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PubMed2003

Porphyrin and tetrabenzoporphyrin dendrimers: tunable membrane-impermeable fluorescent pH nanosensors.

The pH dependencies of the UV-vis and fluorescent spectra of new water-soluble dendritic porphyrins and tetrabenzoporphyrins were studied. Because of extended pi-conjugation and nonplanar distortion, the absorption and the emission bands of tetraaryltetrabenzoporphyrins (Ar(4)TBP) are red-shifted and do not overlap with those of regular tetraarylporphyrins (Ar(4)P). When encapsulated inside dendrimers with hydrophilic outer layers, Ar(4)Ps and Ar(4)TBPs become water soluble and can serve as pH indicators, with pK's adjustable by the peripheral charges on the dendrimers. Two new dendritic porphyrins, Gen 4 polyglutamic porphyrin dendrimer H(2)P-Glu(4)OH (1) with 64 peripheral carboxylates and Gen 1 poly(ester amide) Newkome-type tetrabenzoporphyrin dendrimer H(2)TBP-Nw(1)OH (2) with 36 peripheral carboxylates, were synthesized and characterized. The pK's of the encapsulated porphyrins (pK(H)()2(P)(-)(Glu)()4(OH) = 6.2 and pK(H)()2(TBP)(-)(Nw)()1(OH) = 6.3) were found to be strongly influenced by the dendrimers, revealing significant electrostatic shielding of the cores by the peripheral charges. The titration curves obtained by differential excitation using the mixtures of the dendrimers were shown to be identical to those determined for the dendrimers individually. Due to their peripheral carboxylates and nanometric molecular size, porphyrin dendrimers cannot penetrate through phospholipid membranes. Dendrimer 1 was captured inside phospholipid liposomes, which were suspended in a solution containing dendrimer 2. No response from 1 was detected upon pH changes in the bulk solution, while the response from 2 was predictably strong. When proton channels were created in the liposome walls, both compounds responded equally to the bulk pH changes. These results suggest that porphyrin dendrimers can be used as fluorescent pH indicators for proton gradient measurements.

Benzene Derivatives↗
PubMed2000

Rational syntheses of porphyrins bearing up to four different meso substituents.

Porphyrins bearing specific patterns of substituents are crucial building blocks in biomimetic and materials chemistry. We have developed methodology that avoids statistical reactions, employs minimal chromatography, and affords up to gram quantities of regioisomerically pure porphyrins bearing predesignated patterns of up to four different meso substituents. The methodology is based upon the availability of multigram quantities of dipyrromethanes. A procedure for the diacylation of dipyrromethanes using EtMgBr and an acid chloride has been refined. A new procedure for the preparation of unsymmetrical diacyl dipyrromethanes has been developed that involves (1) monoacylation with EtMgBr and a pyridyl benzothioate followed by (2) introduction of the second acyl unit upon reaction with EtMgBr and an acid chloride. The scope of these acylation methods has been examined by preparing multigram quantities of diacyl dipyrromethanes bearing a variety of substituents. Reduction of the diacyl dipyrromethane to the corresponding dipyrromethane-dicarbinol is achieved with NaBH(4) in methanolic THF. Porphyrin formation involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol and a dipyrromethane followed by oxidation with DDQ. Optimal conditions for the condensation were identified after examining various reaction parameters (solvent, temperature, acid, concentration, time). The conditions identified (2.5 mM reactants in acetonitrile containing 30 mM TFA at room temperature for <7 min) provided reaction without detectable scrambling (LD-MS) for aryl-substituted dipyrromethanes, and trace scrambling for alkyl-substituted dipyrromethanes. The desired porphyrins were obtained in 14-40% yield. The synthesis is compatible with diverse functionalities: amide, aldehyde, carboxylic acid, ester, nitrile, ether, bromo, iodo, ethyne, TMS-ethyne, TIPS-ethyne, perfluoroarene. In total 30 porphyrins of the types A(3)B, trans-A(2)B(2), trans-AB(2)C, cis-A(2)B(2), cis-A(2)BC, and ABCD were prepared, including >1-g quantities of three porphyrins.

