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PubMed1993

Direct exposure of mammalian cells to pure exogenous singlet oxygen (1 delta gO2).

Mammalian cells attached to membrane filters or deposited on filters without attachment were exposed to gas-phase singlet oxygen (1O2) in the absence of any other reactants. Cells were exposed in a monolayer or less, in the absence of external medium, during steady-state 1O2 generation, ensuring that singlet oxygen impinged directly and equally on all cells simultaneously. The current methodology for cell exposure ensures that 1O2 is initially the only reactive species to which the cells are exposed. Results seen with this system can therefore be attributed solely and unambiguously to events initiated by 1O2. Further, all cells in the sample receive the same magnitude of exposure per surface area per time interval, which supports calculations of the amount of 1O2 required for irreversible cell damage, based on measured 1O2 flux and exposed cell surface area. Exposure to pure 1O2 irreversibly damaged a variety of cell types, including rat basophilic leukemia, human squamous carcinoma and Chinese hamster lung fibroblast cell lines, and murine primary hepatocytes. Cell survival curves following exposure to 1O2 followed apparent first-order kinetics. A large number of singlet oxygen collisions (approximately 10(12)-10(13) were required to inactivate a cell, on average, indicating a low probability that singlet oxygen collision will reduce cell survival. Regardless of cell type or the survival endpoint measured, lethal toxicity required a fairly constant number of 1O2 collisions per cell. This poses a serious caveat in the assignment of causality in correlating 1O2-initiated cellular damage with mechanism of death, i.e. most damage observed will not be related to death.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

PubMed1997

Light emission resulting from hydroxylamine-induced singlet oxygen formation of oxidizing LDL particles.

Oxidation of low-density lipoprotein (LDL) by low amounts of cupric ions resulted in the formation of singlet oxygen (1O2, 1 delta g) when hydroxylamine (NH2OH) was added. Direct evidence on this excited species came from partial spectral resolution of the emitted light in the red spectral region (634 nm and 703 nm), which can be attributed to the dimol decay of singlet oxygen. Additional evidence for the existence of singlet oxygen came from the enhancing effect of deuterium oxide buffer (D2O) on chemiluminescence intensity and the quenching effect of sodium azide. A linear correlation between NH2OH-dependent chemiluminescence intensity and the amount of diene conjugates (DC) formed in this reaction was observed. Removal of adventitious transition metals by adequate chelators prevented chemiluminescence in this system; NH2OH was also found to efficiently decrease metabolites of lipid peroxidation (LPO). Our findings are consistent with a sequence of reactions in which NH2OH first converts transition metals to their reduced state, thereby stimulating the formation of alkoxy- and peroxyradicals. Peroxyradicals decompose in a bimolecular Russel reaction to hydroxyl compounds and singlet oxygen while the majority of alkoxy radicals are eliminated by a secondary reaction with NH2OH. Identical effects were observed when reducing antioxidants such as ascorbic acid or trolox C were used instead of hydroxylamine.

Antioxidants↗

PubMed1992

Induction of glomerular injury by singlet oxygen.

The role of the reactive oxygen species (ROS) in the induction of tissue injury has been well documented. Regarding glomerular injury, the focus of past studies has been on superoxide, hydrogen peroxide, hydroxyl radical and C10-. However, whether singlet oxygen, an exceptionally reactive oxygen metabolite, may cause glomerular lesions has not been investigated. In the present study we documented the effects of locally generated singlet oxygen in the kidney. To generate singlet oxygen, kidneys were perfused with the pigment pheophorbide a, which was followed by exposure to light. One hour after irradiation, severe morphological damage of the glomerular cell had developed. Extensive deposits of fibrin and accumulation of platelets were seen in the glomerular capillary lumina. By contrast, kidneys not exposed to light showed no, or only minimal, abnormalities. Glomerular injury was not inhibited by pretreatment with superoxide dismutase. These results suggest that singlet oxygen produced by pheophorbide a by photodynamic reaction leads to tissue injury in vivo.

