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PubMed2003

Cellular defense against singlet oxygen-induced oxidative damage by cytosolic NADP+-dependent isocitrate dehydrogenase.

Singlet oxygen (1O2) is a highly reactive form of molecular oxygen that may harm living systems by oxidizing critical cellular macromolecules. Recently, we have shown that NADP+-dependent isocitrate dehydrogenase is involved in the supply of NADPH needed for GSH production against cellular oxidative damage. In this study, we investigated the role of cytosolic form of NADP+-dependent isocitrate dehydrogenase (IDPc) against singlet oxygen-induced cytotoxicity by comparing the relative degree of cellular responses in three different NIH3T3 cells with stable transfection with the cDNA for mouse IDPc in sense and antisense orientations, where IDPc activities were 2.3-fold higher and 39% lower, respectively, than that in the parental cells carrying the vector alone. Upon exposure to singlet oxygen generated from photoactivated dye, the cells with low levels of IDPc became more sensitive to cell killing. Lipid peroxidation, protein oxidation, oxidative DNA damage and intracellular peroxide generation were higher in the cell-line expressing the lower level of IDPc. However, the cells with the highly over-expressed IDPc exhibited enhanced resistance against singlet oxygen, compared to the control cells. The data indicate that IDPc plays an important role in cellular defense against singlet oxygen-induced oxidative injury.

3T3 Cells↗
PubMed1989

Singlet oxygen induces frank strand breaks as well as alkali- and piperidine-labile sites in supercoiled plasmid DNA.

A covalently closed, circular, supercoiled plasmid was exposed to singlet oxygen by a separated-surface sensitizer. For each exposure, the quantity of single oxygen entering the DNA target solution was estimated by its oxidation of histidine. After singlet oxygen exposure, some DNA samples were treated to disclose occult lesions. Agarose gel electrophoresis was then used to resolve the unrelaxed supercoils from the relaxed circular and linear species, and all bands were quantitated fluorometrically. Exposure of supercoiled plasmid DNA to singlet oxygen induced frank DNA strand breaks, alkali-labile sites (pH 12.5, 90 degrees C, 30 min), and piperidine-labile sites (0.4 M, 60 degrees C, 30 min), all in a dose-dependent manner. Yields of alkali-labile and piperidine-labile sites ranged from one to four times the frank strand break yield. Replacement of buffered H2O by buffered D2O as the DNA solvent for singlet oxygen exposures increased DNA lesion yields by a factor of 2.6 (averaged over lesion classes). Our data for the detection of frank strand breaks is at variance with published results from studies in which singlet oxygen was derived from a thermolabile endoperoxide dissolved in the DNA solution.

Alkalies↗
PubMed1990

EPR studies of trapped singlet oxygen (1O2) generated during photoirradiation of hypocrellin A.

Hypocrellin A, a peryloquinone derivative, has recently been isolated from the sacs of the fungus Hypocrella bambusae. This pigment, in combination with phototherapy, has been used in human medicine to cure various skin diseases. The generation of singlet oxygen during photoirradiation of Hypocrellin A (HA) was detected as an oxidation product of a sterically hindered amine (tetramethylpiperidine oxide; TEMPO) by electron paramagnetic resonance (EPR) spectroscopic techniques. Azide inhibited the EPR signal intensity in a dose-dependent manner with a quenching rate constant of 3.86 x 10(8) M-1s-1 in ethanol. Deuterated solvents, known to increase the lifetime of singlet oxygen, augmented the EPR signal intensity. The rate of production of singlet oxygen was dependent not only upon the concentration of HA and the time of irradiation but also on the oxygen content of the reaction mixture. The hyperfine splitting constant (aN = 16.3 G) and g-value (g = 2.0056) of the photoproduct of TEMP-singlet oxygen and TEMPO were found to be identical. This indicates that the nitroxide species detected by EPR spectroscopy generated by reacting TEMP with photogenerated 1O2 is TEMPO. The rate constant (kT) for the reaction of singlet oxygen with TEMP to form TEMPO radical was found to be 5.3 x 10(5) M-1s-1.

Electron Spin Resonance Spectroscopy↗
PubMed2002

Formation of singlet oxygen by urocanic acid by UVA irradiation and some consequences thereof.

