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PubMed1995

Repair of ultraviolet B and singlet oxygen-induced DNA damage in xeroderma pigmentosum cells.

Ultraviolet B (UVB) (290-320 nm) is capable of damaging the DNA molecule directly by generating predominantly pyrimidine dimers. UVA (320-400 nm) does not alter the DNA molecule directly. However, when it is absorbed by cellular photosensitizers, it can damage the DNA molecule indirectly, e.g., by mediation of singlet oxygen, generating predominantly 8-hydroxyguanine. These indirect effects have been implicated in the mutagenic, genotoxic, and carcinogenic effects of UVA. To study the processing of directly and indirectly UV-induced DNA damage in intact, DNA-repair-proficient and -deficient human cells, we used the replicating plasmid pRSVcat, either irradiated with up to 10 kJ/m2 UVB or treated with the photosensitizer methylene blue plus visible light (which generates singlet oxygen). These treated plasmids were introduced into lymphoblast lines from normal donors or from patients with xeroderma pigmentosum (XP) complementation groups A, C, D, E, and variant. DNA repair was assessed by measuring activity of reactivated chloramphenicol-acetyl-transferase enzyme, encoded by the plasmid's cat gene, in cell extracts after 3 d. As expected, the repair of UVB-induced DNA damage was reduced in all XP cell lines, and the degree varied with the complementation group. XP-A, -D, -E, and -variant cells were normally efficient in the repair of singlet oxygen-induced DNA damage. Only three of four XP-C cell lines showed a markedly reduced repair of these lesions. This indicates differential DNA-repair pathways for directly and indirectly UV-induced DNA damage in human cells and suggests that both may be affected in XP-C.

DNA Damage↗

PubMed1996

Protective action of hydroxyethyl rutosides on singlet oxygen challenged cardiomyocytes.

1. The effect of a standardized mixture of beta-hydroxyethyl rutosides against oxidative damage in singlet oxygen-challenged isolated cardiac myocytes from adult rats was investigated. The morphology of the myocytes was evaluated as an indicator for cell viability (elongated, rod shaped cells vs. hypercontracted, rounded cells). The determination of the production of thiobarbituric acid reactive substances served as an indicator for lipid peroxidation. 2. Exposure to singlet oxygen which was generated by photo-excitation of rose bengal (10(-7) M) reduced the number of rod shaped (vital) cardiomyocytes by 78.5 +/- 2.5% and increased the production of thiobarbituric acid reactive substances by 1180 +/- 150% in comparison to incubation with control buffer. 3. Coincubation of the cells with beta-hydroxyethyl rutosides (concentration range: 6.7 pg ml-1 to 670 micrograms ml-1) increased the number of rod shape cardiomyocytes after exposure to singlet oxygen in a dose-dependent bell-shaped manner. A significant protective effect was observed at beta-hydroxyethyl rutosides concentrations ranging from 0.67 ng ml-1 to 67 ng ml-1. 4. In spite of their protective action, beta-hydroxyethyl rutosides did not reduce the accumulation of thiobarbituric acid reactive substances, used as an indicator for lipid peroxidation. 5. The data suggest that beta-hydroxyethyl rutosides exert a protective action against oxygen radical-induced damage of cardiac myocytes at very low concentrations without interfering with lipid peroxidation.

Animals↗

PubMed1987

Photomodification of biological membranes with emphasis on singlet oxygen mechanisms.

This review discusses photomodification of biological membranes and model membrane systems. Current concepts of membrane structure are first reviewed briefly. The role of preillumination association of sensitizer with membranes as it relates to photomodification rate is discussed, as well as the role of singlet oxygen in membrane photomodification. Finally the characteristics of singlet oxygen generation in membranes are considered. The evidence clearly indicates that membrane photomodification cannot be understood based only on the properties of sensitizers and singlet oxygen in aqueous solution. Rather the properties of sensitizers in association with membranes are the determinants of membrane photomodifcation. These properties differ significantly in aqueous solution and in membranes.

Membranes↗

PubMed1991

Carboxylated zinc-phthalocyanines--II. Dimerization and singlet molecular oxygen sensitization in hexadecyltrimethylammonium bromide micelles.