Acylation↗
PubMed2005

Delayed dissociation of photoexcited porphyrin cations in a storage ring: determination of triplet quantum yields.

A technique is described wherein substituent-dependent excited-state properties of gas-phase porphyrins can be accurately quantified. Dissociation lifetimes of photoexcited porphyrin cations were measured in an electrostatic ion storage ring. From these data, upper limits for the triplet quantum yield of the following protonated porphyrins were obtained: protoporphyrin IX (0.63 +/- 0.04), tetraphenylporphyrin (0.73 +/- 0.03), tetra(p-methylphenyl)porphyrin (0.75 +/- 0.03), and tetra(p-cyanophenyl)porphyrin (0.71 +/- 0.03). The values compare well with those for porphyrins in solution.

Cations↗
PubMed2006

Synergism of porphyrin-core saddling and twisting of meso-aryl substituents.

The structural chemistry of meso-aryl-substituted porhyrins has uncovered a bewildering variety of macrocycle distortions. Saddling angles range up to 40 degrees , while the plane of the phenyl groups at the meso positions may be anywhere between perpendicular to the porphyrin plane (theta = 90 degrees) and tilted to quite acute angles (theta = 30 degrees or even less). These two distortions appear to be correlated. This has naturally been explained by steric hindrance: when the phenyls rotate toward the porphyrin plane, for instance, coerced by packing forces, the pyrrole rings can alleviate the steric hindrance by tilting away to a saddled conformation. We demonstrate, however, that the two motions are intrinsically coupled by electronic factors and are correlated even in the absence of external forces. A saddling motion makes it sterically possible for the phenyl rings to rotate toward the porphyrin plane, which will always happen because of increasingly favorable pi-conjugation interaction with smaller angles theta. The considerable energy lowering due to pi conjugation counteracts the energy cost of the saddling, making the concerted saddling/rotation motion very soft. Unsubstituted meso-aryl porphyrins just do not distort, but an additional driving force may tip the balance in favor of the combined distortion motion. Internal forces having this effect are repulsion of the four hydrogens that occupy the central hole of the ring in porphyrin diacids but also steric repulsion in peripherally crowded porphyrins. These findings lead to a clarification and systematization of the observed structural variety, which indeed shows a remarkable correlation between saddling and phenyl ring tilting.

Models, Chemical↗
PubMed2006

Theoretical solar-to-electrical energy-conversion efficiencies of perylene-porphyrin light-harvesting arrays.

The efficiencies of organic solar cells that incorporate light-harvesting arrays of organic pigments were calculated under 1 sun of air mass 1.5 solar irradiation. In one set of calculations, photocurrent efficiencies were evaluated for porphyrin, phthalocyanine, chlorin, bacteriochlorin, and porphyrin-bis(perylene) pigment arrays of different length and packing densities under the assumption that each solar photon absorbed quantitatively yielded one electron in the external circuit. In another more realistic set of calculations, solar conversion efficiencies were evaluated for arrays comprising porphyrins or porphyrin-(perylene)2 units taking into account competitive excited-state relaxation pathways. A system of coupled differential equations for all reactions in the arrays was solved on the basis of previously published rate constants for (1) energy transfer between the perylene and porphyrin pigments, (2) excited-state relaxation of the perylene and porphyrin pigments, and (3) excited-state electron injection into the semiconductor. This formal analysis enables determination of the optimal number of pigments in an array for solar-to-electrical energy conversion. The optimal number of pigments depends on the molar absorption coefficient and the density at which the arrays can be packed on an electrode surface. Taken together, the ability to employ fundamental photophysical, kinetic, and structural parameters of modular molecular architectures in assessments of the efficiency of solar-to-electrical energy conversion should facilitate the design of molecular-based solar cells.

Electrons↗
PubMed2005

Photoinduced electron transfer in self-assembled monolayers of porphyrin-fullerene dyads on ITO.