Singlet oxygen-initiated decomposition of urocanic acid (UCA) (3-(1H-imidazol-4(5)-yl)-2-propenoic acid) was used to successfully confirm the report that UCA generates singlet oxygen when irradiated with ultraviolet A light (UVA). The UCA-generated singlet oxygen converts UCA to one or more products that then catalyze the further destruction of the UCA with UVA light by singlet oxygen formation. Some nicking of the phiX-174 supercoiled plasmid DNA was observed when UCA was irradiated with UVA to complete destruction of the starting material, and the product mixture was then mixed with the plasmid in the dark. More extensive nicking was seen when the photoproduct mixture and the plasmid were irradiated with UVA light. An "aged" (4 days) solution of UCA photoproduct no longer caused nicking in the dark but retained the capability to nick the plasmid when irradiated. There is evidence for the presence of hydroperoxides in the UCA photolysis product mixture, and the quenching studies with 2-propanol indicate that free radicals are involved in the plasmid-nicking photochemistry. Singlet oxygen does not appear to play a role in the nicking of the plasmid.

Bacteriophage phi X 174↗
PubMed1999

Singlet oxygen-mediated photobleaching of the prosthetic group in hemoglobins and c-phycocyanin.

Proteins bearing colored prosthetic groups, such as the heme group in hemoglobin or the bilin group in c-phycocyanin, quench singlet oxygen by interactions at the apoprotein and the prosthetic group levels. In both proteins, chemical modification of the chromophore constitutes only a minor reaction pathway. While total deactivation of singlet oxygen takes place with rate constants of 4.0 x 10(9) and 4.2 x 10(8) M-1 s-1 for hemoglobin and phycocyanin, respectively, the bleaching of the chromophore takes place with rate constants of 3.2 x 10(6) and approximately 1 x 10(7) M-1 s-1. Irradiation of phycocyanin with red light bleaches the chromophore with low yields (approximately 0.8 x 10(-4)). Part of this bleaching is mediated by singlet oxygen produced by the irradiation of the bilin group. The low relevance of the singlet oxygen pathway is compatible with a low quantum yield (approximately 10(-3)) of free singlet oxygen production after irradiation of the protein.

Cyanobacteria↗
PubMed1986

Singlet oxygen production by bleomycin. A comparison with heme-containing compounds.

Fe(III)-bleomycin catalyzes the decomposition of 13-hydroperoxylinoleic acid and of 15-hydroperoxyarachidonic acid to produce small quantities of singlet oxygen. No singlet oxygen is produced when hydrogen peroxide, ethyl hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide are used as substrates. The heme-containing catalysts, methemoglobin and hematin, have identical hydroperoxide substrate requirements for singlet oxygen production. The hydroperoxide requirements for singlet oxygen production correlate with those reported by Dix et al. (Dix, T.A., Fontana, R., Panthani, A., and Marnett, L.J. (1985) J. Biol. Chem. 260, 5358-5365) for the production of peroxyl radicals in the hematin-catalyzed decomposition of hydroperoxides. The bimolecular reaction of peroxyl radicals is a plausible reaction mechanism for the singlet oxygen production in the systems studied.

Arachidonic Acids↗
PubMed1989

[Role of singlet oxygen in pathogenesis of liver injury in rats treated with D-galactosamine].

A study was conducted to elucidate the possible role of singlet oxygen in pathogenesis of D-galactosamine-induced liver injury. Tissue and plasma levels of singlet oxygen were determined with chemiluminescence analysis. Following results were obtained: 1) Chemiluminescence as well as malondialdehyde, which is regarded as one of terminal products of lipid peroxidation, significantly increased in the liver and plasma of rats treated with D-galactosamine. 2) Elevation of plasma GPT and total bilirubin was also observed in rats with D-galactosamine-induced liver injury. Histological examination of the liver revealed submassive hepatic necrosis. 3) Administration of vitamin E, a radical scavenger of singlet oxygen, significantly inhibited the increases of chemiluminescence and MDA in the liver and plasma as well as the elevations of GPT and total bilirubin in the plasma. Histological changes of the liver were also found to improve significantly by vitamin E administration. In conclusion, singlet oxygen seems to be definitely involved, at least in part, in pathogenesis of liver damage induced by D-galactosamine. In addition, inhibition of the liver injury is possible, to some extent, by administration of vitamin E, one of the potent radical scavengers of singlet oxygen.

Animals↗
PubMed1988

Singlet oxygen production from the peroxidase-catalyzed oxidation of indole-3-acetic acid.