The dimerization of the diamide of zinc-tetracarboxyphthalocyanine was studied spectroscopically in hexadecyltrimethylammonium bromide (CTAB) micelles at surfactant concentrations from 0.026 to 0.1 M and dye concentrations between 0.1 and 10 microM. The apparent dimerization constant in CTAB 0.1 M is 8.6 x 10(5) M-1, while the intramicellar dimerization constant is 1.8 x 10(3). The dimer absorption spectrum was also obtained. Singlet molecular oxygen sensitization was studied by steady state photolysis using 1,3-diphenylisobenzofurane as scavenger in 0.1 M CTAB. The usual sensitization mechanism is extended to include dimer reactions. Singlet molecular oxygen sensitization yields for monomer and dimer in the micelles are 0.7 and 0.1, respectively. With the reported values it is possible to calculate the average yield of singlet molecular oxygen production at any surfactant and dye concentrations.

Cetrimonium↗

PubMed1992

Singlet oxygen quantum yield of sulfur and selenium analogs of psoralen.

The quantum yield of singlet oxygen production by eight newly synthesized sulfur and selenium analogs of psoralen irradiated with UV-A (366 nm) has been determined in CCl4 with the help of the steady state luminescence technique. The new psoralen derivatives are generally better singlet oxygen producers than psoralen itself. In particular, the replacement of selenophene for furan and/or of thiopyrone for pyrone induces an important enhancement of the singlet oxygen quantum yield.

Furocoumarins↗

PubMed1994

Reactivity of singlet oxygen toward amino acids and peptides.

Quenching of singlet oxygen (1O2) in D2O-ethanol by the amino acids tryptophan, tyrosine, histidine, methionine, cysteine and their derivatives was measured by exciting the sensitizers rose bengal or meso-tetra (N-methyl-4-pyridyl)porphyrin tetratosylate in the presence of oxygen and the above quenchers in solution. In our polar solvent, containing 75% D2O on a molar basis it was found that (1) substitution of the aromatic ring in indole, phenol and imidazole by the electron-donating methyl group increases the total (i.e. nonreactive and reactive) quenching rate constant by a factor of five to eight. Free or blocked amino and carboxyl groups removed by two methylene groups from the ring counteract the above increase in the rate constant. The reactive quenching of singlet oxygen, which leads to oxidative destruction of the aromatic ring, correlates with the above substitution effects. It has been proposed that the quenching process takes place by formation of an exciplex between 1O2 and the quencher. Thus our results indicate that the better an electron donor the amino acid residue is the more pronounced is the charge transfer contribution in the exciplex formed with 1O2 and the more likely it is to lead to charge separation and hence to a chemical reaction. (2) Oligopeptides in solution or peptide bonds linked to the amino acid residue have only a minor effect on singlet oxygen. It can therefore be expected that the polypeptide chains per se in the protein network will not interact significantly with the single oxygen molecules present.(ABSTRACT TRUNCATED AT 250 WORDS)

Amino Acids↗

PubMedDate not supplied

Oxidant-induced signaling: effects of peroxynitrite and singlet oxygen.

Following the requirement for cells to cope with oxidative stress, there are cellular adaptation mechanisms at the level of gene expression. Much of what is known about oxidant-induced signaling in mammalian cells was found in experiments using hydrogen peroxide as an oxidant. However, since the biochemical reactivities of various oxidants significantly differ, 'oxidative stress' is not necessarily identical independent of the oxidant employed to bring it about. Here, the biological actions of peroxynitrite and singlet oxygen are presented, focusing on signaling effects. Peroxynitrite is generated in biological systems in the diffusion-controlled reaction of superoxide with nitrogen monoxide and is thus likely to be produced in the vicinity of activated macrophages. Singlet oxygen is generated by stimulated neutrophils in vivo and may further be generated photochemically, e.g. upon exposure of cells to ultraviolet A radiation. Exposure of cells to either of these oxidants elicits a cellular stress response, entailing the activation of signaling cascades that regulate proliferative and apoptotic responses, such as mitogen-activated protein kinase cascades or the phosphoinositide 3-kinase/Akt cascade. Two mechanisms for the oxidant-induced activation of a signaling cascade may be envisaged: (i) the indirect targeting of the cascade by interrupting negative regulation, and (ii) an activating oxidation of one of the constituting components of the cascade. Examples for both mechanisms in relation to peroxynitrite and singlet oxygen are discussed.