Two porphyrin-fullerene dyads were synthesized to form self-assembled monolayers (SAMs) on indium-tin oxide (ITO) electrode, with either ITO-porphyrin-fullerene or ITO-fullerene-porphyrin orientations. The dyads contain two linkers for connecting the porphyrin and fullerene moieties and enforcing them essentially to similar geometries of the donor-acceptor pair, and two linkers to ensure the attachment of the dyads to the ITO surface with two desired opposite orientations. The transient photovoltage responses (Maxwell displacement charge) were measured for the dyad films covered by insulating LB films, thus ensuring that the dyads interact only with the ITO electrode. The direction of the electron transfer was from the photoexcited dyad to ITO independent of the dyad orientation. The response amplitude for the ITO-fullerene-porphyrin structure, where the primary intramolecular electron-transfer direction coincides with the direction of the final electron transfer from the dyad to ITO, was 25 times stronger than that for the opposite ITO-porphyrin-fullerene orientation of the dyad. Static photocurrent measurements in a liquid electrochemical cell, however, show only a minor orientation effect, indicating that the photocurrent generation is controlled by the processes at the SAM-liquid interface.

Electrodes↗
PubMed2006

Electrochemical studies of porphyrin-appended dendrimers.

The electrochemical properties of porphyrin-appended dendrimers containing 2-, 4-, 8-, 16-, 32- and 64-porphyrin macrocycles in their free-base and zinc(II) forms have been investigated. Both series gave diffusional based voltammetric responses in dichloromethane. There was minimal effect of dendrimer generation on the redox potentials. Multiple pi-cation and anion radicals as well as dications and dianions were formed on the surface of the dendrimers on oxidation or reduction as appropriate, with each cyclic voltammetric wave representing electron transfer to or from multiple non-interacting porphyrin sites. Electrostatic interactions in the higher generation dendrimers result in kinetic effects being observed for the highly charged species generated when each porphyrin unit is doubly or triply oxidised. The number of electrons transferred on reduction or oxidation of the dendrimers was evaluated using steady-state microelectrode voltammetry. For the lower generations of species a good correlation was observed between numbers of electrons transferred and number of porphyrin entities per molecule; for the dendrimers containing 32 and 64 units, however, slight negative deviations were observed, possibly due to electrostatic interactions as the porphyrins become closer packed.

Biomimetic Materials↗
PubMed1977

Porphyrins and porphyrinogen carboxy-lase in hexachlorobenzene-induced porphyria.

1. Qualitative and quantitative studies of the porphyrins and the porphyrinogen carboxylyase of the liver, spleen, kidney, harderian gland and erythrocytes from normal rats and from those hexachlorobenzene-induced porphyria were carried out. 2. Hexachlorobenzene has no effect on erythrocyte porphyrin content, but produces a decrease in that of Harderian gland and an increase in the porphyrin content of the kidney and spleen, and a marked increase in the liver (1 mumol/g of tissue). Octacarboxylic (isomer III) and heptacarboxylic porphyrins accumulated in kidney, spleen and liver, the former porphyrin being predominant. 3. Hexachlorobenzene has no effect on the activity of porphyrinogen carboxy-lase in erythrocytes; there is a slight decrease in enzyme activity in the Harderian gland, and a marked decrease in the liver and kidney enzyme activities. In the liver the removal of each carboxyl group from uroporphyrinogen III appears to be affected by this treatment. 4. The liver is the principal site of action of hexachlorobenzene, with the kidney next in decreasing order of effect, and erythropoietic tissue is unaffected. The marked decrease in porphyrinogen carboxy-lyase activities observed in liver and kidney could explain the high accumulation of octacarboxylic and heptacarboxylic porphyrins found in these tissues. 5. The results are discussed in relation to changes promoted by hexachlorobenzene in other enzymes of the haem pathway.

Animals↗
PubMed2002

Designing supramolecular porphyrin arrays that self-organize into nanoscale optical and magnetic materials.