The aerobic oxidation of indole-3-acetic acid catalyzed by horseradish peroxidase produces 1268 nm emission characteristic of singlet oxygen. Lactoperoxidase also oxidizes indole-3-acetic acid to produce singlet oxygen, but in contrast to horseradish peroxidase, this enzyme system requires hydrogen peroxide. In both of these systems, the intensity of the 1268 nm emission is small due to quenching of the singlet oxygen by indole-3-acetic acid and by reaction products derived from indole-3-acetic acid. The biomolecular reaction of peroxyl radicals via a Russell mechanism is a plausible mechanism for the singlet oxygen generation in these systems. Under typical conditions of p2H 4.0, 1 microM horseradish peroxidase, 1 mM indole-3-acetic acid, and 240 microM oxygen, the singlet oxygen yield was 15 +/- 1 microM or 13% of the amount predicted by the Russell mechanism.

Horseradish Peroxidase↗
PubMedDate not supplied

Chemiluminescence of 2-methyl-6-arylimidazo-[1,2-a]pyrazin-3(7H)-one in protic solvents: electron-donating substituent effect on the formation of the neutral singlet excited-state molecule.

2-Methyl-6-arylimidazo[1,2-a]pyrazin-3(7H)-ones with a substituent such as phenyl, 4-methoxyphenyl or 4-trifluoromethoxyphenyl at the 6-position of the imidazo[1,2-a]pyrazin-3(7H)-one ring system, produced chemiluminescence emission in mixtures of water and DMF and in several mixtures of MeOH and DMF under neutral conditions. Under these protic luminescence conditions, the respective light emissions were generated from neutral singlet excited-state molecules. The electron-donating effect of the 4-methoxy substituent on the phenyl group increased the efficiency of the neutral singlet excited state formation, whereas non-substitution and a 4-trifluoromethoxy group having no electron donating ability decreased the efficiency. The compound having the electron-donating methoxy group substituent showed two chemiluminescence emitters, which generated light at lambda(max) 410-420 nm and 460 nm. It was determined that the neutral molecules in the excited state generating light emission at the shorter wavelengths are neutral singlet excited-state molecules suitable for highly efficient singlet excited-state formation. A role of the electron-donating effect of the methoxy group is postulated to be generation of the special neutral singlet excited-state molecules.

Dimethylformamide↗
PubMed1978

Studies on the properties of the singlet oxygen-like factor produced during lipid peroxidation.

The singlet oxygen reaction product of various trapping agents is observed during enzymic and nonenzymic peroxidation of microsomes as well as during the peroxidation of pure lipids extracted from microsomes. We now wish to report that purified fatty acid hydroperoxide alone, as well as peroxidized microsomal lipid and cumene hydroperoxide also form the singlet oxygen reaction product with 2,5-diphenylfuran. The reaction product (cis-1,2-dibenzoylethylene) was observed to be formed in an anaerobic system, with or without EDTA. The data indicate that a reaction of hydroxyl radicals with 2,5-diphenylfuran cannot account for the formation of dibenzoylethylene in these systems. These results are consistent with a hypothesis that the singlet oxygen-like factor was formed from the lipid peroxides per se and, in addition, supports the possibility that either the peroxides can react directly with diphenylfuran to produce dibenzoylethylene or that the self-reaction of organic peroxides may form an intermediate product which can react directly with singlet oxygen-trapping agents to produce substances which are identical to a reaction of the trapping agents with singlets oxygen.

Animals↗
PubMed1981

The relationship of the carcinogenic/mutagenic potential of arylamines to their singlet-triplet nitrenium ion energies.

Utilizing intermediate neglect of differential overlap (INDO) and ab initio methodology, trends in the energy differences between the singlet and triplet states for mono- and polycyclic aryl nitrenium ions have been estimated. Calculations reveal an empirical correlation between the energy separation of the singlet and triplet states of the nitrenium ion and the ability of the parent amine to behave as a carcinogen or mutagen. Non-carcinogenic/non-mutagenic arylamines were characterized by nitrenium ions whose singlet states were much less stable than the triplet. Carcinogenic/mutagenic amines were characterized by nitrenium ions whose singlet states were of similar or greater stability than the triplet. By examination of the charge density at key ring atoms of the singlet and triplet species, a rational approach to the stabilization of one species relative to the other has merged and forms the basis for prediction of genotoxicity in closely related structures. The application of this empirical correlation to the prediction of the carcinogenic/ mutagenic potential of arylamines is discussed.

2-Acetylaminofluorene↗
PubMed1997

MCSCF/MP2 Study of the Cheletropic Addition of Singlet and Triplet CF(2) and C(OH)(2) to the Ethene Double Bond.