Animals↗

PubMedDate not supplied

Neurospora crassa catalases, singlet oxygen and cell differentiation.

The morphogenetic transitions of the N. crassa asexual life cycle are responses to a hyperoxidant state in which probably singlet oxygen is generated. Induction of catalase activity and catalase oxidation by singlet oxygen are consequences of this recurrent hyperoxidant state. Here the biochemical properties and regulation of two large monofunctional catalases are reviewed, and a new catalase-peroxidase gene and activity is described. Catalase-3 is associated to growing and Catalase-1 to non-growing cells. Under stressful conditions one of these catalases is synthesized, depending on whether growth can be continued or a resistant cell has to be made. The catalase-peroxidase Catalase-2 was possibly derived from a bacterial enzyme. In contrast to the other catalases, Catalase-2 had catalase and peroxidase activity. Catalase-2 was expressed under conditions in which vacuolization of hyphae is observed. All three enzymes have a chlorin in its active site instead of ferroprotoheme IX and are resistant to molar concentrations of hydrogen peroxide. These and all other catalases tested so far are oxidized by singlet oxygen, probably at the heme moiety. The catalase activity is virtually unaffected by oxidation, but the enzymes are probably degraded more rapidly than the unmodified ones.

Catalase↗

PubMedDate not supplied

[18O]-labeled singlet oxygen as a tool for mechanistic studies of 8-oxo-7,8-dihydroguanine oxidative damage: detection of spiroiminodihydantoin, imidazolone and oxazolone derivatives.

A water-soluble [18O]-labeled endoperoxide derived from N,N'-di(2,3-dihydroxypropyl)-1,4-naphthalene-dipropanamide (DHPN18O2) has been shown to act as a clean chemical source of [18O]-labeled molecular singlet oxygen. This allows the assessment of the singlet oxygen (1O2) reactivity toward biological targets such as DNA. The present work focuses on the qualitative identification of the main 1O2-oxidation products of 8-oxo-7,8-dihydro-2'-deoxyguanosine, which was achieved using high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Thus, the [18O]-labeled and unlabeled imidazolone and oxazolone, together with the diastereoisomeric spiroiminodihydantoin nucleosides, were detected as the main degradation products. In addition, a modified nucleoside that exhibits similar features as those of the oxidized guanidinohydantoin molecule was detected. Our data strongly suggest that the imidazolone and oxazolone nucleosides are generated via the rearrangement of an unstable 5-hydroperoxide intermediate. Interestingly, the combined use of appropriate tools, including isotopically labeled singlet oxygen and the high- resolution HPLC-ESI-MS/MS technique, has allowed to shed new light on the 1O2-mediated oxidation reactions of guanine DNA components.

Guanine↗

PubMed2004

Singlet oxygen-mediated damage to cellular DNA determined by the comet assay associated with DNA repair enzymes.

The damage profile produced by the reaction of singlet molecular oxygen with cellular DNA was determined using the comet assay associated with DNA repair enzymes. Singlet oxygen was produced intracellularly by thermal decomposition of a water-soluble endoperoxide of a naphthalene derivative which is able to penetrate through the membrane into mammalian cells. We found that the DNA modifications produced by singlet oxygen were almost exclusively oxidised purines recognised by the formamidopyrimidine DNA N-glycosylase. In contrast, significant amounts of direct strand breaks and alkali-labile sites or oxidised pyrimidines, detectable by the bacterial endonuclease III, were not produced.

Animals↗

PubMed2003

Photooxidations initiated or sensitized by biological molecules: singlet oxygen versus radical peroxidation in micelles and human blood plasma.