Tessellation of nine free-base porphyrins into a 3 x 3 array is accomplished by the self-assembly of 21 molecular entities of four different kinds, one central, four corner, and four side porphyrins with 12 trans Pd(II) complexes, by specifically designed and targeted intermolecular interactions. Strikingly, the self-assembly of 30 components into a metalloporphyrin nonamer results from the addition of nine equivalents of a first-row transition metal to the above milieu. In this case each porphyrin in the nonameric array coordinates the same metal such as Mn(II), Ni(II), Co(II), or Zn(II). This feat is accomplished by taking advantage of the highly selective porphyrin complexation kinetics and thermodynamics for different metals. In a second, hierarchical self-assembly process, nonspecific intermolecular interactions can be exploited to form nanoscaled three-dimensional aggregates of the supramolecular porphyrin arrays. In solution, the size of the nanoscaled aggregate can be directed by fine-tuning the properties of the component macrocycles, by choice of metalloporphyrin, and the kinetics of the secondary self-assembly process. As precursors to device formation, nanoscale structures of the porphyrin arrays and aggregates of controlled size may be deposited on surfaces. Atomic force microscopy and scanning tunneling microscopy of these materials show that the choice of surface (gold, mica, glass, etc.) may be used to modulate the aggregate size and thus its photophysical properties. Once on the surface the materials are extremely robust.

Magnetics↗
PubMed2003

Reactions of manganese porphyrins with peroxynitrite and carbonate radical anion.

We have studied the reaction kinetics of ten manganese porphyrins, differing in their meso substituents, with peroxynitrite (ONOO-) and carbonate radical anion (CO3.) using stopped-flow and pulse radiolysis, respectively. Rate constants for the reactions of Mn(III) porphyrins with ONOO- ranged from 1 x 10(5) to 3.4 x 10(7) m(-1) s(-1) and correlated well with previously reported kinetic and thermodynamic data that reflect the resonance and inductive effects of the substituents on the porphyrin ring. Rate constants for the reactions of Mn(III) porphyrins with CO3. ranged from 2 x 10(8) to 1.2 x 10(9) m(-1)s(-1) at pH <or= 8.5 and increased with pH as a consequence of the ionization of the complexes. Mn(II) porphyrins reacted with CO3. with rate constants ranging from 1 x 10(9) to 5 x 10(9) m(-1)s(-1) at pH 10.4. Hence, fast scavenging of ONOO- and CO3. by manganese porphyrins could occur in vivo because of the catalytic reduction at the expense of a number of cellular reductants. Additionally, we determined the pKa of the axial water molecules of the Mn(III) complexes at pH 7.5-13.2 by spectrophotometric titration. Results were consistent with two acid-base equilibria for most of the complexes studied. The pKa values also correlated with the resonance and inductive effects of the substituents. The correlations of E(1/2) with the rate constants with ONOO- and with the pKa values display a deviation from linearity when N-alkylpyridinium substituents included N-alkyl moieties longer than ethyl, which is interpreted in terms of a decrease in the local dielectric constant.

Anions↗
PubMedDate not supplied

Porphyrin status in aluminum foundry workers exposed to hexachlorobenzene and octachlorostyrene.

The possible interference of hexachlorobenzene and octachlorostyrene (i.e., thermal byproducts from hexachloroethane in aluminum degassing) with porphyrin metabolism was investigated in exposed workers. Urine specimens from 9 male aluminum foundry workers (i.e., smelters) at 6 different companies and from 18 controls-matched for sex, age, residence, and socioeconomic status-were analyzed for total porphyrins and porphyrin isomers. Workers exposed to hexachlorobenzene and octachlorostyrene had a statistically significant increase in urinary total porphyrins, compared with controls (mean +/- standard deviation: 13.63 +/- 11.13 micromol/mol creatinine and 6.24 +/- 3.84 micromol/mol creatinine, respectively; p = .02). The authors attributed the results mainly to differences in excretion of coproporphyrins-notably coproporphyrin III. Erythrocyte uroporphyrinogen decarboxylase activity was similar in both groups. There was a high correlation between levels of hexachlorobenzene and octachlorostyrene, respectively, in plasma and urinary excretion of porphyrins; these findings, however, relied heavily on 1 subject for whom extreme values were obtained. The results indicated that occupational exposure to hexachlorobenzene and octachlorostyrene in aluminum degassing with hexachloroethane may affect porphyrin metabolism in a manner consistent with early secondary coproporphyrinuria-the first recognized step in the development of chronic hepatic porphyria. It was also noted that changes remained detectable some years after exposure ceased.