CAS-MCSCF calculations describe the addition of singlet CF(2) and C(OH)(2) to the ethene double bond as a two-step reaction. The energy barriers that separate, in the first rate-determining step, loosely bound pi-complexes from stable CH(2)CH(2)CX(2) diradical intermediates show the expected ordering, smaller for CF(2) than for C(OH)(2). Back-dissociation of the diradicals into reactants requires the overcoming of non-negligible energy barriers. In both diradicals, the CAS-MCSCF activation energy for ring closure is smaller than that required for rotation of their terminal methylenic groups, which models, in these simple systems, an isomerization process. However, when the activation free energies are computed, in the case of the difluoro diradical the isomerization process appears to be less disfavored (and possibly competitive to some extent at higher temperatures); in contrast, in the case of the dioxy diradical, isomerization is never competitive with ring closure. The small energy barriers for ring closure of the diradicals disappear altogether when multireference MP2 energy calculations are carried out on the CAS-MCSCF critical points, casting doubts on the very existence of these intermediates. However, in contrast with the ethene reaction, the addition of singlet CF(2) to isobutene involves the formation of a diradical intermediate whose barrier for ring closure persists also at the MP2 level. These results suggest that cyclopropanation is likely to be a two-step process (with formation of a diradical intermediate) only with bulky substituted alkenes, while the attack to an unsubstituted double bond could be an asynchronous but concerted process. The analogous triplet reactions go through transition and stable structures of lower symmetry than the singlet and see the intervention of diradical intermediates. Their formation is easier than that in the singlet case and their stability with respect to back-dissociation higher. Also the isomerization processes (taking place again through rotation of the terminal methylenic group) are easier than those examined on the singlet surfaces.

Journal Article↗
PubMedDate not supplied

Reaction of singlet oxygen with 2'-deoxyguanosine and DNA. Isolation and characterization of the main oxidation products.

The reaction of singlet molecular oxygen with 2'-deoxyguanosine and DNA was studied. Emphasis was placed on the identification and characterization of the main methylene blue mediated type II (singlet oxygen) oxidation products of 2'-deoxyguanosine and its corresponding 3',5'-di-O-acetylated derivative. Two major oxidation products of 2'-deoxyguanosine were isolated and characterized by mass spectrometry analysis and extensive 1H and 13C NMR measurements as the two 4R* and 4S* diastereomers of 4,8-dihydro-4-hydroxy-8-oxo-2'-deoxyguanosine. The addition of 1O2 was also found to occur to the base moiety of the corresponding 3',5'-di-O-acetylated derivative. Methylene blue mediated photosensitization of 2'-deoxyguanosine led also to the production of 7,8-dihydro-8-oxo-2'-deoxyguanosine, but in a relatively lower yield with respect to the two above diastereomers. The participation of singlet oxygen in the mechanism of formation of these oxidation products was confirmed. A reasonable mechanism involving the transient formation of an unstable endoperoxide produced through a Diels-Alder 1,4-cycloaddition of singlet oxygen to the purine ring is suggested. Quantitative analysis allowed us to demonstrate that the two diastereomers of 4,8-dihydro-4-hydroxy-8-oxo-2'-deoxyguanosine are the main singlet oxygen oxidation products of the guanine moiety within nucleosides, whereas 7,8-dihydro-8-oxoguanine was found to be the major 1O2 oxidation product of guanine in double-stranded DNA.

Circular Dichroism↗
PubMed1996

Singlet oxygen scavengers affect laser-dye impairment of endothelium-dependent responses of brain arterioles.

This study investigates the possible role of singlet oxygen in accounting for the inhibitory effect of laser-dye injury on endothelium-dependent dilations. The combination of helium-neon (HeNe) laser (20-s exposure) and intravascular Evans blue impairs endothelium-dependent dilation of mouse pial arterioles by acetylcholine (ACh), bradykinin (BK), and calcium ionophore A23187. Each has a different endothelium-derived mediator (EDRFACh, EDRFBK, EDRFionophore, respectively). In this study, diameters at a craniotomy site were monitored in vivo with an image splitter-television microscope. The laser-dye injury, as usual, abolished the responses 10 and 30 min after injury, with recovery, complete or partial, at 60 min. Dilations by sodium nitroprusside, an endothelium-independent dilator, were not affected by laser-dye. When the singlet oxygen scavengers L-histidine (10(-3) M) and L-tryptophan (10(-2) M) were added to the suffusate over the site, the responses to ACh at 10 and 30 min were relatively intact, the response to BK was partly protected at 10 min only, and the response to ionophore was still totally impaired at 10 and 30 min. Lysine, a nonscavenging amino acid, had no protective effects with any dilator. We postulate that a heat-induced injury initiates a chain of events resulting in prolonged singlet oxygen generation by the endothelial cell (not by the dye). We postulate further that destruction of EDRFACh by singlet oxygen is responsible for laser-dye inhibition of ACh and that generation of the radical must continue for > or = 30 min. On the other hand, the heat injury itself is probably responsible for the elimination of the response to ionophore. Heat plus singlet oxygen generated by heat-damaged tissue may initially impair the response to BK, but by 30 min only the effects of some other factor, presumably heat injury, account for the impaired response to BK.