Biomolecules common in blood plasma, including 2-methyl-1,4-naphthoquinone (vitamin K-0, 2), 2,3-dimethoxy-5-methyl-1,4-benzoquinone (ubiquinone-0, 3), bilirubin, 4, and urocanic acid, 5, were used as photoactivators for the photooxidation of methyl linoleate (ML) in 0.50 M sodium dodecyl sulfate micelles to mimic a bioenvironment. UV irradiation of 2 in this system initiated H-atom abstraction from ML (Type-I mechanism). The evidence includes kinetics of oxygen uptake, inhibition of oxidation by an antioxidant ((R)-(+)-6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid [Trolox], 7) and the analysis of four geometric hydroperoxides formed (cis, trans to trans, trans ratio of 0.5). In contrast, irradiation with a singlet-oxygen sensitizer, 3,5-di-t-butyl-1,2-benzoquinone, 1, formed six isomers by a Type-II mechanism, yielding a cis, trans to trans, trans isomer ratio of 6. Peroxidation activated by 3 or 4 with visible light occurred by a singlet-oxygen pathway (Type-II mechanism), as shown by kinetics of oxygen uptake and the effect of quenchers. In contrast, peroxidation in the presence of 5 in this system initiated H-atom abstraction from ML as shown by oxygen uptake and inhibition by Trolox. A comparison of thermal free-radical peroxidation with direct photooxidation of human blood plasma samples showed important differences. Blood plasma resisted thermal peroxidation because of natural antioxidants or on the addition of Trolox. In contrast, direct photooxidation involved singlet oxygen, according to the effect of quenchers and the lack of inhibition by antioxidants.

Free Radicals↗

PubMed2003

The embedding of meta-tetra(hydroxyphenyl)-chlorin into silica nanoparticle platforms for photodynamic therapy and their singlet oxygen production and pH-dependent optical properties.

This study relates to nanoparticle (NP) platforms that attach to tumor cells externally and only deliver singlet oxygen for photodynamic therapy (PDT) while conserving the embedded photosensitizers (PS). As a model, we demonstrate the successful embedding of the PS meta-tetra(hydroxyphenyl)-chlorin (m-THPC) in NP that are based on a sol-gel silica matrix and also show its positive effect on the singlet oxygen production. The embedding of m-THPC inside silica NP is accomplished by a modified Stöber sol-gel process, in which (3-aminopropyl)-triethoxysilane is introduced during the reaction. Singlet oxygen delivery by the targetable photodynamic NP exceeds that from free PS molecules. In the physiological pH range, there is no significant pH-induced decrease in the fluorescence of m-THPC embedded in silica NP, which might otherwise affect the efficiency of PDT.

Antineoplastic Agents↗

PubMedDate not supplied

Phototoxic phytoalexins. Processes that compete with the photosensitized production of singlet oxygen by 9-phenylphenalenones.

Experiments were performed to elucidate the excited-state behavior of 9-phenylphenalenones, which are phototoxic plant secondary metabolites involved in mechanisms of light-mediated plant defense. Using a combination of time-resolved and steady-state UV/visible spectroscopies, time-resolved IR absorption spectroscopy, time-resolved singlet oxygen phosphorescence measurements and cyclic voltammetry, we provide evidence of an intramolecular charge-transfer process in the excited singlet and the triplet states of 9-phenylphenalenones that modulates the photosensitized production of singlet oxygen.

Phenalenes↗

PubMedDate not supplied

Ascorbate reacts with singlet oxygen to produce hydrogen peroxide.

Singlet oxygen is a highly reactive electrophilic species that reacts rapidly with electron-rich moieties, such as the double bonds of lipids, thiols, and ascorbate (AscH-). The reaction of ascorbate with singlet oxygen is rapid (k = 3 x 10(8) M(-1) s(-1)). Here we have investigated the stoichiometry of this reaction. Using electrodes to make simultaneous, real-time measurements of oxygen and hydrogen peroxide concentrations, we have investigated the products of this reaction. We have demonstrated that hydrogen peroxide is a product of this reaction. The stoichiometry for the reactants of the reaction (1 1O2 + 1AscH--->1H2O2 + 1dehydroascorbic) is 1:1. The formation of H2O2 results in a very different oxidant that has a longer lifetime and much greater diffusion distance. Thus, locally produced singlet oxygen with a half-life of 1 ns to 1 micros in a biological setting is changed to an oxidant that has a much longer lifetime and thus can diffuse to distant targets to initiate biological oxidations.

Ascorbic Acid↗

PubMedDate not supplied

Singlet oxygen oxidation of isolated and cellular DNA: product formation and mechanistic insights.