Adult↗
PubMed1984

OH radical formation by photolysis of aqueous porphyrin solutions. A spin trapping and e.s.r. study.

Radical production during the photolysis of deaerated aqueous alkaline solutions (pH 11) of some water-soluble porphyrins was investigated. Metal-free and metallo complexes of tetrakis (4-N-methylpyridyl)porphyrin (TMPyP) and tetra (4-sulphonatophenyl)porphyrin (TPPS4) were studied. Evidence for the formation of OH radicals during photolysis at 615, 545, 435, 408 and 335 nm of Fe(III) TPPS4 is presented. Fe(III) TMPyP, Mn(III) TPPS4 and Mn(III) TMPyP also gave OH radicals but only during photolysis at 335 nm. The method of spin trapping with 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) and 4-pyridyl-1-oxide-N-tert-butylnitrone (POBN) combined with e.s.r. was used for the detection of OH, H and hydrated electrons. With the spin trap DMPO, photolysis generated DMPO-OH adducts under certain conditions but no DMPO-H adducts could be observed. With POBN, no POBN-H adducts were found. The formation of OH was confirmed by studying competition reactions for OH between the spin traps and OH scavengers (formate, isopropanol) and the concomitant formation of the CO-2 adduct and the (CH3)2COH adduct with both DMPO and POBN. The photochemical generation of OH radicals was pH dependent; at pH 7.5 no OH radicals could be detected. Photolysis (615-335 nm) of dicyanocomplexes of the Fe(III) porphyrins did not produce OH radicals. When corresponding Cu(II), Ni(II), Zn(II) and metal-free porphyrins were photolysed at 615 and 335 nm, no OH radicals could be spin trapped. These results tend to associate the well-known phenomenon of photoreduction of Fe(III) and Mn(III) porphyrins with the formation of OH radicals. This process is described mainly as the photoreduction of the metal ion by the ligand-bound hydroxyl ion via an intramolecular process.

Electron Spin Resonance Spectroscopy↗
PubMedDate not supplied

Alcohol and porphyrin metabolism.

Alcohol is a porphyrinogenic agent which may cause disturbances in porphyrin metabolism in healthy persons as well as biochemical and clinical manifestations of acute and chronic hepatic porphyrias. After excessive consumption of alcohol, a temporary, clinically asymptomatic secondary hepatic coproporphyrinuria is observable, which can become persistent in cases of alcohol-induced liver damage. Nowadays, the alcohol-liver-porphyrinuria syndrome is the first to be mentioned in secondary hepatic disturbances of porphyrin metabolism. Acute hepatic porphyrias (acute intermittent porphyria, variegate porphyria and hereditary coproporphyria) are considered to be molecular regulatory diseases, in contrast to non-acute, chronic hepatic porphyria, clinically appearing as porphyria cutanea tarda (PCT). Porphyrins do not accumulate in the liver in acute porphyrias, whereas in chronic hepatic porphyrias they do. Thus, chronic hepatic porphyria is a porphyrin-accumulation disease, whereas acute hepatic porphyrias are haem-pathway-dysregulation diseases, characterized in general by induction of delta-aminolevulinic acid synthase in the liver and excessive stimulation of the pathway without storage of porphyrins in the liver. The clinical expression of acute hepatic porphyrias can be triggered by alcohol, because alcohol augments the inducibility of delta-aminolevulinic acid synthase. In chronic hepatic porphyrias, however, which are already associated with liver damage, alcohol potentiates the disturbance of the decarboxylation of uro- and heptacarboxyporphyrinogen, which is followed by a hepatic accumulation of uro- and heptacarboxyporphyrin and their sometimes extreme urinary excretion. Especially in persons with a genetic deficiency of uroporphyrinogen decarboxylase, but also in patients with the so-called sporadic variety of PCT, alcohol is able to transform an asymptomatic coproporphyrinuria into PCT. Alcohol has many biochemical and clinical effects on porphyrin and haem synthesis both in humans and laboratory animals. Ethanol suppresses the activity of porphobilinogen synthase (synonym: delta-aminolevulinic acid dehydratase), uroporphyrinogen decarboxylase, coproporphyrinogen oxidase and ferrochelatase, whereas it induces the first and rate-limiting enzyme in the pathway, delta-aminolevulinic acid synthase and also porphobilinogen deaminase. Therefore, teetotalism is a therapeutically and prophylactically important measure in all types of hepatic porphyrias.