Animals↗

PubMed2002

Yeast thioredoxin peroxidase expression enhances the resistance of Escherichia coli to oxidative stress induced by singlet oxygen.

Singlet oxygen ((1)O(2)) is a highly reactive form of molecular oxygen that may harm living systems by oxidizing critical cellular macromolecules. A soluble protein from Saccharomyces cerevisiae specifically provides protection against a thiol-containing metal-catalyzed oxidation system (thiol/Fe(3+)/O(2)) but not against an oxidation system without thiol. This 25 kDa protein acts as a peroxidase but requires the NADPH-dependent thioredoxin system or a thiol-containing intermediate, and was named thioredoxin peroxidase (TPx). The role of TPx in the cellular defense against oxidative stress induced by singlet oxygen was investigated in Escherichia coli containing an expression vector with a yeast genomic DNA fragment that encodes TPx and mutant in which the catalytically essential amino acid cysteine (Cys-47) has been replaced with alanine by a site-directed mutagenesis. Upon exposure to methylene blue and visible light, which generates singlet oxygen, there was a distinct difference between the two strains in regard to growth kinetics, viability, the accumulation of oxidized proteins and lipids, and modulation of activities of superoxide dismutase and catalase. The results suggest that TPx may play an important protective role in a singlet oxygen-mediated cellular damage.

Cloning, Molecular↗

PubMed2004

Singlet oxygen quenching activity of human serum.

Singlet oxygen is regarded as contributing to the pathogenesis of various diseases including light-induced skin disorders and inflammatory response. In this study, the correlation between singlet oxygen quenching activity (SOQA) of human serum and blood biochemistry or life-style was evaluated. Healthy volunteers were recruited and carried out a measurement of SOQA by using electron paramagnetic resonance (EPR) and a questionnaire survey about a smoking. It was demonstrated that major quenchers of singlet oxygen in serum are proteins, and small molecular anti-oxidants relatively play a minor role. SOQA of whole sera showed no correlation with protein concentration, but positively correlated with SOQA of small molecular fraction. In vitro studies demonstrated that the decrease of sulfhydryl groups by NO or superoxide significantly attenuated SOQA of albumin. Together, these results may imply that the underlying oxidative condition in each individual influences both small molecular antioxidant states and the sulfhydryl content of serum proteins. SOQA of sera from women with a smoking history was significantly lower compared to non-smoking women, suggesting that the smoking habit impaired the defense mechanism against singlet oxygen.

Adolescent↗

PubMedDate not supplied

Study of singlet oxygen equilibrium in dioctadecyldimethylammonium chloride vesicles employing 2-(n-(N,N,N-trimethylamine)-n-alkyl)-5-alkylfuryl halides.

Steady state photolysis and time resolved near infrared luminescence detection were employed to study the reaction kinetics of singlet oxygen with three different lipid-soluble probes incorporated in large unilamellar dioctadecyldimethylammonium chloride (DODAC) vesicles. The probes: 2-(4-(N,N,N-trimethylamine)-butyl)-5-dodecylfuryl bromide (DFTA), 2-(12-(N,N,N-trimethylamine)-dodecyl)-5-hexylfuryl bromide (HFDA) and 2-(1-(N,N,N-trimethylamine)-methyl)-5-methylfuryl iodide (MFMA) are useful in studying both singlet oxygen dynamics and its equilibrium in microcompartmentalized systems because they are actinometers in lipidic microphases. These probes contain a reactive furan ring, which will be located at different depths in the bilayer of DODAC vesicles. In the limit of the approximations, the result indicates an inhomogeneous equilibrium distribution of singlet oxygen across the bilayer. The calculated mean partitioning constant of singlet oxygen equals 2.8 and 8.3 at 20 degrees C and 40 degrees C, respectively, in the order of the previously reported constants for other microorganized systems such as sodium dodecylsulfate and cetyltrimethylammonium halide micelles and water/oil microemulsions.

Infrared Rays↗

PubMed1991

Singlet oxygen production from the reactions of superoxide ion in aprotic solvents: implications for hydrophobic biochemistry.