This survey focuses on recent aspects of the singlet oxygen oxidation of the guanine moiety of nucleosides, oligonucleotides, isolated and cellular DNA that has been shown to be the exclusive DNA target for this biologically relevant photogenerated oxidant. A large body of mechanistic data is now available from studies performed on nucleosides in both aprotic solvents and aqueous solutions. A common process to both reaction conditions is the formation of 8-oxo-7,8-dihydroguanine by reduction of 8-hydroperoxyguanine that arises from the rearrangement of initially formed endoperoxide across the 4,8-bond of the purine moiety. However, in organic solvent the hydroperoxide is converted as a major degradation pathway into a dioxirane that subsequently decomposes into a complex pattern of oxidation products. A different reaction that involved the formation of a highly reactive quinonoid intermediate consecutively to the loss of a water molecule from the 8-hydroperoxide has been shown to occur in aqueous solution. Subsequent addition of a water molecule at C5 leads to the generation of a spiroiminodihy-dantoin compound via a rearrangement that involves an acyl shift. However, in both isolated and cellular DNA the latter decomposition pathway is at the best a minor process, because only 8-oxo-7,8-dihydroguanine has been found to be generated. It is interesting to point out that singlet oxygen has been shown to contribute predominantly to the formation of 8-oxo-7,8-dihydroguanine in the DNA of bacterial and human cells upon exposure to UVA radiation. It may be added that the formation of secondary singlet-oxygen oxidation products of 8-oxo-7,8-dihydroguanine, including spiroiminodihydantoin and oxaluric acid that were characterized in nucleosides and oligonucleotide, respectively, have not yet been found in cellular DNA.

DNA↗

PubMedDate not supplied

Chemiluminescence associated with singlet oxygen reactions with amino acids, peptides and proteins.

Low level chemiluminescence (CL) is observed after protein oxidation mediated by singlet oxygen produced in Rose Bengal (RB) irradiation. This CL lasts for several minutes after the end of the photolysis. In this work, the mechanism of the process was assessed from the spectral characteristics of the CL and the effect of antioxidants (Trolox or ascorbate), Ebselen (a compound with peroxidase-like activity), azide (a singlet oxygen scavenger) and D2O, added prior to or after RB irradiation. It is concluded that most of the light emission is due to formation of excited states generated in the decomposition of peroxides and/or hydroperoxides accumulated during the photolysis. Experiments carried out in the presence of several amino acids (Cys, Met, His, Tyr and Trp) and di- and tripeptides suggest that peroxides (and/or hydroperoxides) of Trp residues are mainly responsible for the CL observed after singlet oxygen-mediated protein oxidation. The much weaker CL observed after the oxidation of proteins without Trp residues supports this conclusion. A comparison of the results obtained employing free Trp, Ala-Trp and Trp-Ala dipeptides, Ala-Trp-Ala tripeptide and Trp-containing proteins supports the conclusion that blocking the amino group of the Trp moiety strongly increases the efficiency of the chemiluminescent process, producing approximately 2.5x10(-8) photons per oxidized Trp group in Ala-Trp. A mechanism comprising two chemiluminescent oxidation pathways of Trp residues is proposed to explain the results.

Amino Acids↗

PubMed1984

Singlet oxygen as a possible factor in human senile nuclear cataract development.

The effects of photodynamically generated singlet oxygen on lens crystallins were investigated. This highly reactive oxidant can produce in crystallins in vitro the oxidative modifications characteristic of proteins from aging and cataractous lens. Additionally species capable of producing singlet oxygen in the presence of near UV radiation are shown to be present in human lenses. These findings are discussed with respect to a possible role of singlet oxygen in the etiology of human senile nuclear cataracts.

Aged↗

PubMed1994

Singlet oxygen induces predominantly G to T transversions on a single-stranded shuttle vector replicated in monkey cells.

To elucidate the mechanisms of mutagenesis by singlet oxygen DNA damage in mammalian cells, a SV40-derived single-stranded shuttle vector was exposed to the water soluble endoperoxide 3,3'-(1,4-naphthylidene) dipropionate (NDPO2). The damaged vector was transfected into monkey COS7 cells and the plasmid progeny exhibited up to 10 fold increase on the mutation frequency in the supF target gene, when compared to untreated vector. The sequence in the supF locus of such mutants revealed that singlet oxygen-induced mutagenesis in single-stranded vector is significantly different from spontaneous mutagenesis. Among the base substitutions, most of the mutations involved deoxyguanosines, being G to T transversions the predominant type of change. The data indicate that mutagenesis by singlet oxygen in mammalian cells may be generated by an error prone bypass of damaged deoxyguanosines at the template DNA.

Animals↗