Acute Disease↗
PubMed1992

Effects of human chorionic gonadotropin and progesterone administration on porphyrin biosynthesis and histology of the Harderian glands in male and female Syrian hamsters.

We investigated the influence of hCG and progesterone on the control of porphyrin biosynthesis and histology in the Syrian hamster Harderian glands. Castration of male hamsters caused a marked elevation in porphyrin biosynthesis as revealed by the concentrations of porphyrins and the mRNA levels of the porphyrin pathway rate-limiting enzyme, 5-aminolevulinate synthase (ALV-S). Injection of hCG into castrated male hamsters also resulted in a significant increase in both porphyrin concentrations and levels of ALV-S mRNA compared with those in saline-injected castrated hamsters. Type II cells, which are filled with large lipid vacuoles and are characteristic of male phenotype, disappeared after castration, but administration of hCG partially prevented this change. On the other hand, neither administration of hCG nor progesterone implants could increase the very high porphyrin concentrations and ALV-S mRNA levels characteristic of female Syrian hamsters. As in the case of castrated male hamsters, injections of 20 IU hCG to female Syrian hamsters increased the relative number of Type II cells per square millimeter, whereas progesterone administration did not modify the relative number of Type II cells. These results indicate that hCG can modify Harderian gland morphology in both male and female hamsters and can exert a positive control in the expression of ALV-S gene in castrated male hamsters.

5-Aminolevulinate Synthetase↗
PubMed1978

Studies on porphyrin-heme biosynthesis in organotypic cultures of chick dorsal root ganglion. I. Observations on neuronal and non-neuronal elements.

Living, mature organotypic cultures of chick dorsal root ganglion maintained in culture for 3 weeks were incubated in medium containing various levels of a precursor of porphyrin and heme formation, delta-aminolevulinic acid (ALA), (0.5 mM to 10 mM) or a combination of ALA (10 MM) and a metal chelator, CaMg-EDTA (5 mM) for up to 48 hours. Although no morphologic changes occurred in the cultures incubated with these compounds as observed by bright-field or dark-field microscopy, fluorescence microscopic study at 12, 24, and 48 hours demonstrated an intense red fluorescence with in the non-neuronal cells of the cultures (Schwann cells, fibroblasts, and macrophages) but not in the nerve cells. Spectrofluorometric analysis of perchloric acid-methanol extracts of the cultures revealed an emission spectrum characteristic of porphyrins. Autoradiographic studies, using 14C-labelled ALA, indicated that ALA was taken up by all cells (nerve cells as well as non-neuronal cells) in the cultures. The cultures incubated with ALA plus the metal chelator CaMg-EDTA showed the same distribution of porphyrin fluorescence, but a 2-fold increase in the amount of porphyrins was generated, when compared to cultures incubated with ALA alone. This observation suggests that a considerable fraction of porphyrins may be utilized to form heme in these cells since CaMa-EDTA blocks ferrochelatase activity, the terminal enzyme in the heme biosynthetic pathway. This is the first demonstration of active porphyrin-heme biosynthesis from ALA in cultured nervous system cells. Our results indicate that this biosynthetic pathway remains active in 3-week old cultures of chick dorsal root ganglion, and further, that the pathway appears to be predominantly present in the non-neuronal cellular elements of the ganglion rather than in nerve cells.