A number of reactions of superoxide ion in aprotic solvents have been reported to produce singlet oxygen. There is strong evidence for singlet oxygen generation from the reactions of superoxide ion with chlorine-containing halocarbons, bromine-containing halocarbons, hexafluorobenzene, diacylperoxides, lead tetraacetate, iodobenzene diacetate, cerium (IV) cation and tetranitromethane. Earlier studies reporting singlet oxygen generation from the reactions of superoxide ion with iodine, ferricenium ion, thianthrene cation radical, tris (N,N'-dioxobipyridyl) manganese (III) cation and di-mu-oxo-bis[phenanthrolinato manganese (IV)] cation need to be repeated because of the methods used to detect singlet oxygen had low specificity. The results of studies of superoxide ion chemistry in aprotic solvents should not be uncritically extrapolated to hydrophobic biological microenvironments, such as the cell membrane.

Chemical Phenomena↗

PubMed2001

Singlet oxygen induces oxidation of cellular DNA.

The aim of the present work was to evaluate the potential for (1)O(2) to induce oxidation of cellular DNA. For this purpose cells were incubated in the presence of a water-soluble endoperoxide whose thermal decomposition leads to the formation of singlet oxygen. Thereafter, DNA was extracted and the level of several modified DNA bases was determined by HPLC analysis coupled to a tandem mass spectrometric detection. A significant increase in the level of 8-oxo-7,8-dihydro-2'-deoxyguanosine was observed upon incubation of the cells with the chemical generator of (1)O(2), whereas the level of the other DNA bases measured remained unchanged. To demonstrate that singlet oxygen is directly involved in the formation of 8-oxo-7, 8-dihydro-2'-deoxyguanosine, the corresponding (18)O-labeled endoperoxide was used. Incubation of the cells with such a generator of (18)O-labeled singlet oxygen results in the formation of (18)O-labeled 8-oxo-7,8-dihydro-2'-deoxyguanosine in the nuclear DNA. This result clearly demonstrates that singlet oxygen, when released within cells, is able to directly oxidize cellular DNA.

8-Hydroxy-2'-Deoxyguanosine↗

PubMed1986

Photodynamic guanine modification by hematoporphyrin is specific for single-stranded DNA with singlet oxygen as a mediator.

Photodynamic modification of DNA by hematoporphyrin (Hp) was characterized by the DNA sequencing technique using 32P-labeled DNA fragments, and the reaction mechanism was investigated by ESR spectroscopy. Mild photodynamic treatment of single-stranded DNA with Hp induced an alteration of guanine residues, and subsequent treatment with piperidine led to chain cleavages at each guanine residue. On the other hand, methylene blue plus light modified the guanine residues in both single-stranded and double-stranded DNA. ESR studies using 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidone as singlet oxygen traps demonstrated that Hp plus light produced almost the same amount of singlet oxygen as methylene blue plus light and that the photochemically generated singlet oxygen reacts significantly with guanylate but only slightly with other mononucleotides. An ESR spin destruction method revealed that photoexcited Hp generated porphyrin radical, but guanylate did not react with this radical. These results indicate that photoexcited Hp reacts with oxygen to generate singlet oxygen which oxidizes the guanine residues of single-stranded DNA and that the difference in photoreactivities of DNA with Hp and methylene blue may be explained in terms of the structural difference in their intercalating abilities.

DNA Restriction Enzymes↗

PubMed1997

The reaction of peroxynitrite with tert-butyl hydroperoxide produces singlet molecular oxygen.

