the form of the diprotonated TPPS4) hampers the continuous protonation of the pyrrole nitrogen of TPPS4 and the hydrophobic cavity may prefer to bind an apolar neutral porphyrin molecule. 1HNMR data support the inclusion conformation of the porphyrin-cyclodextrin supramolecular system, indicating the interaction of meso-phenyl groups of TPPS4 with the cavity of CDs. For this host-guest inclusion model, cyclodextrin, being regarded as the protein component, which acts as a carrier enveloping the active site of heme prosthetic group within its hydrophobic environment, provides a protective sheath for porphyrin, creating artificial analogues of heme-containing proteins. However, the TPPS4, encapsulated within this saccharide-coated barrier, its physico-chemical, photophysical and photochemical properties changed strongly.

2-Hydroxypropyl-beta-cyclodextrin↗

PubMed1999

Comparative study of photophysical properties of isomeric tetrapyridyl- and tetra-(N-hexadecylpyridiniumyl) porphyrins.

Photophysical properties (absorption spectra, fluorescence spectra, lifetimes and quantum yields) were studied for the three isomers of tetrapyridylporphyrins (TPyPs) in CHCl3 and tetra-(N-hexadecylpyridiniumyl) porphyrins (TC16PyPs) in CHCl3, CH3OH and Triton X-100 micelle solution. While the ground-state and excited-state properties are very similar for the three isomers of neutral TPyP, significant differences exist among the isomers of amphiphilic TC16PyP. Amphiphilic porphyrins bearing hydrophilic pyridinium and hydrophobic long-chain alkyl groups are characterized by reduced fluorescence quantum yields, biexponential fluorescence decay, and appreciable aggregation in nonpolar solvents. The observed biexponential fluorescence decay of amphiphilic porphyrins can be interpreted in terms of mixing of the S1 and a close-lying CT state in which an electron is transferred from the porphyrin core to the electron-deficient pyridinium group.

Isomerism↗

PubMed2000

On-line LC-MS analysis of urinary porphyrins.

A reversed-phase high-performance liquid chromatography-mass spectrometry (LC-MS) method is described for the separation and simultaneous analysis of porphyrins related to disorders of heme biosynthesis (uro-, heptacarboxylic, hexacarboxylic, pentacarboxylic, and coproporphyrins). The method involves initial porphyrin esterification and extraction from urine. Detection and quantification is performed from the extracts by separation with a Hypersil BDS column and on-line detection by MS through coupling with an atmospheric pressure chemical ionization interface. The porphyrin esters are detected as protonated molecules [M + H]+. Their mass spectra also exhibit an [M + Na]+ fragment of lower intensity. The analytical performance of this method is compared with those of LC with UV and fluorescence detection. LC-MS used in selective [M + H]+ ion monitoring provides the lowest detection and quantitation limits. In scan mode, this LC-MS method affords, without further isolation or concentration steps, the measurement of mass spectra of unknown compounds present in the urine of patients with altered porphyrin excretion.

Chromatography, High Pressure Liquid↗

PubMed2002

A selective optode membrane for histidine based on fluorescence enhancement of meso-meso-linked porphyrin dimer.

A plasticized polymer film, poly(vinyl chloride) (PVC) incorporated with a specific porphyrin dimer, is shown to exhibit significant and analytical usefulness for optical response toward histidine. The porphyrin dimer containing a free-base porphyrin and a covalently linked metalloporphyrin is shown to be weakly fluorescent as a result of the photoinduced intramolecular electron transfer from the inner free-base porphyrin in singlet excited state to a low-spin cobalt(II). The fluorescence enhancement of the membrane by histidine is based on favorable extraction of histidine into the bulk organic membrane and complexation with the inner metallopophyrin moiety and inhibiting the electron transfer process. With the optode membrane described, histidine in a sample solution from 0.0045 to 1.53 mM can be determined. The calibration curve of the optode membrane for histidine shows a good correlation with the mathematically derived formalism and, thus, confirms the theoretically expected behavior. The sensor presented exhibits high selectivity toward histidine over several amino acids and common inorganic anions. The optical selectivity coefficients obtained for histidine over other biologically relevant amino acids and anions are shown to meet the selectivity requirements for the monitoring concentration levels of histidine in biological samples. The selective characteristic of the sensor has been discussed in the view of the coordination chemistry of metalloporphyrin.

Algorithms↗

PubMed2003

Porphyrin assembly on beta-cyclodextrin for selective sensing and detection of a zinc ion based on the dual emission fluorescence ratio.

In the present paper, a new cyclodextrin/porphyrin supramolecular sensitizer for zinc ion has been proposed based on the porphyrin dual fluorescence emission ratio. In aqueous solution, meso-tetraphenylporphyrin shows weak fluorescence, while in the presence of alkylated beta-cyclodextrin, it exhibits significant fluorescence enhancement by forming a cyclodextrin/porphyrin inclusion complex. Furthermore, the formation of a supramolecular complex causes a remarkable increase of the porphyrin metalation rate following the porphyrin fluorescence emission changes at two different emission wavelengths. The fluorescence emission of tetraphenylporphyrin at 656-nm bands decreases while that at 606 nm increases upon zinc ion interaction. Thus, the inclusion complex can behave as a ratiometric fluorescent sensor. Theoretically derivative equations for fluorescent ratiometry have been proposed for the first time. The feasibility of the proposed method is demonstrated by the performance of fluorometric detection of zinc ion. With the optimum conditions described, zinc ion in aqueous solution can be determined from 5.0 x 10(-7) to 2.5 x 10(-4) M. As the porphyrin electronic absorption and fluorescence emission are located in the visible range, and the fluorescence changes upon zinc ion interaction show high selectivity over biologically relevant cations, the inclusion complex could be used for biomedical application.

Cyclodextrins↗