Aminolevulinic Acid↗
PubMed1977

Studies in porphyria. VI. Biosynthesis of porphyrins in mammalian skin and in the skin of porphyric patients.

Porphyrin biosynthesis in mammalian skin and in skin obtained from patients with selected types of porphyria has been studied. Cutaneous porphyrinogenesis required the precursor delta-aminolevulinic acid (ALA) which, when added to murine, rat, and human skin in vitro, was rapidly converted to porphyrins. Total porphyrin content was quantitated by fluorescence assay, and spectral studies indicated that more than 80% of the porphyrin produced was protoporphyrin. The majority of skin porphyrinogenesis occurrred in epidermis or in epidermal derivatives such as hair roots. Known inducers of hepatic delta-aminolevulinic acid synthetase (ALAS), the rate-limiting enzyme for heme biosynthesis, were not inducers when added to skin in vitro. Skin from patients with acute intermittent porphyria demonstrated a 43% decrease in cutaneous porphyrin production as compared to unaffected normals. This is consistent with the known deficiency of uroporphyrinogen synthetase that has been previously demonstrated in the liver and red blood cells of these patients. Porphyrinogenesis in skin of patients with porphyria cutanea tarda was not different from controls. These studies demonstrate that skin has the enzymatic capacity to synthesize porphyrins from added ALA and that cutaneous porphyrinogenesis from ALA is deficient in patients with acute intermittent porphyria.

Allylisopropylacetamide↗
PubMed1991

Regioselective photoreduction of zinc(II) porphyrins to give chlorins.

The ascorbic acid/organic base photoreduction of zinc(II) porphyrins was investigated. It was established that certain substituents can direct the photoreduction to the site of the macrocycle to which they are attached. For example, zinc(II) vinylporphyrins (8, 12, 16, 20) are photoreduced with cis stereochemistry on the ring bearing the vinyl group to give the corresponding chlorins. Zinc(II) acetylporphyrins (22, 24) were likewise reduced to chlorins such that cis-hydrogenation took place on the ring bearing the acetyl group. Zinc(II) formylporphyrins 33 also appear to reduce at the ring bearing the formyl group. When the zinc(II) acrylic porphyrin 28 was photoreduced, reduction did take place at the ring bearing the acrylic side chain, but migration of the acrylate double bond was very rapid, and the product isolated was the corresponding porphyrin propionate 30. Reduction of a zinc(II) porphyrin 35 bearing both a vinyl group and a nuclear carboxylic ester took place at the ring bearing the carboxylic ester. The reaction provides a general method for regioselective synthesis of chlorins from zinc(II) porphyrins without any evidence of formation of over-reduction products characteristic of many other procedures for formation of chlorins from porphyrin precursors.

Metalloporphyrins↗
PubMed1995

Inhibition of the ATPase activity of P-glycoprotein by porphyrin photosensitization of multidrug-resistant cells in vitro.

The effectiveness of photodynamic therapy against P-glycoprotein ATPase activity in multidrug-resistant cells was studied. Chinese hamster ovary AUXB1 (drug-sensitive) and CR1R12 (multidrug-resistant) cell lines were compared with respect to uptake of 14C-polyhematoporphyrin and porphyrin photosensitization. Phototoxicity of Photofrin was similar in both cell lines, and no major differences in uptake or efflux of 14C-polyhematoporphyrin were observed. Porphyrin photosensitization in vitro of CR1R12 cells or isolated plasma membranes from these cells caused inhibition of P-glycoprotein ATPase activity. Application of porphyrin photosensitization at a sublethal level to CR1R12 cells resulted in a small but significant increase in adriamycin-induced cytotoxicity. The hydrophobic "picket-fence" porphyrin, meso-tetrakis-(o-propionamidophenyl)porphyrin, alpha,alpha,alpha,beta-isomer, was more inhibitory toward P-glycoprotein ATPase activity than the two less hydrophobic porphyrins tetraphenylporphine tetrasulfonate and Photofrin.

ATP Binding Cassette Transporter, Subfamily B, Mem↗