Peroxynitrite, a biological oxidant, can induce lipid peroxidation in biological membranes which leads to the formation of various hydroperoxides. Here, we report the formation of singlet oxygen (1O2) in the reaction of peroxynitrite with tert-butyl hydroperoxide (t-BOOH) used as a model compound for organic hydroperoxides. The formation of singlet oxygen was observed by (i) dimol emission in the red spectral region, (ii) monomol emission in the infrared region at 1270 nm and by (iii) chemical trapping of singlet oxygen with anthracene-9,10-diyldiethyl disulfate (EAS). The emission signal was increased when H2O was replaced by deuterium oxide and was quenched by sodium azide. When singlet oxygen was generated in the reaction of peroxynitrite with t-BOOH, the 1O2 quenching rate constant for sodium azide was estimated from a Stern-Volmer plot as 1.3 x 10(8) M(-1) S(-1) which is in line with known values. The 1O2 generation in the peroxynitrite/t-BOOH reaction was also detected by the formation of the endoperoxide of EAS. These data establish the generation of 1O2 in the reaction of peroxynitrite with t-BOOH and suggest a potential involvement of 1O2 in peroxynitrite-mediated reactions in biological systems.

Deuterium Oxide↗

PubMed2002

Studies on singlet oxygen formation and UVA light-mediated photobleaching of the yellow chromophores in human lenses.

The protein-bound chromophores, which increase with aging in the human lens, act as UVA sensitizers, producing almost exclusively singlet oxygen in vitro. Direct irradiation of whole, aged human lenses with high intensity UVA light (200 mW cm(-2) for 24 hr), however, failed to produce singlet oxygen damage, as evidenced by the lack of either His or Trp photodestruction. Total homogenates of human lenses prepared in a cuvette under air did show destruction of His and Trp residues by UVA light, but no destruction was seen when equivalent homogenates were prepared under argon. These data are consistent with the idea that the low oxygen levels in the lens prevent singlet oxygen damage in vivo.UVA irradiation of aged human lenses in culture caused an extensive photobleaching of the yellow chromophores. A time course indicated that the photobleaching increased with time, with significant color loss apparent after 6 hr. Homogenization of the irradiated and dark control lenses in 6 M guanidine-HCl, followed by determination of the difference spectrum, showed approximately 50% bleaching of compounds with a lambda(max) at 355 nm. Similarly, fluorophores with a lambda(max) for excitation of 355 nm and for emission of 420 nm were 50% destroyed by the UVA light. Similar results were obtained in vitro by the anaerobic irradiation of a sonication-solubilized WI fraction from type II brunescent cataracts and from aged human lenses. In this system, there was an initial bleaching of 15% after 30 min of irradiation, followed by a slow increase over the next 6 hr to a final bleaching of 30%. The addition of 1.0 m M ascorbic acid, but not 1.0 m M glutathione (GSH), increased the photobleaching to 60% under argon, and the loss of ascorbate could be detected under these anaerobic conditions. In the presence of air, UVA light produced no photobleaching, but rather caused a three-fold increase in absorbance at 345 nm, which was prevented by the inclusion of 1.0 m M ascorbic acid and almost 50% inhibited by 1.0 m M GSH. The data are consistent with the conversion of the triplet state of the sensitizers to anion and cation radicals in the absence of oxygen. Photobleaching may occur either by dismutation of the anion radical or by reduction of the anion radical by ascorbate via type I chemistry. UVA irradiation of an enriched fraction of sensitizers from a proteolytic digest from type II cataract lenses produced a 63% bleaching at 330 nm in the absence of oxygen, and the almost complete loss of the A(330) absorbing and 350/450 nm fluorescent peaks upon HPLC separation. This loss correlated with the loss of the ability of the irradiated fraction to produce singlet oxygen in vitro upon subsequent UVA irradiation.

Aged↗

PubMed1998

REMPI Spectroscopy of SO Singlet States.

Three newly found vibrational levels at energies Te(v) = 45127.88(3), 51900.40(4), and 52604.95(3) cm-1 allow the first application of resonance-enhanced multiphoton ionization for detecting the SO radical in its low-energy singlet states, a1Delta and b1Sigma+. The analysis of the spectra is based on the observation of 10 rotationally resolved bands starting from a1Delta v = 0, 6 ellipsis 11 and b1Sigma+ v = 8, covering a typical range of J = 5 ellipsis 40 or 50. Population of these SO singlet states has been achieved by two-photon dissociation of SO2 in a molecular beam environment, applying wavelengths in the 248 to 291 nm range. This paper presents an analysis of the rotational, vibrational, and electronic properties of the new levels. Reviewing earlier works on the singlet states of SO, a revised term energy scheme is provided which connects the singlet and triplet systems of the molecule. Copyright 1998 Academic Press.