Animals↗
PubMed1980

Singlet oxygen and aging in Drosophila.

There was little or no improvement in the median survival times of Drosophila melanogaster fruit flies when fed high concentrations of the singlet oxygen quenchers, beta-carotene and 1,4-diazabicyclo(2.2.2)octane. Singlet oxygen was presumably generated endogenously by inactivating catalse with 3-amino-1,2,4-triazole and feeding NaOCl. This treatment caused reduction in median life span of from 14.3 to 25% depending upon the NaOCl concentration used. beta-Carotene and 1,4-diazabicyclo(2.2.2)octane gave partial protection against the singlet oxygen generated by NaOCl. These data are interpreted to mean that normally occurring singlet oxygen does not contribute to senescence in Drosophila but that artificially produced singlet oxygen accelerates the rate of aging.

Aging↗
PubMed2002

The gold porphyrin first excited singlet state.

Gold porphyrins are often used as electron-accepting chromophores in artificial photosynthetic constructs. Because of the heavy atom effect, the gold porphyrin first-excited singlet state undergoes rapid intersystem crossing to form the triplet state. The lowest triplet state can undergo a reduction by electron donation from a nearby porphyrin or another moiety. In addition, it can be involved in triplet-triplet energy transfer interactions with other chromophores. In contrast, little has been known about the short-lived singlet excited state. In this work, ultrafast time-resolved absorption spectroscopy has been used to investigate the singlet excited state of Au(III) 5,15-bis(3,5-di-t-butylphenyl)-2,8,12,18,-tetraethyl-3,7,13,17-tetramethylporphyrin in ethanol solution. The excited singlet state is found to form with the laser pulse and decay with a time constant of 240 fs to give the triplet state. The triplet returns to the ground state with a life-time of 400 ps. The lifetime of the singlet state is comparable with the time constants for energy and photoinduced electron transfer in some model and natural photosynthetic systems. Thus, it is kinetically competent to take part in such processes in suitably designed supermolecular systems.

Electron Transport↗
PubMed1976

Identification of singlet oxygen as the cytotoxic agent in photoinactivation of a murine tumor.

Singlet oxygen, a metastable state of normal triplet oxygen, has been identified as the cytotoxic agent that is probably responsible for in vitro inactivation of TA-3 mouse mammary carcinoma cells following incorporation of hematoporphyrin and exposure to red light. This photodynamic inactivation can be completely inhibited by intracellular 1,3-diphenylisobenzofuran. This very efficient singlet oxygen trap is not toxic to the cells nor does it absorb the light responsible for hematoporphyrin activation. We have found that the singlet oxygen-trapping product, o-dibenzoylbenzene, is formed nearly quantitatively intracellularly when both the furan and hematoporphyrin are present during illumination but not when only the furan is present during illumination. The protective effect against photodynamic inactivation of the TA-3 cells afforded by 1,3-diphenylisobenzofuran coupled with the nearly quantitative formation of the singlet oxygen-trapping product indicates that singlet oxygen is the probable agent responsible for toxicity in this system.

Animals↗
PubMed1993

Damage to plasmid DNA by singlet oxygen and its protection.

Singlet oxygen, generated by photoexcitation or by chemiexcitation, selectively reacts with the deoxyguanosine moiety in DNA (kq + kr about 5 x 10(6) M-1s-1). The oxidation products include 8-oxo-7,8-dihydroeoxyguanosine (8-oxodG; also called 8-hydroxydeoxyguanosine) and 2,6-diamino-4-hydroxy-5-formamidopyrimidine (FapyGua). Singlet oxygen also causes strand breaks in DNA, studied in plasmids and bacteriophages. The biological consequences include a loss of transforming activity as well as mutagenicity and genotoxicity. Employing shuttle vectors, it was shown that double-stranded vectors carrying singlet-oxygen-induced lesions seem to be processed in mammalian cells by DNA repair mechanisms efficient in preserving the biological activity of the plasmid but highly mutagenic in mammalian cells. Biological protection against singlet oxygen is afforded by quenchers, notably carotenoids (kq = 10(9) - 10(10) M-1s-1) and tocopherols. Whether this activity explains the protective effect of carotenoids on neoplastic transformation is still unknown.

8-Hydroxy-2'-Deoxyguanosine↗