Journal Article↗

PubMed1992

Singlet oxygen: a potential culprit in myocardial injury?

The purpose of this study was to explore the role of singlet oxygen in cardiovascular injury. To accomplish this objective, we investigated the effect of singlet oxygen [generated from photoactivation of rose-bengal] on the calcium transport and Ca(2+)-ATPase activity of cardiac sarcoplasmic reticulum and compared these results with those obtained by superoxide radical, hydrogen peroxide and hydroxyl radical. Isolated cardiac SR exposed to rose bengal (10 nM) irradiated at (560 nm) produced a significant inhibition of Ca2+ uptake; from 2.27 +/- 0.05 to 0.62 +/- 0.05 mumol Ca2+/mg.min (mean +/- SE) (P less than 0.01) and Ca(2+)-ATPase activity from 2.08 +/- 0.05 mumol Pi/min.mg to 0.28 +/- 0.04 mumol Pi/min.mg (mean +/- SE) (P less than 0.01). The inhibition of calcium uptake and Ca(2+)-ATPase activity by rose bengal derived activated oxygen (singlet oxygen) was dependent on the duration of exposure and intensity of light. The singlet oxygen scavengers ascorbic acid and histidine significantly protected SR Ca(2+)-ATPase against rose bengal derived activated oxygen species but superoxide dismutase and catalase did not attenuate the inhibition. SDS-polyacrylamide gel electrophoresis of SR exposed to photoactivated rose bengal up to 14 min, demonstrated complete loss of Ca(2+)-ATPase monomer band which was significantly protected by histidine. Irradiation of rose bengal also caused an 18% loss of total sulfhydryl groups of SR. On the other hand, superoxide (generated from xanthine oxidase action on xanthine) and hydroxyl radical (0.5 mM H2O2 + Fe(2+)-EDTA) as well as H2O2 (12 mM) were without any effect on the 97,000 dalton Ca(2+)-ATPase band of sarcoplasmic reticulum.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

PubMed1992

Singlet oxygen production and fluorescence yields of merocyanine 540: a comparative study in solution and model membrane systems.

Singlet oxygen and fluorescence quantum yields of merocyanine 540 were measured in solution (methanol, ethanol, n-heptanol) and in model membrane systems (cationic micelles, unilamellar dimyristoyl- and dipalmitoylphosphatidylcholine vesicles). Both singlet oxygen quantum yields and fluorescence quantum yields increase with increasing viscosity/rigidity of the surrounding medium: the yield of singlet oxygen production (24 degrees C) goes from 0.002 in methanol to 0.04 in dipalmitoylphosphatidylcholine vesicles, and fluorescence yields (25 degrees C) change from 0.14 to 0.61 in the same media. The data are consistent with previous findings that photoisomerization is in direct competition with intersystem crossing and radiative relaxation. Therefore, a singlet oxygen yield close to the maximum value of 0.11 can only be achieved after both photoisomerization and internal conversion are prevented by a highly viscous environment.

Cell Membrane↗

PubMed1986

Phototoxicity of tetracyclines as related to singlet oxygen production and uptake by polymorphonuclear leukocytes.

The photo-induced singlet oxygen production of six tetracyclines was measured as tryptophan degradation. Demethylchlortetracycline was the most efficient singlet oxygen producer followed by doxycycline. The least efficient producer was minocycline. Doxycycline, however, was the most potent inducer of photodamage to polymorphonuclear leukocytes (PMNLs) followed by demethylchlortetracycline. Accordingly, the singlet oxygen production during irradiation did not correlate with the induction of photodamage to the PMNLs. However, the uptake of doxycycline by the cells was 3 times higher than that of demethylchlortetracycline, and the tetracycline-induced photodamage to the PMNLs correlated with the product of singlet oxygen production during irradiation and the drug uptake by the cells.

Free Radicals↗

PubMed1994

Singlet molecular oxygen production in the reaction of peroxynitrite with hydrogen peroxide.

Peroxynitrite and hydrogen peroxide are mediators of cytotoxicity. This study shows that the peroxynitrite anion reacts with hydrogen peroxide to release oxygen accompanied by emission of chemiluminescence (CL). Direct characterization of this light emission attributes it to the transition of singlet molecular oxygen to the triplet ground state. Chemiluminescence was monitored: (i) by dimol light emission in the red spectral region (> 610 nm) using a red-sensitive photomultiplier; and (ii) by monomol light emission in the infrared (1270 nm) with a liquid nitrogen-cooled germanium diode. These properties of photoemission and the enhancing effect of deuterium oxide on CL intensity as well as the quenching effect of sodium azide are diagnostic of molecular oxygen in the excited singlet state. For comparison, singlet molecular oxygen arising from the thermolysis of the water-soluble endoperoxide of 3,3'-(1,4-naphthylidene)dipropionate or from the hypochlorite/H2O2 system was also monitored. These novel observations identify a potential singlet oxygen-dependent mechanism contributing to cytotoxicity mediated by peroxynitrite and hydrogen peroxide.

Free Radicals↗

PubMed1983

Flexural rigidity of singlet microtubules estimated from statistical analysis of their contour lengths and end-to-end distances.

Microtubules in solutions, observed under a dark-field microscope, show incessant Brownian movement such as translational, rotational and flexing motion. A large number of microtubules, spontaneously stuck to the under surface of a coverslip, were photographed and the contour lengths and end-to-end distances of their images were measured. From the statistical analysis of the contour lengths and end-to-end distances, a value for the parameter lambda representing the flexibility of singlet microtubules was estimated to be lambda = (6.8 +/- 0.8) . 10(-3) micrometers-1. From the value of lambda, the elastic modulus for bending, epsilon, and Young's modulus, Y, of singlet microtubules were computed to be epsilon = approximately 10(-16) and Y = approximately 10(9) dyne . cm-2, respectively. The microscopic elastic constant, k, of bonding between two tubulin monomers neighboring along the singlet microtubule was computed to be k = congruent to 10(2) dyne . cm-1. A singlet microtubule is an order of magnitude as strong against bending and as weak against stretching as an F-actin filament.

Animals↗

PubMed1987

Superoxide, hydrogen peroxide and singlet oxygen in hematoporphyrin derivative-cysteine, -NADH and -light systems.

Hematoporphyrin derivative and light in the presence of cysteine or glutathione were found to convert oxygen to superoxide and hydrogen peroxide at pH less than approx. 6.5, while at pH greater than 6.5 no superoxide or hydrogen peroxide production was observed. However, at pH values greater than 6.5 the rate of oxygen consumption increased. This rate paralleled the acid dissociation curve of the cysteine thiol group and is consistent with the chemical quenching of 1O2 by cysteine. The superoxide and hydrogen peroxide formation observed below pH 6.5 appeared not to be related to the singlet oxygen production of hematoporphyrin derivative. In addition, superoxide and hydrogen peroxide production was observed with hematoporphyrin derivative and light in the presence of NADH, both above and below pH 6.5. Direct detection of singlet oxygen luminescence at 1268 nm in the hematoporphyrin derivative-light system (2H2O as solvent) revealed an apparent linear increase in the singlet oxygen emission intensity as the p2H was raised from 7.0 to 10.0. Azide efficiently quenched this observed emission. In addition, at p2H 7.4, 1 mM cysteine resulted in a 40% reduction of the singlet oxygen luminescence, while at p2H 9.4 the signal was quenched by over 95% (under the experimental conditions employed). In total, we interpret these results as consistent with the chemical quenching of 1O2 by the ionized thiol group of cysteine.

Cysteine↗